CN116589271A - High-thermal-conductivity high-finger-display complex-phase fluorescent ceramic for laser illumination and preparation method thereof - Google Patents
High-thermal-conductivity high-finger-display complex-phase fluorescent ceramic for laser illumination and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 103
- 238000005286 illumination Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 43
- 238000005245 sintering Methods 0.000 claims abstract description 24
- 238000009877 rendering Methods 0.000 claims abstract description 20
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 11
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims description 29
- 239000002994 raw material Substances 0.000 claims description 22
- 238000000498 ball milling Methods 0.000 claims description 17
- 239000011812 mixed powder Substances 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 235000015895 biscuits Nutrition 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 13
- 239000004697 Polyetherimide Substances 0.000 claims description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 238000009694 cold isostatic pressing Methods 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 229920001601 polyetherimide Polymers 0.000 claims description 9
- 238000001513 hot isostatic pressing Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- 239000012856 weighed raw material Substances 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims 1
- 239000012071 phase Substances 0.000 abstract description 86
- 230000005284 excitation Effects 0.000 abstract description 19
- 238000000295 emission spectrum Methods 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000007858 starting material Substances 0.000 abstract description 3
- 238000000695 excitation spectrum Methods 0.000 abstract description 2
- 238000003746 solid phase reaction Methods 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 10
- 229910000420 cerium oxide Inorganic materials 0.000 description 7
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 7
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 7
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 229910000831 Steel Inorganic materials 0.000 description 5
- 239000010959 steel Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 239000002223 garnet Substances 0.000 description 4
- -1 ce) 3 (Al Inorganic materials 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
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Abstract
The invention discloses a high thermal conductivity and high finger display complex-phase fluorescent ceramic for laser illumination and a preparation method thereof, wherein the complex-phase fluorescent ceramic comprises (Gd, ce) as a main phase 3 (Al,Ga) 5 O 12 A phase, and a second phase Al uniformly distributed in the main phase 2 O 3 Wherein the luminescent ion is Ce 3+ The method comprises the steps of carrying out a first treatment on the surface of the By GdGaO 3 、CeO 2 、Al 2 O 3 As the starting material, solid phase reaction sintering was used. The excitation spectrum of the complex phase ceramic prepared by the invention has an emission spectrum main peak between 567 and 582nm and a half-width between 105 and 120nm under the excitation of the wavelength of 460 nm. Under excitation of blue light LD (1-5W) with wavelength of 455nm, warm white light emission is realized, color temperature is 3800-4250K, and color rendering index is 78-84; the heat conductivity is 20-25 Wm ‑1 k ‑1 Compared with single-phase fluorescent ceramics, the thermal conductivity of the single-phase fluorescent ceramics is improved by 40-69%, and the preparation method is simple, green and environment-friendly, and can be used for the industrialized production of LD devices.
Description
Technical Field
The invention relates to the technical field of fluorescent ceramics, in particular to a high-thermal-conductivity high-finger-display complex-phase fluorescent ceramic for laser illumination and a preparation method thereof.
Background
Fluorescent ceramics are light-light conversion functional materials widely applied to the technical fields of high-power illumination, high lumen display and the like. The light source equipment using the laser as the excitation source to excite the fluorescent ceramics has the advantages of high brightness, long range, long service life, small volume and the like, and can be widely applied to the fields of outdoor square illumination, sports stadium, automobile headlight, aviation navigation illumination and the like. But the fluorescent ceramics are used in high power density laser>10W/mm 2 ) Under excitation of (2) the laser irradiated region of the fluorescent ceramic collects a large amount of heat (the main source is energy loss during light conversion), since the thermal conductivity of the fluorescent ceramic is about 14Wm -1 K -1 Insufficient rapid heat dissipation causes rapid rise in the ceramic temperature at the laser spot, resulting in reduction in luminous intensity, saturation of luminescence, and the like. And the fluorescent ceramic emission spectrum of the garnet system is mainly covered with yellow-green light, and lacks enough red light components, so that the color rendering performance is poor (CRI-60) and the color temperature is higher (more than 6000K).
