CN111018512A - Preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with gradient refractive index structure - Google Patents

Preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with gradient refractive index structure Download PDF

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CN111018512A
CN111018512A CN201911394013.0A CN201911394013A CN111018512A CN 111018512 A CN111018512 A CN 111018512A CN 201911394013 A CN201911394013 A CN 201911394013A CN 111018512 A CN111018512 A CN 111018512A
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ceramic
refractive index
casting
gradient refractive
fluorescent ceramic
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CN111018512B (en
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张乐
郗晓倩
孙炳恒
康健
陈东顺
邵岑
黄国灿
李明
陈浩
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Jiangsu Normal University
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Abstract

The invention discloses a preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with a gradient refractive index structure, which comprises the following steps: ball-milling and mixing accurately weighed raw material powder and sintering aid, drying and sieving, calcining, ball-milling and mixing the calcined mixed powder and dispersing agent, adding adhesive and plasticizer, continuing ball-milling, respectively preparing mixed slurry containing different ceramic matrixes, respectively removing bubbles, and then carrying out tape casting to obtain different ceramic matrix tape-casting diaphragms with different thicknesses; sequentially superposing the casting films from bottom to top according to the principle that the refractive index is from large to small to obtain casting sheets, and carrying out warm isostatic pressing on the casting sheets to obtain ceramic biscuit; and (3) removing the adhesive from the ceramic biscuit, sintering in vacuum, annealing and polishing the two sides to obtain the ceramic biscuit. The gradient refractive index structure fluorescent ceramic is prepared by adopting a tape casting method, and the light-light conversion efficiency can reach 260-300 lm/W under the excitation of a blue light LED chip with the light-emitting wavelength of 450-480 nm.

Description

Preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with gradient refractive index structure
Technical Field
The invention relates to the technical field of fluorescent ceramics, in particular to a preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramics with a gradient refractive index structure.
Background
White light LEDs have many advantages of small size, solidification, instant start and fast response, energy conservation, long service life, greenness, high efficiency and the like, are widely applied to various buildings and landscape lighting, automobile lighting, medical treatment, various portable lighting and the like, and have been developed into a fourth generation new lighting source. The most widely used and technically mature white LED technology at present is that a GaN-based blue light chip is added with yellow fluorescent powder (cerium-doped yttrium aluminum garnet, Ce: Y)3Al5O12) The technology is that blue light is excited by a GaN chip, and part of the blue light excites Ce to Y3Al5O12The phosphor produces yellow light which mixes with the remaining blue light to form white light.
The Ce: YAG transparent fluorescent ceramic is adopted to replace 'Ce: YAG fluorescent powder + silica gel', and the formula can be shown inEffectively solving the problems. The fluorescent transparent ceramic has good heat-conducting property, can resist light decay, reduce light scattering and improve the stability of brightness and spectrum. However, ceramic fluorescent materials also have some disadvantages. The fluorescent spectrum in the Ce: YAG is lack of red light components, so that the color temperature of white light obtained after the white light is mixed with a GaN blue light chip is higher, and the color rendering index of the LED is lower due to the lack of red light. To solve this problem, Ce can be doped into the fluorescent ceramic material by doping rare earth elements3+The emission peak is red-shifted or the emission peak of the red light band is introduced to improve. However, the new problems induced by the heavily doped fluorescent ceramic material are that the interaction between different doped ions, energy transfer, etc. are complicated and the luminous efficiency is negatively affected by energy transfer.
CN102531564A, CN102501478A and CN102249660A disclose a white light LED composite transparent ceramic and a preparation method thereof, the composite structure fluorescent ceramic is formed by bonding an upper layer transparent ceramic and a lower layer transparent ceramic through optical cement, and the composite transparent ceramic is a Ce: YAG ceramic chip and Eu respectively3+，Pr3+，Cr3+And compounding the doped YAG ceramics. By doping different rare earths, red light components in the LED spectrum are increased, and the color rendering index and the mild color temperature are improved.
