CN109020558A - A kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof - Google Patents
A kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof, and this method comprises the following steps: according to general formula Cam/2‑x‑yv/2Si12‑m‑nAlm+ nOnN16‑n:xEu2+,yMv+, wherein v is chemical valence, 0.8≤m≤2.0,1.0≤n≤2.0,0 < x≤m/4,0≤y≤m/2v-2x/v, by above-mentioned general formula selection α-Si3N4、AlN、α‑Al2O3、CaCO3、Eu2O3With the raw material containing M, mixture A is obtained, mixture B, mixing is then added, the mixture B is AlN and α-Si3N4Mixture, in which: the quality of mixture B is 5~50wt% of mixture A mass, Si in mixture B3N4Weight ratio with AlN is 0~5:1, ball milling and drying, is sintered using hot pressed sintering or discharge plasma, obtains sintered body；It cuts, grind, be polished to mirror surface, obtain in the case where blue light is excited in broadband emission, dominant wavelength is the Ca- α-sialon:Eu of 570-600nm and Wavelength tunable2+Fluorescent transparent ceramics.Present invention process is simple, and repeatability is strong, and prepared fluorescent transparent ceramics thermal conductivity is high, thermal quenching is had excellent performance, and is suitable for high-power warm white solid-state lighting.
Description
Technical field
The present invention relates to a kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof, belong to
In rare earth luminescent material and solid-state lighting preparation field.
Background technique
Solid-state lighting has many advantages, such as energy conservation and environmental protection, light efficiency height, service life length, high reliablity, small in size, is that most development is latent
The green light source of power.White-light LED illumination is the mainstream of current solid-state lighting, wherein " blue LED die+yellow fluorescent powder " combines
It is to realize the most common mode of White-light LED illumination.However, because used in it epoxy resin or silica gel packaging material it is easy to aging, resistance to
It is further that the problems such as light efficiency decline, color shift, the lost of life of high temperatures difference and its caused LED, limits large power white light LED
Development.Therefore, it is extremely urgent to adapt to large power white light LED illumination to use novel encapsulated mode.Recently, another with higher
Brightness, and solid state illumination technology --- the laser lighting without " efficiency rapid drawdown " phenomenon, then propose fluorescent material and encapsulating material
Higher requirement.
Because having the transparency good, the good comprehensive performances such as thermal conductivity is high, thermal stability is good, fluorescent transparent ceramics replace
" conventional fluorescent powder+organic matter encapsulating material " has evoked intense interest.YAG:Ce at present3+Fluorescent transparent ceramics have started to be applied to
Great power LED and laser lighting, such as BMW laser headlight.However, YAG:Ce3+Fluorescent material is produced because lacking red color components
The disadvantages of raw white light is poor higher with colour temperature there are colour rendering, so that can not be applied in warm white optical arena.For this purpose, research
Personnel increase red emission by various measures.Such as add Gd3+Replace Y3+[Opt.Express,2015,23 14 18243-
18255] make luminescent spectrum entirety red shift, be directly added into emitting red light ion such as Cr3+[shine journal, 2016,37 10 1213-
1216]、Pr3+[J.Eur.Ceram.Soc.,2017,93 11 3403-3409].Although these measures can reduce to a certain extent
Colour temperature, but mostly to sacrifice the luminous efficiency of a part as cost.More it is essential that YAG:Ce3+The thermal quenching temperature of material is opposite
It is lower, as the Gd that certain content is added3+、Ga3+And the Ce of doping high concentration3+(such as commercial product), thermal quenching performance are then shown
Writing reduces.Therefore, YAG:Ce is being continued to optimize3+While fluorescence ceramics performance, it is necessary to seek new fluorescent transparent ceramic body
System is to adapt to high-power or even super high power warm white solid-state lighting.Nearest research has shown that there are part light in (partly) crystalline ceramics
Scattering can not only improve blue light absorption, and can also reduce total internal reflection, thus improve light emission rate [Opt.Express,
2015,23 14 17923-17928].Visible fluorescence crystalline ceramics is not required for having very high transparency, translucent instead
State may obtain better luminescent properties, this provides broader space to seek new fluorescence (partly) crystalline ceramics.
