CN114988862A - High-color-rendering-index fluorescent ceramic for laser lighting and preparation method thereof - Google Patents
High-color-rendering-index fluorescent ceramic for laser lighting and preparation method thereof Download PDFInfo
- Publication number
- CN114988862A CN114988862A CN202210746344.1A CN202210746344A CN114988862A CN 114988862 A CN114988862 A CN 114988862A CN 202210746344 A CN202210746344 A CN 202210746344A CN 114988862 A CN114988862 A CN 114988862A
- Authority
- CN
- China
- Prior art keywords
- fluorescent ceramic
- equal
- color rendering
- rendering index
- ceramic
- 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.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B35/44—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 aluminates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/50—Shaped 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
- C04B35/505—Shaped 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21V—FUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
- F21V9/00—Elements for modifying spectral properties, polarisation or intensity of the light emitted, e.g. filters
- F21V9/30—Elements containing photoluminescent material distinct from or spaced from the light source
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- 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
- C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
- C04B2235/9646—Optical properties
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F21—LIGHTING
- F21Y—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
- F21Y2115/00—Light-generating elements of semiconductor light sources
- F21Y2115/30—Semiconductor lasers
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- General Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a high color rendering index fluorescent ceramic for laser illumination and a preparation method thereof, wherein the chemical formula of the fluorescent ceramic is as follows: (Y) 1‑x Ce x ) 2 Mg(Sc 0.5 Al 0.5‑y Mn y ) 1 Al 2 SiO 12 Wherein x is Ce 3+ Doping with Y 3+ Mole percent of the sites, y being Mn 2+ Doped Al 3+ The molar percentage of the sites is that x is more than or equal to 0.002 and less than or equal to 0.02, and y is more than or equal to 0.001 and less than or equal to 0.015, and the catalyst is prepared by adopting a solid phase reaction method for sintering. The fluorescent ceramic provided by the invention emits under the excitation of 460nm wavelengthThe main peak of the spectrum is between 566 and 585nm, and the full width at half maximum is between 105 and 120 nm; under the excitation of blue light LD (1-5W), warm white light emission is realized, the color temperature is 3800-4250K, and the color rendering index is 80-85; when the ambient temperature is 150 ℃, the luminous intensity of the fluorescent ceramic is kept between 80 and 90 percent, the optical performance is excellent, the preparation is simple, and the fluorescent ceramic can be used in the field of laser illumination.
Description
Technical Field
The invention relates to the technical field of fluorescent ceramics, in particular to a high color rendering index fluorescent ceramic for laser illumination and a preparation method thereof.
Background
White light emitting diodes (leds) have been developed and applied for a long time in the field of solid-state lighting and display as a fourth generation lighting source. Compared with an LED, a Laser Diode (LD) based Laser lighting technology can still maintain high light emitting efficiency in the high power lighting field, and has the significant advantages of higher brightness, smaller volume, longer service life, longer search distance, and the like. Taking a single chip as an example, the brightness of the blue LD is 1000 times as high as that of the LED, and the energy consumption is 2/3 of the LED. LD solid-state lighting technology has become a major development direction in the field of lighting.
At present, the mainstream implementation scheme of the white light LD light source is still blue light LD excited garnet Y 3 Al 5 O 12 Ce (YAG: Ce) yellow fluorescent material. Compared with fluorescent powder, the fluorescent ceramic has good thermal, mechanical and physical and chemical stability, but the emission spectrum of YAG Ce is mainly covered by yellow-green light and insufficient red lightTherefore, the white LD light source also has the problems of poor color rendering property (CRI-60), high color temperature (more than 6000K) and low color quality.