However, the above method has problems that: an air interlayer with a certain thickness exists between the upper and lower ceramic chip interfaces, the refractive index difference between the layers is too large, and sin theta is equal to n according to the total reflection angle1/n2The large difference in refractive index between the ceramic and air results in a too small light exit angle, and a large amount of fluorescence is lost inside the ceramic, so that the light emitting efficiency is reduced.
Disclosure of Invention
The invention aims to provide a preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with a gradient refractive index structure.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with a gradient refractive index structure adopts a tape casting molding method and specifically comprises the following steps:
(1) weighing raw material powder according to the stoichiometric ratio of each element in the chemical formula of the fluorescent ceramic; using absolute ethyl alcohol as a ball milling medium, placing accurately weighed raw material powder and a sintering aid in a ball milling tank for ball milling for 14-16 hours to obtain mixed slurry, drying the ball milled slurry, sieving, and placing in a muffle furnace for calcining;
(2) mixing the calcined mixed powder, a dispersing agent and absolute ethyl alcohol according to a certain proportion, adjusting the pH of the slurry to 10-12, adding a bonding agent and a plasticizer after ball milling for 6-12 h, and continuing ball milling for 6-12 h to respectively prepare mixed slurry containing different ceramic substrates; removing bubbles for 10-60 min respectively;
(3) carrying out tape casting on the slurry subjected to bubble removal to obtain different ceramic matrix tape-cast membranes with different thicknesses; sequentially superposing the casting films from bottom to top according to the principle that the refractive index is from large to small to obtain a casting sheet, placing the casting sheet under the pressure of 150-300 Mpa for warm isostatic pressing, and maintaining the pressure for 1-10 min to obtain a ceramic biscuit;
(4) and placing the ceramic biscuit in a muffle furnace for glue discharging treatment, then placing the biscuit in a vacuum furnace for sintering, finally placing the ceramic in the muffle furnace for annealing in air atmosphere and polishing the two sides to obtain the ceramic.
Preferably, the lowest layer of the fluorescent ceramic is (Ce)xY1-x)3Al5O12Wherein x is more than or equal to 0.0005 and less than or equal to 0.04, and the ceramic matrix of the rest layers is MgAl2O4、MgO、AlON、Al2O3、MgF2、CaF2、Gd2O3At least two kinds of them, and the refractive index of the ceramic matrix satisfies 1.82>n>1。
Preferably, the outermost ceramic matrix is doped with a red-emitting ion comprising Pr3+、Sm3+、Mn3+、Cr3+One or two of them.
Preferably, in the step (1), the addition amount of the sintering aid is 0.1-1% of the total mass of the raw material powder; the muffle furnace calcining temperature is 600-1000 ℃, and the heat preservation time is 4-9 h.
Preferably, in the step (2), the dispersant is one or more of herring oil, fish oil, oleic acid, ammonium citrate, Polyetherimide (PEI) or NP-10; the addition amount of the dispersing agent is 2-10% of the total mass of the mixed powder.
Preferably, in step (2), the binder is polyvinyl butyral (PVB); the addition amount of the binder is 3-10% of the total mass of the mixed powder.
Preferably, in the step (2), the plasticizer is one or two of Butyl Benzyl Phthalate (BBP), tert-butyl peroxypivalate (BPP) and glycerol; the addition amount of the plasticizer is 2-7% of the total mass of the mixed powder.
Preferably, in the step (3), the vacuum pressure of the vacuum defoaming machine is 1to 2 Torr.
Preferably, in the step (3), the total thickness of the flow-casting layer is 1.4-3.0 mm.
Preferably, in the step (4), the glue discharging temperature is 600-900 ℃; the vacuum sintering temperature is 1650-1870 ℃, and the vacuum degree in the furnace chamber is kept at 10-3～10-4Pa; the ceramic annealing temperature is 1200-1600 ℃.