As α-Si3N4Solid solution, α-sialon (chemical general formula Mm/vSi12-m-nAlm+nOnN16-n, M Li, Mg, Ca
And most of rare earth ions, v are stabilizing ion chemical valence) it is for a long time considered as a kind of high temperature knot that performance is very excellent
Structure material.Because having strong covalent bond and close crystal structure, which shows excellent mechanical property, and very high chemistry is steady
Qualitative and high-temperature stability.On the other hand, there are two big holes in α-sialon structure cell, these holes can accommodate dilute
Native light emitting ionic Ren+(such as Eu2+、Ce3+、Yb2+Deng) and form the shorter Re-N covalent bond of bond distance.This strongly covalent Re-N key with
And N3-Higher formal charge is (with O2-Compared to) be conducive to generate electron cloud bulking effect and crystalline field cleavage effect, to promote
Into red shift of the emission spectra.In addition, due to its rigid structure, thermal quenching is had excellent performance.So far, for blue light activated rare earth
α-sialon the fluorescent powder of light emitting ionic doping is largely reported, such as Li- α-sialon:Eu2+[Appl.Phys.Lett.,
2006,89 24 241103]、Mg-α-sialon:Yb2+[J.Phys.Chem.B,2005,109 19 9490-9494]、Lu-α-
sialon:Ce3+[J.Am.Ceram.Soc., 2009,92 11 2738-2744] etc..Wherein, because can effectively be excited by blue light, and
Emission spectrum is in yellow light, green wavelength, Eu2+α-the sialon of doping is more favored.
With other α-sialon:Eu2+It compares, Ca- α-sialon:Eu2+Red shift becomes apparent from, and quantum efficiency is higher, and high temperature is steady
Qualitative more preferable, rare earth luminous ion solid solubility is bigger, has higher practical value, thus correlative study is more concentrated.Research
Show: Ca- α-sialon:Eu2+Fluorescent material has than YAG:Ce3+More red color light components, higher thermal conductivity and thermal quenching
Temperature, thus be very suitable to prepare high-power warm white solid-state lighting fluorescence ceramics.But so far in relation to Ca- α-
sialon:Eu2+Research have focused largely on powder, and reported in relation to the fluorescence ceramics of Ca- α-sialon also seldom.2002,
R.J.Xie etc. uses hot pressed sintering in 1750 DEG C of prepared compositions for the Ca- α-sialon:Eu of m=2n=1.52+Fluorescence ceramics, examination
The consistency of sample is more than 97% [J.Am.Ceram.Soc., 2002,85 5 1229-1234].2013, Y.J.Park etc. passed through
Gas pressure sintering prepares the Ca- α-sialon:Eu of different component at 1800-2000 DEG C2+Fluorescence ceramics, but sample highest is fine and close
Degree is only 90% [J.Kor.Ceram.Soc., 2013,50 4 280-287].Based on translucency to ceramic inner air vent and second
The microstructure requirement of phase (glass phase), can determine whether that above two sample is not (partly) transparent.2002, J.Krevel etc. was used
HIP sintering is prepared for (Ca0.3125Ce0.209)-α-sialon fluorescent transparent ceramics, but Ca- α-sialon:Eu2+Fluorescence
Crystalline ceramics does not report [J.Solid State Chem., 2002,165 19-24].Moreover, α-the sialon is total electricity price
Equal double ion is stablized, this is not only difficult to luminous ion concentration be adjusted (the usual content of luminous ion concentration is less),
At the same time it is difficult to ensure single ion Ca2+Or mainly by Ca2+Stable α-sialon is able to achieve transparent.In addition, this method is to equipment
It is required that the problems such as very high and very high there are cost.And on the other hand, other ion stabilized α-sialon fluorescent transparent ceramics
It has been be reported that, such as Mg- α-sialon:Eu2+[J.Alloy Compd.,2015,631 38-45].Patent
(CN201510174020.5) it then discloses with different rare earth ions such as Eu2+、Tb3+As light emitting ionic, by rare earth ion Y3+Or
Gd3+The preparation method of stable α-sialon fluorescent transparent ceramics.As described above, although there is excellent mechanics, calorifics and hair
Optical property, but Ca- α-sialon:Eu2+Fluorescent transparent ceramics are difficult to prepare.This key factor is in Ca- alpha -- sialon ceramic
It is easy to the glass phase that residual is also easy to produce strong light scattering and light absorption, and is difficult to eliminate with preparation method using conventional proportions residual
Remaining glass phase, this proves [J.Eur.Ceram.Soc., 1999,19 553-560] by lot of documents.Although patent
(CN201510174020.5) Ca- α-sialon:Eu is disclosed2+The preparation method of fluorescent transparent ceramics, but patent use
It is conventional proportions, this proportion is it is difficult to ensure that eliminate most glass phase.Patent (CN201110178303.9) discloses