There are a great deal of literature currently on the development of garnet fluorescent ceramics in order to achieve the luminescence modulation of fluorescent ceramicsAnd (5) controlling. Literature ((Ce, gd): YAG-Al 2 O 3 composite ceramics for high-brightness yellow light-patterning diode applications journal of the European Ceramic Society,2022 (3), 42, 1121-1131) report on the doping by Gd 3+ Can make Ce 3+ The emission peak of the ion is red shifted, and the improvement of the color rendering index is obvious, but the thermal stability is extremely poor. Thus, again by introducing Al 2 O 3 The second phase is used for improving the thermal conductivity of the fluorescent ceramic, but the density of the prepared ceramic is not high, mainly because when the Gd doping amount is too high, (Ce, gd) the YAG is decomposed at high temperature, so that the thermal conductivity is not obviously improved. Document (Effects of Ga substitution for Al on the fabrication and optical properties of transparent Ce: GAGG based ceramics Journal of the European Ceramic Society,2017 (37), 13, 4109-4114) reports the use of Ga 3+ Substituted for Al 3+ The GAGG crystal lattice is more stable and is not easy to decompose at high temperature, but has poor heat conductivity, if Al is introduced 2 O 3 When the thermal conductivity is improved as a second phase, ga is extremely easy to cause 3+ (in Ga) 2 O 3 When starting material) cannot replace Al entering garnet 3+ The GAGG phase is not normally produced. CN111995398A discloses that doping red light ions improves the color rendering index of fluorescent ceramics, realizes the supplementation of red light, but reduces the thermal conductivity of ceramics, and greatly limits the application of fluorescent ceramics under high-power laser illumination.
Disclosure of Invention
The invention aims to provide a high-thermal-conductivity high-finger-rendering complex-phase fluorescent ceramic for laser illumination, which has the advantages of high thermal conductivity and high color rendering index as a luminescent material.
The invention aims at providing a preparation method of high-thermal-conductivity high-apparent-index complex-phase fluorescent ceramic for laser illumination, which is simple to operate and easy to realize industrial production.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect, the invention provides a high thermal conductivity and high finger rendering complex-phase fluorescent ceramic for laser illumination, wherein the complex-phase fluorescent ceramic is wrappedIncluding as the main phase (Gd, ce) 3 (Al,Ga) 5 O 12 A phase, and a second phase Al uniformly distributed in the main phase 2 O 3 Wherein the luminescent ion is Ce 3+ 。
Under 460nm wavelength excitation, the main peak of the emission spectrum of the complex-phase fluorescent ceramic is 567-582 nm, and the half-width is 105-120 nm. Under excitation of blue light LD (1-5W) with wavelength of 455nm, warm white light emission is realized, color temperature is 3800-4250K, and color rendering index is 78-84. The thermal conductivity of the complex-phase fluorescent ceramic is 20-25 Wm -1 k -1 。
In a second aspect, the present invention further provides a method for preparing the high thermal conductivity and high color rendering index complex phase fluorescent ceramic for laser illumination, which adopts a solid phase reaction method for sintering, and specifically includes the following steps:
(1) According to the chemical formula (Gd) 1-x Ce x ) 3 (Al 2+3x Ga 3-3x )O 12 The stoichiometric ratio of each element is respectively weighed GdGaO 3 、CeO 2 、Al 2 O 3 As initial raw material, wherein x is Ce 3+ The mol percentage of the doped Gd position is more than or equal to 0.005 and less than or equal to 0.02; weighing alumina accounting for 20-60% of the total mass of the raw material powder to be used as a second phase of the ceramic;
(2) Mixing the weighed raw material powder and the dispersant polyetherimide, adding absolute ethyl alcohol, ball-milling and mixing, drying and sieving the obtained mixed slurry, and then placing the mixed powder in a muffle furnace for calcination;
(3) Placing the calcined powder into a grinding tool for dry pressing and forming, and then performing cold isostatic pressing to obtain a biscuit with the relative density of 50-55%;
(4) And sintering the biscuit at high temperature, cooling to room temperature, and then performing double-sided polishing treatment to obtain the complex-phase fluorescent ceramic.
Preferably, in the step (2), the adding amount of the dispersant polyetherimide is 0.8-1 wt.% of the total mass of the raw material powder, and the mass ratio of the total mass of the raw material powder to the absolute ethyl alcohol is 1:1.5-3.