Fluorescent ceramic biscuits with different refractive indexes and emission of red light wave bands are prepared by a tape casting forming method, 3-5 layers of tape casting biscuits are stacked from bottom to top on the basis of the principle that the refractive indexes are decreased progressively, and the thickness d of the tape casting biscuits is increased in sequence to meet the requirement that d is not less than 1.5x/dx-1X is not less than 2 (not less than 2 and not more than 5), and x is the stacking ordinal number from bottom to top; the casting biscuit of the uppermost layer is doped with red light emitting ions.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with the gradient-refractive-index-structure fluorescent ceramic and the non-gradient-refractive-index-structure fluorescent ceramic, the gradient-refractive-index-structure fluorescent ceramic has the advantages that the refraction index is reduced in a gradient manner, so that the front light emergence angle is obviously improved, the light-light conversion efficiency is obviously improved, and the light-light conversion efficiency can reach 260-300 lm/W under the excitation of a blue light LED chip with the light-emitting wavelength of 450-480 nm.
(2) The casting biscuit with the smallest refractive index of the outermost layer is doped with red light wave band emission ions, and the casting biscuit is increased in proportion from bottom to top based on the principle of decreasing refractive index.
Drawings
FIG. 1 is a schematic structural diagram of a fluorescent ceramic according to the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Unless otherwise stated, the starting materials used in the following examples are all commercially available products.
The structure of the fluorescent ceramic is shown in figure 1, the fluorescent ceramic is divided into 3-5 parts, and the chemical composition of the lowermost part of the fluorescent ceramic body in the figure is (Ce)xY1-x)3Al5O12Wherein x is more than or equal to 0.0005 and less than or equal to 0.04, the refractive indexes of the rest parts are sequentially reduced from bottom to top, and the ceramic matrix can be MgAl2O4(n＝1.720)、MgO(n＝1.736)、AlON(n＝1.660)、Al2O3(n＝1.768)、MgF2(n＝1.730)、CaF2(n＝1.450)、Gd2O3(n-1.800), etc., the red light emitting ion partially doped in the uppermost layer may be Pr3+、Sm3+、Mn3+Or Cr3+One or two of the components are doped with m, wherein m is more than or equal to 0.001 and less than or equal to 0.006. The fluorescent ceramic is prepared by tape casting, warm isostatic pressing, glue discharging and vacuum sintering.
Example 1
(1) According to the chemical formula (Ce)0.0005Y0.9995)3Al5O12，MgAl2O4、(Al0.999Cr0.001) Weighing 60g of raw material powder according to the stoichiometric ratio of each element in ON; using absolute ethyl alcohol as a ball milling medium, placing accurately weighed raw material powder, 0.06g of MgO and 0.33ml of TEOS in a ball milling tank, and ball milling for 15 hours at 180r/min to obtain uniformly mixed slurry; drying and sieving the ball-milled slurry, and calcining the dried and sieved slurry in a muffle furnace at 600 ℃;
(2) placing the calcined powder into absolute ethyl alcohol, adding 0.6g of fish oil and 0.6g of NP-10, regulating the pH value to 10, ball-milling for 6h, and addingBall milling is carried out on 1.8g of PVB and 1.2g of BPP for 6 hours, and then the slurry is placed in a vacuum bubble removing machine with the vacuum pressure of 1Torr for vacuum bubble removal for 10 minutes to respectively prepare Ce, YAG and MgAl2O4Cr is slurry of AlON;
(3) sequentially casting the slurry after bubble removal to obtain a Ce: YAG casting film with the thickness of 0.2mm and MgAl with the thickness of 0.4mm2O4Casting diaphragms and Cr-AlON casting diaphragms with the thickness of 0.8mm, wherein the casting diaphragms are respectively superposed from bottom to top according to the principle that the refractive index is from large to small and then the ceramic biscuit is obtained at the temperature of 150Mpa and the like;
(4) placing the ceramic biscuit in a muffle furnace for glue discharging at 600 ℃, then placing the biscuit in a vacuum furnace for sintering at 1650 ℃, wherein the vacuum degree in the furnace chamber is 10-3Pa the ceramic was finally annealed in a muffle furnace at 1200 ℃ and polished to 1mm on both sides.
Under the excitation of 450nm blue light, the luminous efficiency of the ceramic can reach 260lm/W, and the display index can reach 85.
