CN110253986B - Fluorescent ceramic and preparation method thereof - Google Patents

Fluorescent ceramic and preparation method thereof Download PDF

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CN110253986B
CN110253986B CN201910153568.XA CN201910153568A CN110253986B CN 110253986 B CN110253986 B CN 110253986B CN 201910153568 A CN201910153568 A CN 201910153568A CN 110253986 B CN110253986 B CN 110253986B
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ceramic
fluorescent
graphene
heating
red fluorescent
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CN110253986A (en
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罗雪方
张甜甜
陈文娟
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Luohuaxin display technology development (Jiangsu) Co.,Ltd.
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Luohuaxin Display Technology Development Jiangsu Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • C01B32/186—Preparation by chemical vapour deposition [CVD]
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B19/00—Other methods of shaping glass
    • C03B19/06—Other methods of shaping glass by sintering, e.g. by cold isostatic pressing of powders and subsequent sintering, by hot pressing of powders, by sintering slurries or dispersions not undergoing a liquid phase reaction
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
    • C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/02—Compositions for glass with special properties for coloured glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass

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  • Ceramic Engineering (AREA)
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  • Luminescent Compositions (AREA)
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Abstract

The invention provides a preparation method of fluorescent ceramic, which comprises the steps of mixing a ceramic raw material and nitride red fluorescent powder, pressing the mixture into a green body, further pressing the green body into a compact biscuit, sintering the biscuit, preserving heat, and cooling to obtain a red fluorescent glass sheet; preparing a graphene layer; and attaching the red fluorescent glass sheet and the conventional ceramic sheet to two sides of the graphene layer to obtain the fluorescent ceramic with the 3-layer structure. The preparation method of the fluorescent ceramic provided by the invention has high efficiency, the prepared fluorescent ceramic has a simple structure, and the blue laser and non-radiative heat on the surface of red fluorescent glass are reduced to the minimum by the design of a fluorescent ceramic device with a 3-layer structure and the action of heat conduction of yellow/green fluorescent ceramic and super heat conduction of a transparent single-layer graphene layer, so that the whole fluorescent ceramic device is not burnt under the excitation of high-power laser, and has higher luminous efficiency and color rendering index at high temperature.