Additional nitride is added on the basis of conventional proportions to be reduced glass phase and obtains Ca2+The system of stable alpha-sialon semitransparent ceramics
Preparation Method, but it is not directed to the report added in terms of rare earth luminous ion obtains luminescent properties.As described above, with other α-
Sialon is compared, Ca- α-sialon:Eu2+Fluorescent transparent ceramics red shift becomes apparent from, and quantum efficiency is higher, therefore, prepares Ca- α-
sialon:Eu2+Fluorescent transparent ceramics have more practical significance to high-power or even super high power warm white solid-state lighting is developed.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of high-power warm white solid-state lighting is saturating with SiAlON fluorescence
Bright ceramics and preparation method thereof.Hot pressed sintering or discharge plasma sintering method can be used in the present invention, and simple process repeats
Property it is strong, sintering temperature is low, be able to achieve bulk industrial production.Ceramic material obtained is complete densification Eu2+Activate Ca- α-
SiAlON fluorescent transparent ceramics.The ceramics can produce yellow orange light emitting under blue light excitation and wavelength can be by component and Eu2+It is dense
Degree is regulated and controled, which also has quenching temperature height, quantum efficiency height, excellent in mechanical performance, high-temperature stability good and hot
The characteristics such as conductance height.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: a kind of high-power warm white solid-state lighting use
SiAlON fluorescent transparent ceramics and preparation method thereof, it is characterised in that it includes the following steps:
1. a kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof, it is characterised in that
It includes the following steps:
(1) according to general formula Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+, wherein v be chemical valence, 0.8≤m≤
2.0,1.0≤n≤2.0,0 < x≤m/4,0≤y≤m/2v-2x/v choose α-Si by above-mentioned stoichiometric ratio3N4、AlN、α-
Al2O3、CaCO3、Eu2O3With the raw material mixing containing M, mixture A is obtained, mixture B, mixing, the mixture B is then added
For AlN and α-Si3N4Mixture, in which: the quality of mixture B is 5~50wt% of mixture A mass, in mixture B
Si3N4Weight ratio with AlN is 0~5:1；
(2) mixture for obtaining step (1) ball milling at least 24 hours, obtains slurry using dehydrated alcohol as decentralized medium；
(3) the slurry rotary evaporation for obtaining step (2) is dry, is then dried in vacuo at least for 24 hours, and 100 mesh are crossed in grinding
Sieve, obtains screenings；
(4) screenings after step (3) sieving is sintered using hot pressed sintering or discharge plasma sintering process, institute
The hot pressed sintering stated is that screenings is put into hot-pressed sintering furnace, is not less than 30MPa and N in sintering pressure2Under protection, with 5~
The heating rate of 30 DEG C/min is warming up to 950~1050 DEG C of 10~60min of heat preservation, then with the heating rate of 5~20 DEG C/min
It is warming up to 1600~1850 DEG C to be sintered 0.5~2 hour, furnace cooling obtains sintered body；The discharge plasma is sintered
Screenings is put into discharge plasma sintering furnace, is not less than 30MPa and N in sintering pressure2Under protection, with 50~500 DEG C/
The heating rate of min is warming up to 950~1050 DEG C of 1~2min of heat preservation, is then warming up to the heating rate of 50~500 DEG C/min
1600~1850 DEG C, it is sintered 0~20min, furnace cooling obtains sintered body；
(5) sintered body that step (4) obtains cut, grind, be polished to mirror surface, with a thickness of 0.1-1.0mm to get arriving
Ca-α-sialon:Eu2+Fluorescent transparent ceramics.
Raw material containing M described in step (1) is oxide or carbonate Li2CO3、MgO、SrCO3、Y2O3、Sc2O3、
La2O3、CeO2、Pr2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3One of.
According to the above scheme, ball milling described in step (2) is with Si3N4Ball is ball-milling medium, ratio of grinding media to material 4:1.
According to the above scheme, the α-Si3N4Oxygen content≤1.6wt%, average grain diameter≤0.2 μm.
According to the above scheme, oxygen content≤1.0wt% of the AlN, average grain diameter≤0.8 μm.
According to the above scheme, the α-Al2O3Purity be > 99.5%, average grain diameter≤500nm.
According to the above scheme, the CaCO3Purity be > 99.5%, average grain diameter≤500nm.
According to the above scheme, the Eu2O3Purity be > 99.99%, average grain diameter≤1 μm.
According to the above scheme, the oxide or carbonic acid purity salt containing M is > 99.5%, average grain diameter≤1 μm.
According to the above scheme, the N2N under protection2Pressure is 0.01~0.1MPa.