Example 2
(1) According to the chemical formula (Ce)0.04Y0.96)3Al5O12、MgO、Al2O3、(Pr0.004Mg0.996)Al2O4Weighing 60g of raw material powder according to the stoichiometric ratio of each element in the raw material powder; using absolute ethyl alcohol as ball milling medium, accurately weighing raw material powder and 0.2g ZrO20.35ml of TEOS is put into a ball milling tank to be ball milled for 15 hours at 180r/min, evenly mixed slurry is obtained, the slurry after ball milling is dried, sieved and calcined in a muffle furnace at 800 ℃;
(2) placing the calcined powder into absolute ethyl alcohol, adding 2g of ammonium citrate and 1.5g of NP-10, adjusting the pH value to 11, ball-milling for 6.5h, adding 3g of PVB, 3g of BPP and 1.2g of glycerol, ball-milling for 7h, then placing the slurry into a vacuum bubble removing machine with the vacuum pressure of 1.5Torr, and removing bubbles for 35min in vacuum to respectively prepare Ce, YAG, MgO and Al2O3、Pr:MgAl2O4The slurry of (4);
(3) sequentially casting the slurry after bubble removal to obtain a Ce: YAG casting membrane with the thickness of 0.4mm, a MgO casting membrane with the thickness of 0.6mm and a MgO casting membrane with the thickness of 0.8mmAl2O3Casting film, 1.2mm thick Pr: MgAl2O4Casting a membrane; respectively superposing the casting films from bottom to top according to the principle that the refractive index is from large to small, and then obtaining ceramic biscuit at the temperature of 250Mpa and the like;
(4) placing the ceramic biscuit in a muffle furnace for binder removal at 800 ℃, then placing the biscuit in a vacuum furnace for sintering at 1780 ℃, wherein the vacuum degree in the furnace chamber is 10-3Pa the ceramic was finally annealed in a muffle furnace at 1350 ℃ and polished to 1.5mm on both sides.
Under the excitation of 470nm blue light LED, the obtained ceramic has luminous efficiency up to 280lm/W and the display index up to 88.
Example 3
(1) According to the chemical formula (Ce)0.01Y0.99)3Al5O12、Gd2O3、MgO、CaF2、(Mn0.002Sm0.004)MgF2Weighing 60g of raw material powder according to the stoichiometric ratio of each element in the raw material powder; using absolute ethyl alcohol as ball milling medium, accurately weighing raw material powder and 0.6g ZrO20.06ml of TEOS is put into a ball milling tank to be ball milled for 15h at 160r/min, so as to obtain evenly mixed slurry, the slurry after ball milling is dried, sieved and put into a muffle furnace to be calcined at 800 ℃;
(2) putting the calcined powder into absolute ethyl alcohol, adding 4g of PEI and 2g of oleic acid, mixing, adjusting the pH value to 12, ball-milling for 10 hours, adding 6g of PVB, 2.4g of BBP and 1.2g of glycerol, ball-milling for 12 hours, and then putting the slurry into a vacuum bubble removing machine with the vacuum pressure of 2Torr for vacuum bubble removal for 60 minutes. Respectively prepare Ce, YAG and Gd2O3、MgO、CaF2、Mn,Sm:MgF2The slurry of (4);
(3) sequentially casting the slurry after bubble removal to obtain a Ce: YAG casting membrane with the thickness of 0.2mm and Gd with the thickness of 0.3mm2O3Casting membrane, MgO casting membrane with thickness of 0.5mm, CaF with thickness of 0.7mm2Casting film, Mn, Sm and MgF with thickness of 1.0mm2Casting membranes, namely respectively superposing the casting membranes from bottom to top according to the principle that the refractive index is from large to small, and then heating at 300Mpa to obtain ceramic biscuit;
(4) placing the ceramic biscuit in a muffle furnace for binder removal at 900 ℃, then placing the biscuit in a vacuum furnace for sintering at 1870 ℃, wherein the vacuum degree in the furnace chamber is 10-3Pa, finally the ceramic is placed in a muffle furnace to be annealed at 1600 ℃ and polished to 2mm on both sides.
Under the excitation of 480nm blue light LED, the obtained ceramic has luminous efficiency up to 300lm/W and the display index up to 95.