Description

Fluorescent ceramic and preparation method thereof
Technical Field
The invention relates to the field of lighting materials, in particular to fluorescent ceramic and a preparation method thereof.
Background
The technology realizes light output of different colors by the rotation of a fluorescent powder color wheel with multiple colors of red, green, blue and the like excited by blue laser, but the fluorescent powder can generate a thermal quenching phenomenon to cause the reduction of luminous intensity due to the long-time irradiation of laser with high energy density on the fluorescent powder color wheel, and meanwhile, the temperature of a device is continuously increased due to non-radiative heat release, thereby causing the aging, cracking, yellowing and sharp reduction of luminous efficiency of resin and silica gel. The fluorescent ceramic has excellent optical characteristics, chemical stability and thermal conductivity, is suitable for high-power LEDs and laser illumination display, and the existing relatively mature transparent ceramic phosphor is garnet doped with rare earth ions, mainly comprises yellow/green transparent fluorescent ceramic of Ce: Y/LuAG, but white light obtained by combining the fluorescent ceramic with blue light has low color rendering index and low chroma due to lack of red components. Therefore, the increase of the red light component in the spectrum by adding the red transparent fluorescent ceramic is important for improving the color chroma. However, the preparation conditions of the nitride red fluorescent ceramic are harsh, the oxide with high heat rate cannot be added under the high-temperature condition, and the single-phase red fluorescent ceramic has the heat conductivity of 1-4W/mk and is easily burnt by high-energy laser.
Disclosure of Invention
In view of the above, there is a need for a method for preparing a fluorescent ceramic, which is not burned out under high-power laser excitation and has high conversion efficiency at high temperature.
The invention provides a preparation method of fluorescent ceramic, which comprises the following steps:
step 1, mixing a ceramic raw material and nitride red fluorescent powder, pressing the mixture into a green body, further pressing the green body into a compact biscuit, sintering the biscuit, preserving heat, and cooling to obtain a red fluorescent glass sheet;
step 2, heating the Cu foil to a certain temperature in the presence of protective gas, preserving heat, stopping introducing the protective gas after heat preservation, introducing methane gas, performing heating and heat preservation until methane is cracked, then introducing hydrogen in proportion, maintaining a certain pressure, preserving heat, stopping introducing the hydrogen and the methane, continuing introducing the protective gas until the temperature is cooled to room temperature, and obtaining the Cu foil with the surface covered with graphene;
and 3, coating a PMMA acetone solution on the surface of the graphene coated with the graphene Cu foil prepared in the step 2 to enable the ceramic plate to be adhered to the surface of the graphene, heating to enable the Cu foil to be automatically separated from the graphene and enable the graphene to be tightly adhered to the ceramic plate, coating a PMMA acetone solution on the other surface of the graphene, adhering the red fluorescent glass plate to the red fluorescent glass plate, heating to enable the red fluorescent glass plate to be tightly adhered to the red fluorescent glass plate, and cooling to obtain the fluorescent ceramic with the 3-layer structure.
Further, in the step 1, the pressure for pressing the ceramic raw material and the nitride red fluorescent powder into the blank is 3-20t, the pressure maintaining time is 5-20min, the pressure for pressing the blank into the biscuit is 50-300MPa, and the pressure maintaining time is 5-20 min.
Further, the ceramic raw material in the step 1 comprises Bi2O3、SiO2、ZnO、B2O3、BaO、Al2O3、Na2O、Li2O、K2A plurality of combinations of O.
Further, the sintering temperature in the step 1 is 400-.
Further, the heating temperature of the Cu foil in the step 2 is 800-.
Further, the flow rate of methane in the step 2 is 20-100ml/min, and the cracking temperature of methane is 800-1200 ℃; the heat preservation time is 0.5-4h, and the heating rate is 1-5 ℃/min.
Further, the gas ratio of hydrogen to methane in the step 2 is 2-1100: 1, the pressure is 2-750mbar, and the time for introducing hydrogen is 0.5-4 h.
Further, the protective gas in step 2 comprises one or a combination of helium, argon and nitrogen, and the flow rate of the protective gas is 200-.
Further, the concentration of the PMMA acetone solution in the step 3 is 0.5-8g/L, the heating temperature is 60-200 ℃, and the heating time is 0.5-2 h.
The fluorescent ceramic comprises a ceramic sheet layer, a graphene layer and a red fluorescent glass sheet layer, wherein the ceramic sheet layer and the red fluorescent glass sheet layer are respectively arranged on two sides of the graphene layer.
The preparation method of the fluorescent ceramic provided by the invention has high efficiency, the prepared fluorescent ceramic has a simple structure, and the blue laser and non-radiative heat on the surface of red fluorescent glass are reduced to the minimum by the design of a fluorescent ceramic device with a 3-layer structure and the action of heat conduction of yellow/green fluorescent ceramic and super heat conduction of a transparent single-layer graphene layer, so that the whole fluorescent ceramic device is not burnt under the excitation of high-power laser, and has higher luminous efficiency and color rendering index at high temperature.
Drawings
Fig. 1 is a schematic flow chart of a method for preparing a fluorescent ceramic according to an embodiment of the present invention.
The following detailed description will further illustrate the invention in conjunction with the above-described figures.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "or/and" includes any and all combinations of one or more of the associated listed items.
PMMA in this context is polymethyl methacrylate