At present, a great deal of documents report the modification treatment of the Ce: YAG fluorescent ceramic, so as to realize the regulation and control of the luminescence behavior of the Ce: YAG fluorescent ceramic. The literature (thermal and metabolic properties students of transient Ce: GdYAG ceramic by Gd Substitution for white LEDs, optical Materials,2019,94,172-181) reports on the use of co-doping with Gd 3+ Can make Ce 3+ The ion luminescence peak position generates red shift, but the moving range is very limited, and the color temperature improvement effect is not obvious. CN110218085A discloses that red, green and yellow coupled luminescence is realized by designing composite structure fluorescent ceramic, warm white light is obtained, but its thermal stability is also gradually reduced, and its manufacturing cost is higher and process is more complex. CN108264899A discloses a multi-element doped transparent ceramic for LED illumination instead of fluorescent powder, which emits white light after being excited by a blue light chip, however, the afterglow time of the ceramic is long, the luminous efficiency is greatly limited, and the light quantity loss of the device is serious.
Disclosure of Invention
The invention aims to provide a high-color-rendering-index fluorescent ceramic for laser illumination, which can realize the emission of warm white light, white light or light red light.
The invention also aims to provide a preparation method of the high-color-rendering-index fluorescent ceramic for laser illumination, which is easy to realize industrial production.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the present invention provides a high color rendering index fluorescent ceramic for laser illumination, the chemical formula of the fluorescent ceramic is:
(Y 1-x Ce x ) 2 Mg(Sc 0.5 Al 0.5-y Mn y ) 1 Al 2 SiO 12
wherein x is Ce 3+ Doping with Y 3+ Mole percent of the sites, y being Mn 2+ Doped Al 3+ The mole percentage of the sites is,0.002≤x≤0.02，0.001≤y≤0.015。
under the excitation of 460nm wavelength, the main peak of the emission spectrum of the fluorescent ceramic provided by the invention is 566-585 nm, and the full width at half maximum is 105-120 nm. Under the excitation of blue light LD (1-5W), warm white light emission is realized, the color temperature is 3800-4250K, and the color rendering index is 80-85. When the ambient temperature is 150 ℃, the luminous intensity of the fluorescent ceramic is kept between 80 and 90 percent.
In a second aspect, the invention further provides a preparation method of the high color rendering index fluorescent ceramic for laser illumination, which adopts a solid-phase reaction method for sintering, and specifically comprises the following steps:
(1) according to the formula (Y) 1-x Ce x ) 2 Mg(Sc 0.5 Al 0.5-y Mn y ) 1 Al 2 SiO 12 X is more than or equal to 0.002 and less than or equal to 0.02, y is more than or equal to 0.001 and less than or equal to 0.015, and yttrium oxide, aluminum oxide, cerium oxide, magnesium oxide, silicon dioxide, scandium oxide and manganese carbonate are respectively weighed as raw material powder according to the stoichiometric ratio of the elements; mixing and ball-milling the raw material powder and a ball-milling medium according to a certain proportion to obtain mixed slurry;
(2) placing the mixed slurry obtained in the step (1) in a drying oven for drying, and sieving the dried mixed powder;
(3) putting the powder sieved in the step (2) into a grinding tool for dry pressing forming, and then carrying out cold isostatic pressing forming to obtain a biscuit with the relative density of 50-55%;
(4) sintering the biscuit obtained in the step (3) in a vacuum furnace at 1550-1650 ℃, keeping the temperature for 1-24 h, and ensuring the sintering vacuum degree to be not less than 10 -3 Pa, obtaining fluorescent ceramic;
(5) and (3) annealing the fluorescent ceramic obtained in the step (4) in air at the annealing temperature of 1300-1450 ℃ for 8-24 h to obtain the fluorescent ceramic with the relative density of 99.5-99.9%.
Preferably, in the step (1), the ball milling rotation speed is 180-200 r/min, and the ball milling time is 15-20 h.
Preferably, in the step (1), the ball milling medium is absolute ethyl alcohol, and the mass-to-volume ratio of the raw material powder to the ball milling medium is 1 g: (1.5-3.5) mL.
Preferably, in the step (2), the drying time is 20-30 h, and the drying temperature is 80-90 ℃.
Preferably, in the step (2), the number of the sieved screens is 50-200 meshes, and the sieving frequency is 1-3 times.