Preferably, the ball milling rotating speed in the step (2) is 180-250 rpm, and the ball milling time is 15-30 h.
Preferably, the temperature of the drying in the step (2) is 50-80 ℃ and the drying time is 8-12 h.
Preferably, the temperature rising system of the calcination in the step (2) is to rise to 600-800 ℃ at the temperature rising rate of 2-10 ℃/min and keep the temperature for 5-7 h.
Preferably, the cold isostatic pressing pressure maintaining pressure in the step (3) is 150-200 Mpa, and the pressure maintaining time is 200-400 s.
Preferably, the high temperature sintering of step (3) is divided into two stages: pressureless presintering and hot isostatic pressing sintering, pressureless presintering: sintering at 1500-1700 deg.c for 8-10 hr; and (3) hot isostatic pressing sintering: sintering at 1500-1750 deg.c and pressure of 150-300 MPa for 5-8 hr.
In the present invention, the new raw material powder GdGaO is used 3 Prepared (Gd, ce) 3 (Al,Ga) 5 O 12 As the main phase, al 2 O 3 The fluorescent ceramic is two-phase complex-phase fluorescent ceramic, has high heat conductivity and wide half-width, and greatly improves the color rendering index and the heat stability of the ceramic. With GdGaO in the main phase 3 As a raw material, ga is avoided 3+ (in Ga) 2 O 3 When starting material) cannot replace Al entering garnet 3+ The GAGG phase is not normally produced.
Compared with the prior art, the invention has the following beneficial effects:
1. the excitation spectrum of the complex phase ceramic prepared by the invention has an emission spectrum main peak between 567 and 582nm and a half-width between 105 and 120nm under the excitation of the wavelength of 460 nm. Under excitation of blue light LD (1-5W) with wavelength of 455nm, warm white light emission is realized, color temperature is 3800-4250K, and color rendering index is 78-84; the thermal conductivity of the prepared complex-phase fluorescent ceramic is 20-25 Wm -1 k -1 Compared with single-phase fluorescent ceramics, the thermal conductivity of the single-phase fluorescent ceramics is improved by 40 to 69 percent, when Al 2 O 3 At a content of 50% (Gd, ce) 3 (Al,Ga) 5 O 12 -Al 2 O 3 To achieve the optimum thermal conductivity of 25Wm -1 k -1 At the same time the color rendering index reaches 82.
2. Al in the present invention 2 O 3 Not only used as the raw material of fluorescent ceramics, but also used as the two phases of complex phase ceramics, avoiding the introduction of impurity phases, and the two phases of Al 2 O 3 The ceramic has the advantages of improving the heat conductivity of the ceramic, inhibiting the growth of crystal grains, enabling the distribution of main phase particles to be small and uniform, and effectively improving the light extraction rate.
3. The complex-phase fluorescent ceramic prepared by the method has the characteristics of high color rendering index and high thermal conductivity, greatly improves the application value and service life of the device, is simple in preparation method, is environment-friendly, and can be used for the industrialized production of LD devices.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an X-ray diffraction chart of the complex-phase fluorescent ceramics prepared in examples 1 to 5 of the present invention;
FIG. 2 is a graph showing the emission spectrum of the complex-phase fluorescent ceramics prepared in examples 1 to 5 according to the present invention under 460nm wavelength excitation;
FIG. 3 is a surface SEM image of a complex-phase fluorescent ceramic sample prepared according to example 3 of the present invention;
FIG. 4 is a graph showing the thermal conductivity of the complex phase fluorescent ceramics prepared in examples 1 to 5 of the present invention.
Detailed Description
The invention will be described in further detail with reference to the drawings and the specific examples.
The raw material powders used in the following examples were all commercially available and had purities of more than 99.9%.