Referring to fig. 1, fig. 1 is a schematic flow chart of a method for preparing a fluorescent ceramic according to an embodiment of the present invention, which includes the following steps:
step S11, mixing the ceramic raw material and the nitride red fluorescent powder and pressing the mixture into a green body, further pressing the green body into a compact biscuit, sintering the biscuit, preserving heat, and cooling to obtain a red fluorescent glass sheet;
step S12, heating the Cu foil to a certain temperature in the presence of protective gas, preserving heat, stopping introducing the protective gas after preserving heat, introducing methane gas, carrying out heating and heat preservation until the methane is cracked, then introducing hydrogen in proportion, keeping a certain pressure, preserving heat, stopping introducing the hydrogen and the methane, continuing introducing the protective gas until the temperature is cooled to room temperature, and obtaining the Cu foil with the surface covered with graphene;
step S13, coating a PMMA acetone solution on the graphene surface coated with the graphene Cu foil prepared in the step S12 to enable the ceramic sheet to be adhered to the graphene surface, then heating to enable the Cu foil to be automatically separated from the graphene, enabling the graphene to be tightly attached to the ceramic sheet, coating a PMMA acetone solution on the other side of the graphene, attaching the red fluorescent glass sheet to the red fluorescent glass sheet, heating to enable the red fluorescent glass sheet and the graphene to be tightly attached, and cooling to obtain the fluorescent ceramic with the 3-layer structure.
In this embodiment, the ceramic raw material and the nitride red phosphor are mixed using a ball mill in step S11.
In this embodiment, the ceramic raw material in step S11 includes Bi2O3、SiO2、ZnO、B2O3、BaO、Al2O3、Na2O、Li2O、K2A plurality of combinations of O. By adjusting the component proportion among the ceramic raw materials, the oxidation of the red fluorescent powder can be effectively avoided, and the content of the red fluorescent powder is changed to obtain the red fluorescent glass with different colors.
In this embodiment, in step S11, the ceramic raw material and the red nitride phosphor are pressed into a green body by using a hydraulic press, and the green body is further pressed into a dense green body by using a cold isostatic press, wherein the green body is pressed from the ceramic raw material and the red nitride phosphor at a pressure of 3-20t for a pressure of 5-20min, and the green body is pressed into a green body at a pressure of 50-300MPa for a pressure of 5-20 min.
In this embodiment, in the step S11, the biscuit is sintered in a high temperature resistance furnace, wherein the sintering temperature is 400-.
In this embodiment, the protective gas in step S12 includes one or a combination of helium, argon, and nitrogen, and the flow rate of the protective gas is 200-1000 ml/min.
In this embodiment, the heating temperature of the Cu foil in the step S12 is 800-. The cracking temperature of methane is 800-1200 ℃; the heat preservation time is 0.5-4h, and the heating rate is 1-5 ℃/min. The flow rate of the methane is 20-100ml/min, and the gas ratio of the hydrogen to the methane is 2-1100: 1, introducing hydrogen under the pressure of 2-750mbar for 0.5-4 h.
In this embodiment, the concentration of the PMMA acetone solution in step S13 is 0.5-8g/L, PMMA is polymethyl methacrylate, and the two heating processes are performed in an oven, the heating temperature is 60-200 ℃, and the heating time is 0.5-2 h.
In this embodiment, the ceramic sheet in step S13 is an existing yellow or green fluorescent ceramic sheet, and has high thermal conductivity, blue light absorption rate, and quantum efficiency, and can effectively convert blue light into yellow/green/white light, and at the same time, can timely guide out heat generated by non-radiation, and improve luminous intensity, and the ceramic sheet has a thermal conductivity of 10-30W/MK, a blue light absorption efficiency of 80-95%, and a quantum efficiency of 80-95%. The parameters of the yellow fluorescent ceramic sheet are 0.4233 CIE X and 0.5560 CIE Y, the parameters of the green fluorescent ceramic sheet are 0.3354 CIE X and 0.5883 CIE Y.
The invention also provides the fluorescent ceramic prepared by the preparation method of the fluorescent ceramic, and the fluorescent ceramic comprises a ceramic sheet layer, a graphene layer and a red fluorescent glass sheet layer, wherein the ceramic sheet layer and the red fluorescent glass sheet layer are respectively arranged on two sides of the graphene layer. The graphene layer is a transparent graphene layer, the thermal conductivity of the transparent graphene layer reaches 1000W/MK, and the heat on the surface of the ceramic wafer layer can be rapidly dissipated due to the ultrahigh thermal conductivity, so that the red fluorescent glass wafer layer is excited at a lower temperature and is not easy to burn, the stability is improved, and the luminous efficiency is also improved.
The present invention will be further explained below by way of specific embodiments.
Comparative example 1
Yellow fluorescent ceramic sheets (CIE X is 0.4233, CIE Y is 0.5560, thickness is 0.15mm, diameter is 20mm) are placed in a transmission type laser device to be lightened, the irradiation distance is 3m, the laser current is 1.3A, the voltage is 12.4V, the test is carried out by a far-distance SPIC-200 illuminometer, and the test parameters comprise 8500lx, CCT5600K and color rendering index Ra 60.
Example 1
Separately weighing SiO2 6g、B2O3 4g、BaO 2g、ZnO 1g、Na2O 1g、Al2O3Adding 0.5g of nitride red fluorescent powder 630 K83.625 g into a ball mill, ball-milling for 10 hours at the rotating speed of 400r/min to obtain a mixture, then keeping the pressure of the mixture for 10 minutes by using a hydraulic press to obtain a blank, then putting the blank into a vacuum packaging bag, keeping the pressure of the vacuum packaging bag in a cold isostatic press with the pressure of 250MPa for 10 minutes to obtain a biscuit, then heating the biscuit to 600 ℃ at the speed of 2 ℃/min in a high-temperature resistance furnace, keeping the temperature for 0.5 hour, and cutting and polishing the prepared red glass to obtain a red fluorescent glass sheet with the thickness of 0.15 mm.