Preferably, in the step (3), the cold isostatic pressing pressure maintaining pressure is 150-200 Mpa, and the pressure maintaining time is 200-400 s.
Preferably, in the step (4), the temperature rise rate in the vacuum sintering stage is 1-10 ℃/min, and the temperature drop rate after sintering is 1-10 ℃/min.
Compared with the prior art, the invention has the following beneficial effects:
1. the fluorescent ceramic of a pure garnet phase is obtained by controlling the chemical mixture ratio and a solid-phase reaction method, and under the excitation of the wavelength of 460nm, the main peak of the emission spectrum of the fluorescent ceramic is 566-585 nm, and the full width at half maximum is 105-120 nm; under the excitation of blue light LD (1-5W), warm white light emission is realized, the color temperature is 3800-4250K, and the color rendering index is 80-85.
2. The magnesium oxide adopted by the invention is not only a raw material of a fluorescent material, but also plays a role of a cosolvent, thereby avoiding the introduction of impurity ions caused by adding the cosolvent and also omitting the impurity removal step;
3. the invention refers to the ion radius matching principle and the crystal field regulation principle, and adopts Mg 2+ -Si 4+ Non-equivalent substitution of Al by ion pairs 3+ -Al 3+ Ion pair, which increases the lattice distortion of the ion, makes Ce 3+ 5d of ion 1 And 5d 1 Is increased in the degree of energy level cleavage of (A), resulting in Ce 3+ 5d of 1 The energy level is lowered so that Ce 3+ The energy for the electrons of the ions to transit to the ground state is relatively reduced, thereby producing Ce 3+ The red shift of the emitted light and the effective broadening of the emission peak value are realized, and the prepared fluorescent ceramic has excellent optical indexes and is applied to laser illumination.
4. The invention introduces transition metal Mn 2+ Ion, successful substitution of octahedral Al 3+ The ion emits red light at 580nm, increasing redThe light emission remarkably improves the color rendering index of the fluorescent material.
5. Sc introduced in the invention 3+ As the ions with the smallest ionic radius and the largest electronegativity in the transition ions, the octahedral Al is successfully occupied 3+ The excessive large degree of lattice distortion caused by Mg-Si co-substitution is avoided, so that Mn is prevented 2+ High-concentration doping of (2) becomes possible; at the same time, Sc 3+ The introduction of (2) relaxes the covalent bond tension of the nearest adjacent bond (Ce-O bond), and increases Ce 3 + The local symmetry of the dodecahedron of the ions is beneficial to enhancing the rigidity of the ceramic structure, the thermal stability of the fluorescent ceramic is obviously improved, the luminous intensity is attenuated by 10 to 20 percent at 150 ℃, and the thermal stability is good.
Drawings
FIG. 1 is an XRD pattern of a fluorescent ceramic produced in examples 1-3 of the present invention;
FIG. 2 is a graph showing the emission spectra of the fluorescent ceramics obtained in examples 1 to 3 of the present invention under the excitation of 460nm wavelength;
FIG. 3 is a Gaussian peak plot of the emission spectrum of a fluorescent ceramic sample prepared in example 1 of the present invention;
FIG. 4 is a surface SEM image and EDS map of a fluorescent ceramic sample prepared in example 1 of the present invention;
FIG. 5 is a graph of the fluorescence temperature change spectrum of a fluorescent ceramic sample prepared in example 1 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
The raw material powders used in the following examples are all commercially available products, and the purity thereof was more than 99.9%.
Example 1: preparation of the chemical formula (Y) 0.998 Ce 0.002 ) 3 Mg(Sc 0.5 Al 0.498 Mn 0.002 ) 1 Al 2 SiO 12 The fluorescent ceramic of (1).