Example 1: the preparation chemical formula is (Gd 0.995 Ce 0.005 ) 3 (Al 2.015 Ga 2.985 )O 12 —20％Al 2 O 3 In (2) complex phase fluorescent ceramics, wherein Al 2 O 3 Accounting for 20 percent of the total mass of the powder
(1) The target product mass was set to 60.007g, according to (Gd 0.995 Ce 0.005 ) 3 (Al 2.015 Ga 2.985 )O 12 —20％Al 2 O 3 The stoichiometric ratio of each element is respectively weighed GdGaO 3 (42.5474g)、CeO 2 (0.1338g)、Al 2 O 3 (17.3250 g) as a raw material powder. Mixing 400 mu L of polyether imide serving as a dispersing agent, adding absolute ethyl alcohol, mixing gadolinium gallate, cerium oxide and alumina powder serving as raw materials, wherein the ratio of the total mass of gadolinium gallate, cerium oxide and alumina powder to the absolute ethyl alcohol is 1:1.5, fully mixing by adopting a planetary ball mill, wherein the ball milling speed is 180rpm, ball milling is carried out for 20 hours, drying the ball-milled mixed slurry in an oven at 80 ℃ for 13 hours to obtain mixed powder, sieving the mixed powder twice, and calcining the mixed powder at 800 ℃ for 5 hours. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 200MPa and dwell time for 200s to obtain the biscuit with the relative density of 50%. Followed by pressureless presintering: sintering at 1550 ℃ for 8 hours, and then performing hot isostatic pressing sintering: sintering temperature is 1600 ℃, pressure is 200MPa, and sintering is carried out for 5 hours. Finally, double-sided polishing is carried out on the complex-phase fluorescent ceramic to obtain the Ce in the shape of a sheet 3+ Activated yellow-green fluorescent ceramic. The diameter of the complex-phase fluorescent ceramic is about 17mm, and the thickness is 2mm, so that the compact complex-phase fluorescent ceramic is obtained.
The (Gd) obtained in this example 0.995 Ce 0.005 ) 3 (Al 2.015 Ga 2.985 )O 12 —20％Al 2 O 3 XRD testing of the complex-phase fluorescent ceramic shows that: the prepared material consists of GAGG phase and Al 2 O 3 The phase composition is as in fig. 1.
The (Gd) obtained in this example 0.995 Ce 0.005 ) 3 (Al 2.015 Ga 2.985 )O 12 —20％Al 2 O 3 The main peak of the emission spectrum of the complex-phase fluorescent ceramic is 582nm under 460nm wavelength excitation, as shown in figure 2; the ceramic realizes the emission from warm white light under the excitation of high-power blue light LD 3W, and has a color temperature 3800K and a color rendering index of 84; thermal conductivity of 20.2Wm -1 k -1 As shown in fig. 4.
Example 2: the preparation chemical formula is (Gd 0.99 Ce 0.01 ) 3 (Al 2.03 Ga 2.97 )O 12 —40％Al 2 O 3 In (2) complex phase fluorescent ceramics, wherein Al 2 O 3 Accounting for 40 percent of the total mass of the powder
(1) The target product mass was set to 60.010g, according to (Gd 0.99 Ce 0.01 ) 3 (Al 2.03 Ga 2.97 )O 12 —40％Al 2 O 3 The stoichiometric ratio of each element is respectively weighed GdGaO 3 (31.7810g)、CeO 2 (0.2009g)、Al 2 O 3 (28.0274 g) as a raw material powder. Mixing 400 mu L of polyether imide serving as a dispersing agent, adding absolute ethyl alcohol, mixing gadolinium gallate, cerium oxide and alumina powder serving as raw materials, wherein the ratio of the total mass of gadolinium gallate, cerium oxide and alumina powder to the absolute ethyl alcohol is 1:1.5, fully mixing by adopting a planetary ball mill, wherein the ball milling speed is 180rpm, ball milling is carried out for 20 hours, drying the ball-milled mixed slurry in an oven at 60 ℃ for 10 hours to obtain mixed powder, sieving the mixed powder twice, and calcining the mixed powder at 800 ℃ for 5 hours. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 150MPa and dwell time for 240s to obtain the biscuit with the relative density of 51%. And then sintering for 9h at 1650 ℃ under the condition of pressureless presintering, and sintering for 7h at 1600 ℃ under 260MPa under the condition of hot isostatic pressing. Finally, double-sided polishing is carried out on the complex-phase fluorescent ceramic to obtain the Ce in the shape of a sheet 3+ Activated yellow-green fluorescent ceramic. The diameter of the complex-phase fluorescent ceramic is about 17mm, and the thickness is 2mm, so that the compact complex-phase fluorescent ceramic is obtained.