The principle of the present invention is: passing through Si3N4-AlN-Al2O3In-CaO phase G- Design α-SiAlON plane at branch,
AlN and Si is added on this basis and additionally3N4Mixture, be located at total ingredient point under α-SiAlON plane, be conducive to
Intergranular amount of glassy phase is reduced, to reduce light scattering and light absorption.A small amount of light emitting ionic Eu is used on this basis2+Replace
Ca2+, while a small amount of M can be addedv+Further to promote red shift or increase red color light component or green color components etc..Swash when using blue light
When hair, a part of blue light is absorbed and generates radiation transistion and form the transmitting light that dominant wavelength is located at yellow orange light region, this part
Yellow orange light and another part transmitted through blue light to form warm white.
Beneficial outcomes of the invention: 1, discharge plasma sintering can be used in the present invention, and hot-pressing sintering method also can be used
Prepare Ca- α-sialon:Eu2+Fluorescent transparent ceramics, simple process, repeatability is strong, and widely applicable, sintering temperature is moderate；2,
Prepared ceramic Ca- α-sialon:Eu2+Fluorescent transparent ceramics are broadband emission, and dominant wavelength is located at 570-600nm, and wave
Length can pass through component and Eu2+Concentration is regulated and controled, and quantum efficiency is high；In addition, the fluorescent transparent ceramics also have excellent mechanical property
Energy, thermal conductivity and good thermal quenching, especially suitable for high-power or even super high power warm white solid-state lighting field.
Detailed description of the invention
Fig. 1 is Ca- α-sialon:Eu obtained in the embodiment of the present invention 12+The XRD spectra of fluorescent transparent ceramics.
Fig. 2 is Ca- α-sialon:Eu obtained in the embodiment of the present invention 12+The scanning electron microscope of fluorescent transparent ceramics is shone
Piece.
Fig. 3 is Ca- α-sialon:Eu obtained in the embodiment of the present invention 12+The excitation-emission light of fluorescent transparent ceramics
Spectrum.
Fig. 4 is Ca- α-sialon:Eu obtained in the embodiment of the present invention 12+The effect photo of fluorescent transparent ceramics.
Specific embodiment
For a better understanding of the present invention, the content that the present invention is furture elucidated with reference to the accompanying drawings and examples, but this
The content of invention is not limited solely to the following examples.
Embodiment 1:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3And Eu2O3For
Raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+The chemistry of (m=0.8, n=1.0, x=0.02, y=0)
It measures than choosing the above-mentioned raw materials that total weight is 50g, mixing, and 2.5g AlN is additionally added in the mixture, by above-mentioned original
Material mixes in plastic bottle, with Si3N4Ball is ball-milling medium, and ball material mass ratio is 4:1, and 400ml dehydrated alcohol, roller ball is added
Mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum oven and are dried under vacuum to
It is few to further take out for 24 hours, 20min is ground, sieves with 100 mesh sieve, obtains screenings；Screenings after sieving is packed into the stone that diameter is 48mm
It in black mold, is then placed in hot-pressed sintering furnace, in N2Under conditions of protection and sintering pressure are 30MPa, the N2Pressure is
0.1MPa rises to 950 DEG C of heat preservation 10min with the heating rate of 30 DEG C/min, then rises to 1600 with the heating rate of 5 DEG C/min
DEG C, heat preservation sintering 1 hour, then with furnace natural cooling；Sintered body after cooling is obtained into 0.5mm after cutting, grinding, polishing
Thick Ca- α-sialon:Eu2+Fluorescent transparent ceramics.(see Fig. 4).
Ca- α-the sialon:Eu that the present embodiment is obtained2+Fluorescent transparent ceramics carry out XRD test (see Fig. 1), and Fig. 1 is said
Bright: prepared material is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.
It carries out SEM test (see Fig. 2), Fig. 2 explanation: prepared material is mainly equiax crystal, homogeneous grain size.