Putting the Cu foil into a furnace, introducing argon protective gas at a rate of 500ml/min, heating to 1000 ℃ at a rate of 3 ℃/min, preserving heat for 30min, then stopping introducing the protective gas, introducing methane gas at a rate of 40ml/min, preserving heat for 0.5h, introducing hydrogen at a rate of 500ml/min under the pressure of 400mbar, preserving heat for 1h, stopping introducing hydrogen and methane, introducing argon protective gas at a rate of 500ml/min, cooling to room temperature, and taking out the Cu foil to obtain the graphene on the Cu foil.
Firstly coating 2g of PMMA acetone solution with the concentration of 1g/L on the surface of graphene, then adhering a yellow fluorescent ceramic plate to one surface of the graphene through the PMMA acetone solution, putting the graphene into an oven to bake for 1h at the temperature of 80 ℃, automatically separating a Cu foil from the graphene, simultaneously heating to enable the graphene to be closely adhered with the ceramic plate, then coating 2g of PMMA acetone solution with the concentration of 1g/L on the other surface of the graphene, adhering a red fluorescent glass plate with the red fluorescent glass plate, putting the red fluorescent glass plate into the oven to bake for 1h at the temperature of 80 ℃ to enable the red fluorescent glass plate and the ceramic plate to be closely adhered, and cooling to obtain the fluorescent ceramic with the 3-layer structure. The fluorescent ceramic with the 3-layer structure is placed in a transmission type laser device to be lightened, the irradiation distance is 3m, the laser current is 1.3A, the voltage is 12.4V, and the remote SPIC-200 illuminometer is used for testing the parameters of illumination 9500lx, color temperature CCT5000K and color rendering index Ra 85.
Comparative example 2
The green fluorescent ceramic plate (CIE X is 0.3354, CIE Y is 0.5883, thickness is 0.15mm, diameter is 20mm) is placed in a transmission type laser device to be lighted, the irradiation distance is 3m, the laser current is 1.3A, the voltage is 12.4V, the test is carried out by a remote SPIC-200 illuminometer, and the test parameters comprise 9200lx, CCT73 7300K and color rendering index Ra 65.
Example 2
Separately weighing SiO2 6g、B2O3 4g、BaO 2g、ZnO 1g、Na2O 1g、Al2O3Adding 0.5g of nitride red fluorescent powder 630 K83.625 g into a ball mill, ball-milling for 10 hours at the rotating speed of 400r/min to obtain a mixture, then keeping the pressure of the mixture for 10 minutes by using a hydraulic press to obtain a blank, then putting the blank into a vacuum packaging bag, keeping the pressure of the vacuum packaging bag in a cold isostatic press with the pressure of 250MPa for 10 minutes to obtain a biscuit, then heating the biscuit to 600 ℃ at the speed of 2 ℃/min in a high-temperature resistance furnace, keeping the temperature for 0.5 hour, and cutting and polishing the prepared red glass to obtain a red fluorescent glass sheet with the thickness of 0.15 mm.
Putting the Cu foil into a furnace, introducing argon protective gas at a rate of 500ml/min, heating to 1000 ℃ at a rate of 3 ℃/min, preserving heat for 30min, then stopping introducing the protective gas, introducing methane gas at a rate of 40ml/min, preserving heat for 0.5h, introducing hydrogen at a rate of 500ml/min under the pressure of 400mbar, preserving heat for 1h, stopping introducing hydrogen and methane, introducing argon protective gas at a rate of 500ml/min, cooling to room temperature, and taking out the Cu foil to obtain the graphene on the Cu foil.
Firstly coating 2g of PMMA acetone solution with the concentration of 1g/L on the surface of graphene, then adhering a green fluorescent ceramic plate to one surface of the graphene through the PMMA acetone solution, putting the graphene into an oven to bake for 1h at the temperature of 80 ℃, automatically separating a Cu foil from the graphene, simultaneously heating to enable the graphene to be closely adhered with the ceramic plate, then coating 2g of PMMA acetone solution with the concentration of 1g/L on the other surface of the graphene, adhering a red fluorescent glass plate with the red fluorescent glass plate, putting the red fluorescent glass plate into the oven to bake for 1h at the temperature of 80 ℃ to enable the red fluorescent glass plate and the ceramic plate to be closely adhered, and cooling to obtain the fluorescent ceramic with the 3-layer structure. The fluorescent ceramic with the 3-layer structure is placed in a transmission type laser device to be lightened, the irradiation distance is 3m, the laser current is 1.3A, the voltage is 12.4V, and the test is carried out by a remote SPIC-200 illuminometer, and the tested parameters comprise the illumination 10300lx, the color temperature CCT5600K and the color rendering index Ra 90.
As can be seen from the test parameters, example 1, example 2 had higher luminous efficiency and color rendering index than comparative example 1 and comparative example 2.
The preparation method of the fluorescent ceramic provided by the invention has high efficiency, the prepared fluorescent ceramic has a simple structure, and the blue laser and non-radiative heat on the surface of red fluorescent glass are reduced to the minimum by the design of a fluorescent ceramic device with a 3-layer structure and the action of heat conduction of yellow/green fluorescent ceramic and super heat conduction of a transparent single-layer graphene layer, so that the whole fluorescent ceramic device is not burnt under the excitation of high-power laser, and has higher luminous efficiency and color rendering index at high temperature.
It should be understood by those skilled in the art that the above embodiments are only for illustrating the present invention and are not to be used as a limitation of the present invention, and that suitable changes and modifications of the above embodiments are within the scope of the claimed invention as long as they are within the spirit and scope of the present invention.