The (Gd) obtained in this example 0.99 Ce 0.01 ) 3 (Al 2.03 Ga 2.97 )O 12 —40％Al 2 O 3 XRD testing of the complex-phase fluorescent ceramic shows that: the prepared material consists of GAGG phase and Al 2 O 3 The phase composition is as in fig. 1.
The (Gd) obtained in this example 0.99 Ce 0.01 ) 3 (Al 2.03 Ga 2.97 )O 12 —40％Al 2 O 3 The complex-phase fluorescent ceramic emits under the excitation of 460nm wavelengthThe main peak of the spectrum is 576nm as shown in FIG. 2; the ceramic realizes the emission from warm white light under the excitation of high-power blue light LD 3W, and has a color temperature of 3980K and a color rendering index of 82; thermal conductivity 23.2Wm -1 k -1 As shown in fig. 4.
Example 3: the preparation chemical formula is (Gd 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —40％Al 2 O 3 In (2) complex phase fluorescent ceramics, wherein Al 2 O 3 Accounting for 40 percent of the total mass of the powder
(1) The target product mass was set to 60.0140g, according to (Gd 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —40％Al 2 O 3 The stoichiometric ratio of each element is respectively weighed GdGaO 3 (31.6512g)、CeO 2 (0.3017g)、Al 2 O 3 (28.0611 g) as a raw material powder. Mixing 400 mu L of polyether imide serving as a dispersant, adding absolute ethyl alcohol, and enabling the ratio of the total mass of gadolinium gallate, cerium oxide and alumina powder serving as raw materials to the absolute ethyl alcohol to be 1:2; fully mixing by adopting a planetary ball mill, wherein the ball milling rotating speed is 250rpm, ball milling is carried out for 30 hours, the ball-milled mixed slurry is dried in an oven at 50 ℃ for 12 hours to obtain mixed powder, the mixed powder is screened by a 200-mesh screen for two times, and the mixed powder is calcined for 7 hours at 600 ℃. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 170MPa and dwell time for 200s to obtain the biscuit with the relative density of 52%. And then sintering for 8 hours at 1500 ℃ under the condition of pressureless presintering, and sintering for 8 hours at 1750 ℃ under the condition of 300MPa under the condition of hot isostatic pressing. Finally, double-sided polishing is carried out on the complex-phase fluorescent ceramic to obtain the Ce in the shape of a sheet 3+ Activated yellow-green fluorescent ceramic. The diameter of the complex-phase fluorescent ceramic is about 17mm, and the thickness is 2mm, so that the compact complex-phase fluorescent ceramic is obtained.
The (Gd) obtained in this example 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —40％Al 2 O 3 XRD testing of the complex-phase fluorescent ceramic shows that: the prepared material consists of GAGG phase and Al 2 O 3 The phase composition is as in fig. 1.
The (Gd) obtained in this example 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —40％Al 2 O 3 The main peak of the emission spectrum of the complex-phase fluorescent ceramic is 572nm under the excitation of 460nm wavelength, as shown in figure 2; the SEM image of the measured fluorescent ceramic surface has compact crystal grains, and the size of the crystal grains is 2-3 mu m, as shown in figure 3; the ceramic realizes the emission from warm white light under the excitation of high-power blue light LD 3W, and has a color temperature of 3950K and a color rendering index of 80; thermal conductivity of 23.3Wm -1 k -1 As shown in fig. 4.