It carrying out excitation-emission spectrum test (see Fig. 3), Fig. 3 explanation: prepared material can effectively be excited by blue light, when
When 450nm is excited, emission spectrum is in broadband emission, and dominant wavelength 585nm, being formed by light is yellow orange light.Using ultraviolet-visible
It is 10% that spectrophotometer, which measures straight line transmittance at 600nm, uses indentation method to measure microhardness as 20.5GPa, is broken tough
Property is 4.6MPam1/2.Thermal conductivity 15.8Wm is measured using laser flash method-1·K-1。
Embodiment 2:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
Y2O3For raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=0.8, n=1.0, x=0.02, y=
0.05) stoichiometric ratio chooses the above-mentioned raw materials that total weight is 50g, and 20g AlN is additionally added in the mixture, will be upper
It states raw material to mix in plastic bottle, with Si3N4Ball is ball-milling medium, and 400ml dehydrated alcohol, roller ball is added in ratio of grinding media to material 4:1
Mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum oven and are dried under vacuum to
It is few to further take out for 24 hours, 20min is ground, sieves with 100 mesh sieve, obtains screenings；Screenings after sieving is packed into the stone that diameter is 48mm
It in black mold, is then placed in hot-pressed sintering furnace, in N2Under conditions of protection and sintering pressure are 30MPa, the N2Pressure is
0.05MPa is risen to 950 DEG C of heat preservation 10min with the heating rate of 30 DEG C/min, is then risen to the heating rate of 5 DEG C/min
1600 DEG C, heat preservation sintering 1 hour, then with furnace natural cooling；Sintered body after cooling is obtained after cutting, grinding, polishing
0.1mm thickness Ca- α-sialon:Eu2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 16% at the sample 600nm of 0.2mm thickness out, and emission spectrum dominant wavelength is 590nm, and microhardness is
20.3GPa, fracture toughness 4.3MPam1/2, thermal conductivity 12.3Wm-1·K-1。
Embodiment 3:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
Sc2O3For raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=1.6, n=2.0, x=0.04, y=
0.03) it is 50g above-mentioned raw materials that stoichiometric ratio, which chooses total weight, and 16g Si is additionally added in the mixture3N4And 4g
The compound of AlN mixes above-mentioned raw materials, in plastic bottle with Si3N4Ball is ball-milling medium, and 400ml is added in ratio of grinding media to material 4:1
Dehydrated alcohol roller ball mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum
Drying box is dried in vacuo at least for 24 hours, is further taken out, and is ground 20min, is sieved with 100 mesh sieve, obtain screenings；By the screenings dress after sieving
Enter in the graphite jig that diameter is 48mm, is then placed in hot-pressed sintering furnace, in N2The condition that protection and sintering pressure are 30MPa
Under, the N2Pressure is 0.01MPa, 950 DEG C of heat preservation 10min is risen to the heating rate of 30 DEG C/min, then with 5 DEG C/min's
Heating rate rises to 1750 DEG C, and heat preservation sintering 1 hour, then with furnace natural cooling；By sintered body after cooling by cutting, grinding
0.3mm thickness Ca- α-sialon:Eu is obtained after mill, polishing2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 8% at the sample 600nm of 0.3mm thickness out, and emission spectrum dominant wavelength is 592nm, and microhardness is
20.1GPa, fracture toughness 4.0MPam1/2, thermal conductivity 16.2Wm-1·K-1。
Embodiment 4:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
MgO is raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=1.0, n=1.5, x=0.4, y=0.1)
Stoichiometric ratio choose total weight be 50g above-mentioned raw materials, and in the mixture additionally be added 15g Si3N4With 10g AlN
Compound, above-mentioned raw materials are mixed in plastic bottle, with Si3N4Ball is ball-milling medium, ratio of grinding media to material 4:1, be added 400ml without
Water-ethanol roller ball mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, and it is dry to be then placed in vacuum
Dry case vacuum drying at least for 24 hours, further takes out, grinds 20min, sieve with 100 mesh sieve, obtain screenings；Screenings after sieving is packed into
Diameter is to be then placed in hot-pressed sintering furnace, in the graphite jig of 48mm in N2The condition that protection and sintering pressure are 30MPa
Under, the N2Pressure is 0.1MPa, 950 DEG C of heat preservation 60min is risen to the heating rate of 10 DEG C/min, then with 5 DEG C/min's
Heating rate rises to 1850 DEG C, and heat preservation sintering 1 hour, then with furnace natural cooling；By sintered body after cooling by cutting, grinding
0.8mm thickness Ca- α-sialon:Eu is obtained after mill, polishing2+Fluorescent transparent ceramics.