Claims (10)

1. A preparation method of high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with a gradient refractive index structure is characterized in that a tape casting molding method is adopted, and the method specifically comprises the following steps:
(1) weighing raw material powder according to the stoichiometric ratio of each element in the chemical formula of the fluorescent ceramic; using absolute ethyl alcohol as a ball milling medium, placing accurately weighed raw material powder and a sintering aid in a ball milling tank for ball milling for 14-16 hours to obtain mixed powder, drying the ball milled powder, sieving, and placing in a muffle furnace for calcining;
(2) mixing the calcined mixed powder, a dispersing agent and absolute ethyl alcohol according to a certain proportion, adjusting the pH of the slurry to 10-12, adding a bonding agent and a plasticizer after ball milling for 6-12 h, and continuing ball milling for 6-12 h to respectively prepare mixed slurry containing different ceramic substrates; removing bubbles for 10-60 min respectively;
(3) carrying out tape casting on the slurry subjected to bubble removal to obtain different ceramic matrix tape-cast membranes with different thicknesses; superposing the casting films from bottom to top according to the principle that the refractive index is from large to small to obtain a casting sheet, placing the casting sheet under the pressure of 150-300 Mpa for warm isostatic pressing, and maintaining the pressure for 1-10 min to obtain a ceramic biscuit;
(4) and placing the ceramic biscuit in a muffle furnace for glue discharging treatment, then placing the biscuit in a vacuum furnace for sintering, finally placing the ceramic in the muffle furnace for annealing in air atmosphere and polishing the two sides to obtain the ceramic.
2. The method for preparing high luminous efficacy and high color rendering index fluorescent ceramic with gradient refractive index structure according to claim 1, wherein the lowest layer of the fluorescent ceramic is (Ce)xY1-x)3Al5O12Wherein x is more than or equal to 0.0005 and less than or equal to 0.04, and the ceramic matrix of the rest layers is MgAl2O4、MgO、AlON、Al2O3、MgF2、CaF2、Gd2O3At least two kinds of them, and the refractive index of the ceramic matrix satisfies 1.82>n>1。
3. The method of claim 1, wherein the outermost ceramic matrix is doped with red light emitting ions including Pr3+、Sm3+、Mn3+、Cr3+One or two of them.
4. The preparation method of the high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with the gradient refractive index structure according to claim 1, characterized in that in the step (1), the addition amount of the sintering aid is 0.1-1% of the total mass of the raw material powder; the muffle furnace calcining temperature is 600-1000 ℃, and the heat preservation time is 4-9 h.
5. The method for preparing a high luminous efficacy and high color rendering index fluorescent ceramic with a gradient refractive index structure according to claim 1, wherein in the step (2), the dispersant is one or more of herring oil, fish oil, oleic acid, ammonium citrate, polyetherimide or NP-10; the addition amount of the dispersing agent is 2-10% of the total mass of the mixed powder.
6. The method for preparing a high luminous efficacy and high color rendering index fluorescent ceramic with a gradient refractive index structure as claimed in claim 1, wherein in the step (2), the binder is polyvinyl butyral; the addition amount of the binder is 3-10% of the total mass of the mixed powder.
7. The method for preparing high luminous efficacy and high color rendering index fluorescent ceramic with a gradient refractive index structure according to claim 1, wherein in the step (2), the plasticizer is one or two of butyl benzyl phthalate, tert-butyl peroxypivalate and glycerol; the addition amount of the plasticizer is 2-7% of the total mass of the mixed powder.
8. The method for preparing high luminous efficiency and high color rendering index fluorescent ceramic with a gradient refractive index structure according to claim 1, wherein in the step (3), the vacuum pressure of the vacuum bubble removing machine is 1-2 Torr.
9. The method for preparing high luminous efficacy and high color rendering index fluorescent ceramic with a gradient refractive index structure according to claim 1, wherein in the step (3), the total thickness of the flow-extension layer is 1.4-3.0 mm.
10. The preparation method of the high-luminous-efficiency and high-color-rendering-index fluorescent ceramic with the gradient refractive index structure according to claim 1, wherein in the step (4), the glue removing temperature is 600-900 ℃, and the heating rate is 0.5-2 ℃/min; the vacuum sintering temperature is 1650-1870 ℃, and the vacuum degree in the furnace chamber is kept at 10-3～10-4Pa; the ceramic annealing temperature is 1200-1600 ℃.
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