(1) The target product mass was set to 60.011g according to the formula (Y) 0.998 Ce 0.002 ) 3 Mg(Sc 0.5 Al 0.498 Mn 0.002 ) 1 Al 2 SiO 12 In the stoichiometric ratio of each element, yttrium oxide (33.725g), aluminum oxide (12.705g), cerium oxide (0.103g), magnesium oxide (4.021g), silicon dioxide (5.994g), scandium oxide (3.440g) and manganese carbonate (0.023g) were weighed as raw material powders. Mixing the raw material powder with 100mL of absolute ethyl alcohol, and carrying out ball milling in a ball milling tank, wherein the ball milling rotation speed is 180r/min, and the ball milling time is 15 h.
(2) And (2) placing the mixed slurry subjected to ball milling in the step (1) into a forced air drying oven at 80 ℃ for drying for 20 hours, and sieving the dried mixed powder with a 50-mesh sieve for 2 times.
(3) And (3) putting the calcined powder in the step (2) into a grinding tool for dry pressing and forming, and then carrying out cold isostatic pressing and forming, wherein the relative density of the formed biscuit is 50%.
(4) Sintering the ceramic biscuit obtained in the step (4) in a vacuum furnace, wherein the sintering temperature is 1650 ℃, the heat preservation time is 1h, the heating rate is 1 ℃/min, and the cooling rate is 1 ℃/min after sintering; the relative density of the ceramic was 99.9%.
(5) And polishing the two surfaces of the sintered fluorescent ceramic until the thickness of the ceramic is 1.0mm to obtain the fluorescent ceramic.
(Y) obtained in this example 0.998 Ce 0.002 ) 3 Mg(Sc 0.5 Al 0.498 Mn 0.002 ) 1 Al 2 SiO 12 XRD test of the fluorescent ceramic shows that: the prepared material is a pure garnet phase, as shown in figure 1.
(Y) obtained in the present example 0.998 Ce 0.002 ) 3 Mg(Sc 0.5 Al 0.498 Mn 0.002 ) 1 Al 2 SiO 12 Under the excitation of the wavelength of 460nm, the main peak of the emission spectrum of the fluorescent ceramic is 566nm, and the full width at half maximum is 105nm, as shown in FIG. 2; the emission spectrum is divided into peaks, and the main emission peak of the fluorescent ceramic at 566nm is shown by Ce at 452nm 3+ Emission and Mn at 580nm 2+ As shown in fig. 3; the measured SEM image of the surface of the fluorescent ceramic has clear grain boundary, and an EDS map shows that each element ion is successfully doped into a garnet structure, as shown in figure 4; the ceramic can realize warm white light emission under the excitation of high-power blue light LD (1W), the color temperature is 3800K, and the color rendering index is 82. When the ambient temperature is 150 ℃, the luminous intensity of the fluorescent ceramic is kept at 85 percent, as shown in figure 5.
Example 2: preparation of the formula (Y) 0.99 Ce 0.01 ) 3 Mg(Sc 0.5 Al 0.492 Mn 0.008 ) 1 Al 2 SiO 12 The fluorescent ceramic of (1).
(1) The target product mass was set to 60.053g according to the formula (Y) 0.99 Ce 0.01 ) 3 Mg(Sc 0.5 Al 0.492 Mn 0.008 ) 1 Al 2 SiO 12 In the stoichiometric ratio of each element, yttrium oxide (33.377g), aluminum oxide (12.645g), cerium oxide (0.514g), magnesium oxide (4.012g), silicon dioxide (5.981g), scandium oxide (3.432g), and manganese carbonate (0.092g) were weighed as raw material powders. Mixing the raw material powder with 150mL of absolute ethyl alcohol, and carrying out ball milling in a ball milling tank, wherein the ball milling rotation speed is 190r/min, and the ball milling time is 15 h.
(2) And (2) placing the mixed slurry subjected to ball milling in the step (1) into a 90 ℃ forced air drying oven for drying for 20 hours, and sieving the dried mixed powder with a 100-mesh sieve for 2 times.
(3) And (3) putting the calcined powder in the step (2) into a grinding tool for dry pressing and forming, and then carrying out cold isostatic pressing and forming, wherein the relative density of the formed biscuit is 50%.