Example 4: the preparation chemical formula is (Gd 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —50％Al 2 O 3 In (2) complex phase fluorescent ceramics, wherein Al 2 O 3 Accounting for 50 percent of the total mass of the powder
(1) The target product mass was set to 60.012g, according to (Gd 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —50％Al 2 O 3 The stoichiometric ratio of each element is respectively weighed GdGaO 3 (26.3760g)、CeO 2 (0.2514g)、Al 2 O 3 (33.3843 g) as a raw material powder. Mixing 400 mu L of polyether imide serving as a dispersant, adding absolute ethyl alcohol, and enabling the ratio of the total mass of gadolinium gallate, cerium oxide and alumina powder serving as raw materials to the absolute ethyl alcohol to be 1:2.5; fully mixing by adopting a planetary ball mill, wherein the ball milling rotating speed is 200rpm, ball milling is carried out for 20 hours, the mixed slurry after ball milling is dried in an oven at 80 ℃ for 9 hours to obtain mixed powder, sieving the mixed powder by a 200-mesh sieve for two times, and calcining the mixed powder for 6 hours at 800 ℃. And then drying and pressing the mixture in a steel mould to obtain a biscuit, and carrying out cold isostatic pressing for 200MPa and dwell time for 200s to obtain the biscuit with the relative density of 54%. And then sintering for 8h at 1550 ℃ under the conditions of 1750 ℃ and 200MPa for 5h. Finally, double-sided polishing is carried out on the complex-phase fluorescent ceramic to obtain the Ce in the shape of a sheet 3+ Activated yellow-green fluorescent ceramic. The diameter of the complex-phase fluorescent ceramic is about 17mm, and the thickness is 2mm, so that the compact complex-phase fluorescent ceramic is obtained.
The (Gd) obtained in this example 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —50％Al 2 O 3 XRD testing of the complex-phase fluorescent ceramic shows that: the prepared material consists of GAGG phase and Al 2 O 3 The phase composition is as in fig. 1.
The (Gd) obtained in this example 0.985 Ce 0.015 ) 3 (Al 2.045 Ga 2.955 )O 12 —50％Al 2 O 3 The main peak of the emission spectrum of the complex-phase fluorescent ceramic is 568nm under the excitation of 460nm wavelength, as shown in figure 2; the ceramic realizes the emission from warm white light under the excitation of high-power blue light LD 3W, and has a color temperature of 3960K and a color rendering index of 83; thermal conductivity of 25Wm -1 k -1 As shown in fig. 4.
Example 5: the preparation chemical formula is (Gd 0.98 Ce 0.02 ) 3 (Al 2.06 Ga 2.94 )O 12 —60％Al 2 O 3 In (2) complex phase fluorescent ceramics, wherein Al 2 O 3 Accounting for 60 percent of the total mass of the powder
(1) The target product mass was set to 60.012g, according to (Gd 0.98 Ce 0.02 ) 3 (Al 2.06 Ga 2.94 )O 12 —60％Al 2 O 3 The stoichiometric ratio of each element is respectively weighed GdGaO 3 (21.0141g)、CeO 2 (0.2684g)、Al 2 O 3 (38.7299 g) as a raw material powder. Mixing 400 mu L of polyether imide serving as a dispersant, adding absolute ethyl alcohol, and enabling the ratio of the total mass of gadolinium gallate, cerium oxide and alumina powder serving as raw materials to the absolute ethyl alcohol to be 1:3; fully mixing by adopting a planetary ball mill, wherein the ball milling rotating speed is 180rpm, ball milling is carried out for 30 hours, the ball-milled mixed slurry is dried in an oven at 80 ℃ for 8 hours to obtain mixed powder, the mixed powder is sieved by a 200-mesh sieve for 2 times, and the mixed powder is calcined for 5 hours at 800 ℃. And then drying and pressing the mixture in a steel mould to form a biscuit, and carrying out cold isostatic pressing for 150MPa and dwell time for 400s. And then sintering for 10 hours at 1700 ℃ under the conditions of pressureless presintering temperature, 1500 ℃ under the conditions of 300MPa and 5 hours under the conditions of hot isostatic pressing. Finally, double-sided polishing is carried out on the complex-phase fluorescent ceramics to obtain a sheetCe in the shape of 3+ Activated yellow-green fluorescent ceramic. The diameter of the complex-phase fluorescent ceramic is about 17mm, and the thickness is 2mm, so that the compact complex-phase fluorescent ceramic is obtained.
The (Gd) obtained in this example 0.98 Ce 0.02 ) 3 (Al 2.06 Ga 2.94 )O 12 —60％Al 2 O 3 XRD testing of the complex-phase fluorescent ceramic shows that: the prepared material consists of GAGG phase and Al 2 O 3 The phase composition is as in fig. 1.