After measured, ceramic block is α-SiAlON.Straight line transmittance is at the sample 600nm for the 0.3mm thickness prepared
5%, emission spectrum dominant wavelength is 582nm, microhardness 20.7GPa, fracture toughness 4.8MPam1/2, thermal conductivity is
14.5W·m-1·K-1。
Embodiment 5:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3For original
Material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+The chemistry meter of (m=1.6, n=2.0, x=0.1, y=0)
Amount is 50g above-mentioned raw materials than choosing total weight, and 7.5g Si is additionally added in the mixture3N4It is compound with 7.5g AlN
Object mixes above-mentioned raw materials, in plastic bottle with Si3N4Ball is ball-milling medium, and 400ml dehydrated alcohol is added in ratio of grinding media to material 4:1,
Roller ball mill 24 hours, obtain slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum oven vacuum
It is dry to further take out at least for 24 hours, 20min is ground, sieves with 100 mesh sieve, obtains screenings；Screenings after sieving, which is packed into diameter, is
It in the graphite jig of 48mm, is then placed in hot-pressed sintering furnace, in N2Under conditions of protection and sintering pressure are 30MPa, the N2
Pressure is 0.1MPa, 950 DEG C of heat preservation 30min is risen to the heating rate of 20 DEG C/min, then with the heating rate of 10 DEG C/min
Rise to 1700 DEG C, heat preservation sintering 1 hour, then with furnace natural cooling；By sintered body after cooling after cutting, grinding, polishing
Obtain 0.2mm thickness Ca- α-sialon:Eu2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 16% at the sample 600nm of 0.3mm thickness out, and emission spectrum dominant wavelength is 584nm, and microhardness is
20.0GPa, fracture toughness 5.0MPam1/2, thermal conductivity 16.2Wm-1·K-1。
Embodiment 6:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3For original
Material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+The chemistry meter of (m=2.0, n=2.0, x=0.2, y=0)
Amount is 50g above-mentioned raw materials than choosing total weight, and 10g Si is additionally added in the mixture3N4It, will with the compound of 5g AlN
Above-mentioned raw materials mix in plastic bottle, with Si3N4Ball is ball-milling medium, and 400ml dehydrated alcohol, roller is added in ratio of grinding media to material 4:1
Ball milling 24 hours, obtain slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum oven vacuum drying
At least for 24 hours, it further takes out, grinds 20min, sieve with 100 mesh sieve, obtain screenings；It is 48mm's that screenings after sieving, which is packed into diameter,
It in graphite jig, is then placed in hot-pressed sintering furnace, in N2Under conditions of protection and sintering pressure are 30MPa, the N2Pressure is
0.1MPa is risen to 950 DEG C of heat preservation 10min with the heating rate of 30 DEG C/min, is then risen to the heating rate of 20 DEG C/min
1700 DEG C, heat preservation sintering 1 hour, sintered body after cooling is obtained to 0.6mm thickness Ca- α-after cutting, grinding, polishing
sialon:Eu2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 11% at the sample 600nm of 0.3mm thickness out, and emission spectrum dominant wavelength is 586nm, and microhardness is
20.5GPa, fracture toughness 4.4MPam1/2, thermal conductivity 15.9Wm-1·K-1。
Embodiment 7:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
Pr2O3For raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=1.2, n=1.5, x=0.2, y=
0.02) it is 50g above-mentioned raw materials that stoichiometric ratio, which chooses total weight, and 15g Si is additionally added in the mixture3N4And 5g
The compound of AlN mixes above-mentioned raw materials, in plastic bottle with Si3N4Ball is ball-milling medium, and 400ml is added in ratio of grinding media to material 4:1
Dehydrated alcohol roller ball mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum
Drying box is dried in vacuo at least for 24 hours, is further taken out, and is ground 20min, is sieved with 100 mesh sieve, obtain screenings；By the screenings dress after sieving
Enter in the graphite jig that diameter is 48mm, is then placed in hot-pressed sintering furnace, in N2The condition that protection and sintering pressure are 30MPa
Under, the N2Pressure is 0.1MPa, 950 DEG C of heat preservation 30min is risen to the heating rate of 20 DEG C/min, then with 10 DEG C/min's
Heating rate rises to 1700 DEG C, and heat preservation sintering 2 hours, then with furnace natural cooling；By sintered body after cooling by cutting, grinding
0.5mm thickness Ca- α-sialon:Eu is obtained after mill, polishing2+Fluorescent transparent ceramics.