(4) Sintering the ceramic biscuit obtained in the step (4) in a vacuum furnace, wherein the sintering temperature is 1600 ℃, the heat preservation time is 8 hours, the heating rate is 5 ℃/min, and the cooling rate is 5 ℃/min after sintering; the relative density of the ceramic was 99.8%.
(5) And polishing the two surfaces of the sintered fluorescent ceramic until the thickness of the ceramic is 1.0mm to obtain the fluorescent ceramic.
(Y) obtained in this example 0.99 Ce 0.01 ) 3 Mg(Sc 0.5 Al 0.492 Mn 0.008 ) 1 Al 2 SiO 12 XRD test of the fluorescent ceramic shows that: the prepared material is a pure garnet phase, as shown in figure 1.
(Y) obtained in the present example 0.99 Ce 0.01 ) 3 Mg(Sc 0.5 Al 0.492 Mn 0.008 ) 1 Al 2 SiO 12 The fluorescent ceramic has an emission spectrum with a main peak of 578nm and a full width at half maximum of 110nm under the excitation of a wavelength of 460nm, as shown in figure 2. The ceramic can realize white light emission under the excitation of high-power blue light LD (5W), the color temperature is 4060K, and the color rendering index is 85. When the ambient temperature is 150 ℃, the luminous intensity of the fluorescent ceramic is kept at 83 percent.
Example 3: preparation of the chemical formula (Y) 0.98 Ce 0.02 ) 3 Mg(Sc 0.5 Al 0.485 Mn 0.015 ) 1 Al 2 SiO 12 The fluorescent ceramic of (1).
(1) The target product mass was set to 60.101g according to the formula (Y) 0.98 Ce 0.02 ) 3 Mg(Sc 0.5 Al 0.485 Mn 0.015 ) 1 Al 2 SiO 12 In the stoichiometric ratio of each element, yttrium oxide (32.946g), aluminum oxide (12.574g), cerium oxide (1.025 g), magnesium oxide (4.000g), silicon dioxide (5.963g), scandium oxide (3.422g) and manganese carbonate (0.171g) were weighed as raw material powders. Mixing the raw material powder with 200mL of absolute ethyl alcohol, and carrying out ball milling in a ball milling tank, wherein the ball milling rotation speed is 200r/min, and the ball milling time is 20 h.
(2) And (2) placing the mixed slurry subjected to ball milling in the step (1) into a 90 ℃ forced air drying oven for drying for 30 hours, and sieving the dried mixed powder with a 200-mesh sieve for 1 time.
(3) And (3) putting the calcined powder in the step (2) into a grinding tool for dry pressing forming, and then carrying out cold isostatic pressing forming, wherein the relative density of the formed biscuit is 55%.
(4) Sintering the ceramic biscuit obtained in the step (4) in a vacuum furnace, wherein the sintering temperature is 1550 ℃, the heat preservation time is 24 hours, the heating rate is 10 ℃/min, and the cooling rate is 10 ℃/min after sintering; the relative density of the ceramic was 99.5%.
(5) And polishing the two surfaces of the sintered fluorescent ceramic until the thickness of the ceramic is 1.0mm to obtain the fluorescent ceramic.
(Y) obtained in this example 0.98 Ce 0.02 ) 3 Mg(Sc 0.5 Al 0.485 Mn 0.015 ) 1 Al 2 SiO 12 XRD test of the fluorescent ceramic shows that: the prepared material is a pure garnet phase, as shown in figure 1.
(Y) obtained in the present example 0.98 Ce 0.02 ) 3 Mg(Sc 0.5 Al 0.485 Mn 0.015 ) 1 Al 2 SiO 12 Under the excitation of the wavelength of 460nm, the main peak of the emission spectrum of the fluorescent ceramic is 585nm, and the full width at half maximum is 120nm, as shown in figure 2; the ceramic is excited by high-power blue light LD (3W) to realize light red light emission, the color temperature is 4250K, and the color rendering index is 80. When the ambient temperature is 150 ℃, the luminous intensity of the fluorescent ceramic is kept at 80 percent.