The (Gd) obtained in this example 0.98 Ce 0.02 ) 3 (Al 2.06 Ga 2.94 )O 12 —60％Al 2 O 3 The main peak of the emission spectrum of the complex-phase fluorescent ceramic is 567nm under the excitation of 460nm wavelength, as shown in figure 2; the ceramic realizes the emission from warm white light under the excitation of high-power blue light LD 3W, the color temperature is 4250K, and the color rendering index is 78; thermal conductivity of 24.9Wm -1 k -1 As shown in fig. 4.
The foregoing is merely illustrative of specific embodiments of the present invention, and the scope of the invention is not limited thereto, but any modifications, equivalents, improvements and alternatives falling within the spirit and principles of the present invention will be apparent to those skilled in the art within the scope of the present invention.
Claims (8)
1. A high thermal conductivity and high finger display complex phase fluorescent ceramic for laser illumination is characterized in that the complex phase fluorescent ceramic comprises (Gd, ce) as a main phase 3 (Al,Ga) 5 O 12 A phase, and a second phase Al uniformly distributed in the main phase 2 O 3 Wherein the luminescent ion is Ce 3+ 。
2. A method for preparing the high thermal conductivity and high finger rendering complex phase fluorescent ceramic for laser illumination according to claim 1, which is characterized by comprising the following steps:
(1) According to the chemical formula (Gd) 1-x Ce x ) 3 (Al 2+3x Ga 3-3x )O 12 Chemistry of each element in (3)The measurement ratio is to weigh GdGaO respectively 3 、CeO 2 、Al 2 O 3 As initial raw material, wherein x is Ce 3+ The mol percentage of the doped Gd position is more than or equal to 0.005 and less than or equal to 0.02; weighing alumina accounting for 20-60% of the total mass of the raw material powder to be used as a second phase of the ceramic;
(2) Mixing the weighed raw material powder and the dispersant polyetherimide, adding absolute ethyl alcohol, ball-milling and mixing, drying and sieving the obtained mixed slurry, and then placing the mixed powder in a muffle furnace for calcination;
(3) Placing the calcined powder into a grinding tool for dry pressing and forming, and then performing cold isostatic pressing to obtain a biscuit with the relative density of 50-55%;
(4) And sintering the biscuit at high temperature, cooling to room temperature, and then performing double-sided polishing treatment to obtain the complex-phase fluorescent ceramic.
3. The method for preparing the high-thermal-conductivity high-finger-rendering complex-phase fluorescent ceramic for laser illumination according to claim 2, wherein in the step (2), the adding amount of the dispersant polyetherimide is 0.8-1 wt.% of the total mass of the raw material powder, and the mass ratio of the total mass of the raw material powder to the absolute ethyl alcohol is 1:1.5-3.
4. The method for preparing the high thermal conductivity and high finger-displaying complex phase fluorescent ceramic for laser illumination according to claim 2, wherein in the step (2), the ball milling rotating speed is 180-250 rpm, and the ball milling time is 15-30 h.
5. The method for preparing the high thermal conductivity and high finger complex phase fluorescent ceramic for laser illumination according to claim 2, wherein in the step (2), the drying temperature is 50-80 ℃ and the drying time is 8-12 h.
6. The method for preparing the high thermal conductivity and high finger complex phase fluorescent ceramic for laser illumination according to claim 2, wherein in the step (2), the temperature rising system of calcination is that the temperature rises to 600-800 ℃ at the temperature rising rate of 2-10 ℃/min, and the temperature is kept for 5-7 h.
7. The method for preparing high thermal conductivity and high finger complex phase fluorescent ceramic for laser illumination according to claim 2, wherein in the step (3), the cold isostatic pressing pressure is 150-200 Mpa, and the holding time is 200-400 s.
8. The method for preparing high thermal conductivity and high finger complex phase fluorescent ceramic for laser illumination according to claim 2, wherein in the step (4), the high temperature sintering is divided into two stages: pressureless presintering and hot isostatic pressing sintering, pressureless presintering: sintering at 1500-1700 deg.c for 8-10 hr; and (3) hot isostatic pressing sintering: sintering at 1500-1750 deg.c and pressure of 150-300 MPa for 5-8 hr.
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