After measured, ceramic block is predominantly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.System
Straight line transmittance is 14% at the sample 600nm of standby 0.5mm thickness out, and emission spectrum dominant wavelength is 594nm, and microhardness is
20.9GPa, fracture toughness 5.2MPam1/2, thermal conductivity 15.8Wm-1·K-1。
Embodiment 8:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
La2O3For raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=1.2, n=1.5, x=0.3, y=
0.04) it is 50g above-mentioned raw materials that stoichiometric ratio, which chooses total weight, and 1.5g Si is additionally added in the mixture3N4With
The compound of 13.5g AlN mixes above-mentioned raw materials, in plastic bottle with Si3N4Ball is ball-milling medium, and ratio of grinding media to material 4:1 adds
Enter 400ml dehydrated alcohol, roller ball mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then put
Enter vacuum oven vacuum drying at least for 24 hours, further take out, grinds 20min, sieve with 100 mesh sieve, obtain screenings；By the sieve after sieving
Lower object is fitted into the graphite jig that diameter is 48mm, is then placed in hot-pressed sintering furnace, in N2Protection and sintering pressure are 10MPa
Under conditions of, the N2Pressure is 0.1MPa, 1050 DEG C of heat preservation 30min is risen to the heating rate of 20 DEG C/min, then with 15
DEG C/heating rate of min rises to 1700 DEG C, heat preservation sintering 2 hours, then with furnace natural cooling；Sintered body after cooling is passed through
0.15mm thickness Ca- α-sialon:Eu is obtained after cutting, grinding, polishing2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 17% at the sample 600nm of 0.15mm thickness out, and emission spectrum dominant wavelength is 588nm, and microhardness is
21.5GPa, fracture toughness 4.5MPam1/2, thermal conductivity 16.2Wm-1·K-1。
Embodiment 9:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
Lu2O3For raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=1.2, n=1.5, x=0.3, y=
0.05) it is 50g above-mentioned raw materials that stoichiometric ratio, which chooses total weight, and 10g Si is additionally added in the mixture3N4And 5g
The compound of AlN mixes above-mentioned raw materials, in plastic bottle with Si3N4Ball is ball-milling medium, and 400ml is added in ratio of grinding media to material 4:1
Dehydrated alcohol roller ball mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum
Drying box is dried in vacuo at least for 24 hours, is further taken out, and is ground 20min, is sieved with 100 mesh sieve, obtain screenings；By the screenings dress after sieving
Enter in the graphite jig that diameter is 20mm, is then placed in discharge plasma sintering furnace, in N2Protection and sintering pressure are
Under conditions of 30MPa, the N2Pressure is 0.01MPa, is warming up to 1050 DEG C of heat preservation 1min with the heating rate of 50 DEG C/min, so
1850 DEG C are warming up to the heating rate of 50 DEG C/min afterwards, at once with furnace natural cooling；Sintered body after cooling process is cut,
0.4mm thickness Ca- α-sialon:Eu is obtained after grinding, polishing2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 6% at the sample 600nm of 0.4mm thickness out, and emission spectrum dominant wavelength is 585nm, and microhardness is
20.8GPa, fracture toughness 5.1MPam1/2, thermal conductivity 15.9Wm-1·K-1。
Embodiment 10:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
Tb2O3For raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=1.2, n=1.5, x=0.3, y=
0.05) it is 50g above-mentioned raw materials that stoichiometric ratio, which chooses total weight, and 15g Si is additionally added in the mixture3N4And 5g
The compound of AlN mixes above-mentioned raw materials, in plastic bottle with Si3N4Ball is ball-milling medium, and 400ml is added in ratio of grinding media to material 4:1
Dehydrated alcohol roller ball mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then placed in vacuum
Drying box is dried in vacuo at least for 24 hours, is further taken out, and is ground 20min, is sieved with 100 mesh sieve, obtain screenings；By the screenings dress after sieving
Enter in the graphite jig that diameter is 20mm, is then placed in discharge plasma sintering furnace, in N2Protection and sintering pressure are
Under conditions of 30MPa, the N2Pressure is 0.05MPa, is warming up to 950 DEG C of heat preservation 1min with the heating rate of 200 DEG C/min, so
1600 DEG C of sintering 10min are warming up to the heating rate of 300 DEG C/min afterwards, then with furnace natural cooling；By sintered body after cooling
0.2mm thickness Ca- α-sialon:Eu is obtained after cutting, grinding, polishing2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 8% at the sample 600nm of 0.2mm thickness out, and emission spectrum dominant wavelength is 578nm, and microhardness is
20.5GPa, fracture toughness 4.6MPam1/2, thermal conductivity 16.2Wm-1·K-1。
Embodiment 11:
It is the α-Si of 1.5wt% with oxygen content3N4, oxygen content is the AlN, α-Al of 1.0wt%2O3, CaCO3、Eu2O3With
Yb2O3For raw material, according to Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+(m=1.2, n=1.5, x=0.3, y=
0.05) it is 50g above-mentioned raw materials that stoichiometric ratio, which chooses total weight, and 1.5g Si is additionally added in the mixture3N4With
The compound of 13.5g AlN mixes above-mentioned raw materials, in plastic bottle with Si3N4Ball is ball-milling medium, and ratio of grinding media to material 4:1 adds
Enter 400ml dehydrated alcohol, roller ball mill 24 hours, obtains slurry；By slurry, 60 DEG C of rotations are evaporated in Rotary Evaporators, are then put
Enter vacuum oven vacuum drying at least for 24 hours, further take out, grinds 20min, sieve with 100 mesh sieve, obtain screenings；By the sieve after sieving
Lower object is fitted into the graphite jig that diameter is 20mm, is then placed in discharge plasma sintering furnace, in N2Protection and sintering pressure
Under conditions of power is 10MPa, the N2Pressure is 0.1MPa, is warming up to 1000 DEG C of heat preservations with the heating rate of 500 DEG C/min
Then 1min is warming up to 1750 DEG C of sintering 20min with the heating rate of 500 DEG C/min, then with furnace natural cooling；It will be after cooling
Sintered body obtains 0.2mm thickness Ca- α-sialon:Eu after cutting, grinding, polishing2+Fluorescent transparent ceramics.