The above description is only for the purpose of illustrating the embodiments of the present invention, and the scope of the present invention should not be limited thereto, and any modifications, equivalents and improvements made by those skilled in the art within the technical scope of the present invention as disclosed in the present invention should be covered by the scope of the present invention.
Claims (8)
1. A high color rendering index fluorescent ceramic for laser lighting, characterized in that the chemical formula of the fluorescent ceramic is:
(Y 1-x Ce x ) 2 Mg(Sc 0.5 Al 0.5-y Mn y ) 1 Al 2 SiO 12
wherein x is Ce 3+ Doping with Y 3+ Mole percent of the sites, y being Mn 2+ Doped Al 3+ The mole percentage of the sites is that x is more than or equal to 0.002 and less than or equal to 0.02, and y is more than or equal to 0.001 and less than or equal to 0.015.
2. The preparation method of the high color rendering index fluorescent ceramic for laser illumination according to claim 1, characterized by sintering by a solid phase reaction method, comprising the following steps:
(1) according to the formula (Y) 1-x Ce x ) 2 Mg(Sc 0.5 Al 0.5-y Mn y ) 1 Al 2 SiO 12 Respectively weighing yttrium oxide and oxidation according to the stoichiometric ratio of each element of x being more than or equal to 0.002 and less than or equal to 0.02 and y being more than or equal to 0.001 and less than or equal to 0.015Aluminum, cerium oxide, magnesium oxide, silicon dioxide, scandium oxide and manganese carbonate are used as raw material powder; mixing and ball-milling the raw material powder and a ball-milling medium according to a certain proportion to obtain mixed slurry;
(2) placing the mixed slurry obtained in the step (1) in a drying oven for drying, and sieving the dried mixed powder;
(3) putting the powder sieved in the step (2) into a grinding tool for dry pressing and forming, and then carrying out cold isostatic pressing to obtain a biscuit with the relative density of 50-55%;
(4) sintering the biscuit obtained in the step (3) in a vacuum furnace at 1550-1650 ℃, keeping the temperature for 1-24 h and ensuring the sintering vacuum degree to be not less than 10 -3 Pa, obtaining fluorescent ceramic;
(5) and (3) annealing the fluorescent ceramic obtained in the step (4) in air at the annealing temperature of 1300-1450 ℃ for 8-24 h to obtain the fluorescent ceramic with the relative density of 99.5-99.9%.
3. The preparation method of the high color rendering index fluorescent ceramic for laser illumination according to claim 2, wherein in the step (1), the ball milling rotation speed is 180-200 r/min, and the ball milling time is 15-20 h.
4. The method for preparing the fluorescent ceramic with the high color rendering index for laser illumination according to claim 2, wherein in the step (1), the ball milling medium is absolute ethyl alcohol, and the mass-to-volume ratio of the raw material powder to the ball milling medium is 1 g: 1.5-3.5 mL.
5. The method for preparing a fluorescent ceramic with a high color rendering index for laser illumination according to claim 2, wherein in the step (2), the drying time is 20-30 h, and the drying temperature is 80-90 ℃.
6. The method for preparing a fluorescent ceramic with a high color rendering index for laser illumination according to claim 2, wherein in the step (2), the number of the sieved screens is 50-200 meshes, and the number of the sieved screens is 1-3.
7. The method for preparing a fluorescent ceramic with high color rendering index for laser illumination according to claim 2, wherein in the step (3), the cold isostatic pressing pressure is 150 to 200Mpa, and the pressure holding time is 200 to 400 s.