Claims (10)

1. The preparation method of the fluorescent ceramic is characterized by comprising the following steps of:
step 1, mixing a ceramic raw material and nitride red fluorescent powder, pressing the mixture into a green body, further pressing the green body into a compact biscuit, sintering the biscuit, preserving heat, and cooling to obtain a red fluorescent glass sheet;
step 2, heating the Cu foil to a certain temperature in the presence of protective gas, preserving heat, stopping introducing the protective gas after heat preservation, introducing methane gas, performing heating and heat preservation until methane is cracked, then introducing hydrogen in proportion, maintaining pressure, preserving heat, stopping introducing the hydrogen and the methane, continuing introducing the protective gas until the temperature is cooled to room temperature, and obtaining the Cu foil with the surface covered with graphene;
and 3, coating a PMMA acetone solution on the surface of the graphene coated with the graphene Cu foil prepared in the step 2 to enable the ceramic plate to be adhered to the surface of the graphene, heating to enable the Cu foil to be automatically separated from the graphene and enable the graphene to be tightly adhered to the ceramic plate, coating a PMMA acetone solution on the other surface of the graphene, adhering the red fluorescent glass plate to the red fluorescent glass plate, heating to enable the red fluorescent glass plate to be tightly adhered to the red fluorescent glass plate, and cooling to obtain the fluorescent ceramic with the 3-layer structure.
2. The method of preparing a fluorescent ceramic according to claim 1, wherein: in the step 1, the ceramic raw material and the nitride red fluorescent powder are pressed into a green body under the pressure of 3-20t for 5-20min, and the green body is pressed into a biscuit under the pressure of 50-300MPa for 5-20 min.
3. The method of preparing a fluorescent ceramic according to claim 1, wherein: the ceramic raw material in the step 1 comprises Bi2O3、SiO2、ZnO、B2O3、BaO、Al2O3、Na2O、Li2O、K2A plurality of combinations of O.
4. The method of preparing a fluorescent ceramic according to claim 1, wherein: the sintering temperature in the step 1 is 400-700 ℃, the heating efficiency is 1-10 ℃/min, and the heat preservation time is 0.5-5 h.
5. The method of preparing a fluorescent ceramic according to claim 1, wherein: the heating temperature of the Cu foil before the methane gas is introduced in the step 2 is 800-.
6. The method of preparing a fluorescent ceramic according to claim 1, wherein: in the step 2, the flow rate of methane is 20-100ml/min, and the cracking temperature of methane is 800-1200 ℃; the heat preservation time is 0.5-4h, and the heating rate is 1-5 ℃/min.
7. The method of preparing a fluorescent ceramic according to claim 1, wherein: the gas ratio of hydrogen to methane in the step 2 is 2-1100: 1, the pressure is 2-750mbar, and the time for introducing hydrogen is 0.5-4 h.
8. The method of preparing a fluorescent ceramic according to claim 1, wherein: the protective gas in the step 2 comprises one or a combination of helium, argon and nitrogen, and the flow rate of the protective gas is 200-1000 ml/min.
9. The method of preparing a fluorescent ceramic according to claim 1, wherein: in the step 3, the concentration of the PMMA acetone solution is 0.5-8g/L, the heating temperature of the ceramic plate after being adhered to the surface of the graphene is 60-200 ℃, the heating time is 0.5-2h, the heating temperature of the red fluorescent glass plate after being adhered to the other surface of the graphene is 60-200 ℃, and the heating time is 0.5-2 h.
10. The fluorescent ceramic prepared by the preparation method of the fluorescent ceramic according to any one of claims 1 to 9, wherein the fluorescent ceramic comprises a ceramic sheet layer, a graphene layer and a red fluorescent glass sheet layer, and the ceramic sheet layer and the red fluorescent glass sheet layer are respectively arranged on two sides of the graphene layer.
CN201910153568.XA 2019-02-28 2019-02-28 Fluorescent ceramic and preparation method thereof Active CN110253986B (en)

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