After measured, ceramic block is mainly α-SiAlON, also containing the AlN polytype not being stimulated by blue light on a small quantity.Preparation
Straight line transmittance is 8% at the sample 600nm of 0.2mm thickness out, and emission spectrum dominant wavelength is 578nm, and microhardness is
20.5GPa, fracture toughness 4.6MPam1/2, thermal conductivity 16.2Wm-1·K-1。
Claims (10)
1. a kind of high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics and preparation method thereof, it is characterised in that it is wrapped
Include following steps:
(1) according to general formula Cam/2-x-yv/2Si12-m-nAlm+nOnN16-n:xEu2+,yMv+, wherein v be chemical valence, 0.8≤m≤2.0,
1.0≤n≤2.0,0 < x≤m/4,0≤y≤m/2v-2x/v choose α-Si by above-mentioned stoichiometric ratio3N4、AlN、α-Al2O3、
CaCO3、Eu2O3With the raw material mixing containing M, mixture A is obtained, mixture B, mixing is then added, the mixture B is AlN
With α-Si3N4Mixture, in which: the quality of mixture B is 5~50wt% of mixture A mass, Si in mixture B3N4With
The weight ratio of AlN is 0~5:1；
(2) mixture for obtaining step (1) ball milling at least 24 hours, obtains slurry using dehydrated alcohol as decentralized medium；
(3) the slurry rotary evaporation for obtaining step (2) is dry, is then dried in vacuo at least for 24 hours, and grinding is sieved with 100 mesh sieve, obtained
To screenings；
(4) screenings after step (3) sieving is sintered using hot pressed sintering or discharge plasma sintering process, it is described
Hot pressed sintering is that screenings is put into hot-pressed sintering furnace, is not less than 30MPa and N in sintering pressure2Under protection, with 5~30 DEG C/
The heating rate of min is warming up to 950~1050 DEG C of 10~60min of heat preservation, is then warming up to the heating rate of 5~20 DEG C/min
1600~1850 DEG C are sintered 0.5~2 hour, and furnace cooling obtains sintered body；The discharge plasma sintering is under sieving
Object is put into discharge plasma sintering furnace, is not less than 30MPa and N in sintering pressure2Under protection, with 50~500 DEG C/min's
Heating rate is warming up to 950~1050 DEG C of 1~2min of heat preservation, is then warming up to 1600 with the heating rate of 50~500 DEG C/min
~1850 DEG C, it is sintered 0~20min, furnace cooling obtains sintered body；
(5) sintered body that step (4) obtains cut, grind, be polished to mirror surface, with a thickness of 0.1-1.0mm to get arrive Ca- α-
sialon:Eu2+Fluorescent transparent ceramics；
Raw material containing M described in step (1) is oxide or carbonate Li2CO3、MgO、SrCO3、Y2O3、Sc2O3、La2O3、
CeO2、Pr2O3、Sm2O3、Gd2O3、Tb2O3、Dy2O3、Ho2O3、Er2O3、Tm2O3、Yb2O3、Lu2O3One of.
2. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: ball milling described in step (2) is with Si3N4Ball is ball-milling medium, ratio of grinding media to material 4:1.
3. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: the α-Si3N4Oxygen content≤1.6wt%, average grain diameter≤0.2 μm.
4. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: oxygen content≤1.0wt% of the AlN, average grain diameter≤0.8 μm.
5. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: the α-Al2O3Purity be > 99.5%, average grain diameter≤500nm.
6. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: the CaCO3Purity be > 99.5%, average grain diameter≤500nm.
7. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: the Eu2O3Purity be > 99.99%, average grain diameter≤1 μm.
8. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: the raw material of the M is that the purity of oxide or carbonate is > 99.5%, average grain diameter≤1 μm.
9. high-power warm white solid-state lighting according to claim 1 SiAlON fluorescent transparent ceramics and its preparation side
Method, it is characterised in that: the N2N under protection2Pressure is 0.01~0.1MPa.
10. high-power warm white solid-state lighting SiAlON fluorescent transparent ceramics, it is characterised in that: it is according to claim 1
The high-power warm white solid-state lighting obtains prepared by SiAlON fluorescent transparent ceramic preparation.
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| WO2021133300A1 (en) * | 2019-12-27 | 2021-07-01 | Eskisehir Teknik Universitesi | Production method of transparent polycristalline silicon nitride ceramics with spark plasma sintering technique |
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