8. The method for preparing the fluorescent ceramic with high color rendering index for laser illumination according to claim 2, wherein in the step (4), the temperature rise rate in the vacuum sintering stage is 1-10 ℃/min, and the temperature fall rate after sintering is 1-10 ℃/min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210746344.1A CN114988862B (en) | 2022-06-29 | 2022-06-29 | High-color-rendering-index fluorescent ceramic for laser illumination and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210746344.1A CN114988862B (en) | 2022-06-29 | 2022-06-29 | High-color-rendering-index fluorescent ceramic for laser illumination and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114988862A true CN114988862A (en) | 2022-09-02 |
| CN114988862B CN114988862B (en) | 2023-06-23 |
Family
ID=83037081
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210746344.1A Active CN114988862B (en) | 2022-06-29 | 2022-06-29 | High-color-rendering-index fluorescent ceramic for laser illumination and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114988862B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115677349A (en) * | 2022-10-12 | 2023-02-03 | 中国科学院上海光学精密机械研究所 | Fluorescent ceramic material with broad-spectrum red light emission and preparation method thereof |
| CN116444271A (en) * | 2023-05-06 | 2023-07-18 | 江苏师范大学 | High-color-rendering-index high-thermal-stability fluorescent ceramic for LD/LED and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160312116A1 (en) * | 2013-04-09 | 2016-10-27 | Daejoo Electronic Materials Co., Ltd | Fluorescent material for white light emitting diode and preparation method thereof |
| JP2017179219A (en) * | 2016-03-31 | 2017-10-05 | 信越化学工業株式会社 | Fluorescence material, and method of producing the same |
| CN108503352A (en) * | 2018-03-27 | 2018-09-07 | 中国科学院上海硅酸盐研究所 | A kind of garnet-base red fluorescence ceramic material and preparation method thereof |
| CN109592978A (en) * | 2018-12-03 | 2019-04-09 | 江苏师范大学 | High-capacity LED/LD illumination refers to fluorescence ceramics and the preparation method and application thereof with warm white height is aobvious |
| CN111285682A (en) * | 2018-12-07 | 2020-06-16 | 上海航空电器有限公司 | Full-spectrum complex phase fluorescent ceramic for laser illumination and display and preparation method thereof |
| CN111393166A (en) * | 2020-03-27 | 2020-07-10 | 徐州凹凸光电科技有限公司 | High-thermal-stability fluorescent ceramic for white light L ED/L D and preparation method thereof |
| CN112159220A (en) * | 2020-09-24 | 2021-01-01 | 徐州凹凸光电科技有限公司 | High-thermal-stability high-quantum-efficiency fluorescent ceramic for white light LED/LD and preparation method thereof |
| CN112174646A (en) * | 2020-09-28 | 2021-01-05 | 东北大学 | High-thermal-conductivity fluorescent ceramic for laser illumination and preparation method thereof |
| CN113582679A (en) * | 2021-07-26 | 2021-11-02 | 江苏师范大学 | Fluorescent ceramic with high color rendering index and high thermal stability for white light illumination and preparation method thereof |
-
2022
- 2022-06-29 CN CN202210746344.1A patent/CN114988862B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160312116A1 (en) * | 2013-04-09 | 2016-10-27 | Daejoo Electronic Materials Co., Ltd | Fluorescent material for white light emitting diode and preparation method thereof |
| JP2017179219A (en) * | 2016-03-31 | 2017-10-05 | 信越化学工業株式会社 | Fluorescence material, and method of producing the same |
| CN108503352A (en) * | 2018-03-27 | 2018-09-07 | 中国科学院上海硅酸盐研究所 | A kind of garnet-base red fluorescence ceramic material and preparation method thereof |
| CN109592978A (en) * | 2018-12-03 | 2019-04-09 | 江苏师范大学 | High-capacity LED/LD illumination refers to fluorescence ceramics and the preparation method and application thereof with warm white height is aobvious |
| CN111285682A (en) * | 2018-12-07 | 2020-06-16 | 上海航空电器有限公司 | Full-spectrum complex phase fluorescent ceramic for laser illumination and display and preparation method thereof |
| CN111393166A (en) * | 2020-03-27 | 2020-07-10 | 徐州凹凸光电科技有限公司 | High-thermal-stability fluorescent ceramic for white light L ED/L D and preparation method thereof |
| CN112159220A (en) * | 2020-09-24 | 2021-01-01 | 徐州凹凸光电科技有限公司 | High-thermal-stability high-quantum-efficiency fluorescent ceramic for white light LED/LD and preparation method thereof |
| CN112174646A (en) * | 2020-09-28 | 2021-01-05 | 东北大学 | High-thermal-conductivity fluorescent ceramic for laser illumination and preparation method thereof |
| CN113582679A (en) * | 2021-07-26 | 2021-11-02 | 江苏师范大学 | Fluorescent ceramic with high color rendering index and high thermal stability for white light illumination and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115677349A (en) * | 2022-10-12 | 2023-02-03 | 中国科学院上海光学精密机械研究所 | Fluorescent ceramic material with broad-spectrum red light emission and preparation method thereof |
| CN115677349B (en) * | 2022-10-12 | 2023-05-12 | 中国科学院上海光学精密机械研究所 | Fluorescent ceramic material with broad spectrum red light emission and preparation method thereof |
| CN116444271A (en) * | 2023-05-06 | 2023-07-18 | 江苏师范大学 | High-color-rendering-index high-thermal-stability fluorescent ceramic for LD/LED and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114988862B (en) | 2023-06-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114988862A (en) | High-color-rendering-index fluorescent ceramic for laser lighting and preparation method thereof | |
| CN111205081B (en) | Single-structure type low-color-temperature high-color-rendering-index fluorescent ceramic and preparation method and application thereof | |
| CN108503352B (en) | Garnet-based red fluorescent ceramic material and preparation method thereof | |
| CN101663371B (en) | White emitting light source and luminescent material with improved color stability | |
| CN112159220B (en) | High-thermal-stability high-quantum-efficiency fluorescent ceramic for white light LED/LD and preparation method thereof | |
| CN111995397A (en) | Fluorescent ceramic and preparation method and application thereof | |
| KR20190013977A (en) | Fluorescent powder, a method for producing the same, and a light emitting element having the same | |
| CN113582679B (en) | Fluorescent ceramic with high color rendering index and high thermal stability for white light illumination and preparation method thereof | |
| CN112266239B (en) | High-thermal-stability high-color-rendering-index fluorescent ceramic for white light LED/LD and preparation method thereof | |
| JP2014503605A (en) | Nitrogen compound luminescent material, method for preparing the same, and illumination light source manufactured thereby | |
| CN111393166B (en) | High-thermal-stability fluorescent ceramic for white light LED/LD and preparation method thereof | |
| CN112209714A (en) | Preparation technology of one-step-formed sintered aluminum-based garnet type luminescent ceramic | |
| CN115838286B (en) | Preparation and application of fluorescent ceramic for high-apparent-finger white light LED/LD | |
| CN113683407B (en) | High-brightness high-thermal-stability yellow-green fluorescent ceramic and preparation method thereof | |
| CN114031400B (en) | Single-phase warm white fluorescent ceramic and preparation method and application thereof | |
| CN112552038B (en) | Green fluorescent composite ceramic and preparation method and application thereof | |
| CN114477989B (en) | Graphene modified green light transparent ceramic material and preparation method and application thereof | |
| CN111072384A (en) | Ultraviolet excited fluorescent ceramic and preparation method thereof | |
| CN110283588B (en) | Fluorescent powder for white light LED for illumination display and preparation and application thereof | |
| CN114478008B (en) | Fluorescent ceramic with high color rendering index and high thermal stability for solid-state lighting and preparation method thereof | |
| CN113930244A (en) | Luminescent material, preparation method and application thereof | |
| CN111995398B (en) | Fluorescent ceramic for high-color-rendering-index laser illumination and preparation method thereof | |
| CN116444271A (en) | High-color-rendering-index high-thermal-stability fluorescent ceramic for LD/LED and preparation method thereof | |
| CN115180948B (en) | High-light-efficiency complex-phase fluorescent ceramic for laser illumination and preparation method thereof | |
| CN114196402B (en) | Eu-doped ultrahigh chromogenic borophosphate and preparation method and application thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |