CN111302801A - Up-conversion luminescent ceramic and preparation method thereof - Google Patents

Up-conversion luminescent ceramic and preparation method thereof Download PDF

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CN111302801A
CN111302801A CN201811511369.3A CN201811511369A CN111302801A CN 111302801 A CN111302801 A CN 111302801A CN 201811511369 A CN201811511369 A CN 201811511369A CN 111302801 A CN111302801 A CN 111302801A
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luminescent ceramic
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CN111302801B (en
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刘永福
周丽华
蒋俊
江浩川
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Ningbo Institute of Material Technology and Engineering of CAS
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Abstract

The invention relates to an up-conversion luminescent ceramic and a preparation method thereof. Specifically, the invention discloses a general formula of (1-x-y-z) Ln2O3·nMO2xPr yBi zRe, wherein A, Ln, M, Re, M, n, x, y, z are defined in the specification, the luminescent ceramic has the characteristics of long service life and high ultraviolet light conversion efficiency.

Description

Up-conversion luminescent ceramic and preparation method thereof
Technical Field
The invention relates to the field of luminescent materials, in particular to up-conversion luminescent ceramic and a preparation method thereof.
Background
TiO2Because of its high photocatalytic activity, good stability, low cost and non-toxic characteristics, it is the most widely used photocatalyst and widely used for various waste water treatments. TiO 22The band gap of the material is Eg ═ 3.2eV, and the material can be photo-catalyzed only under the irradiation of ultraviolet light with the wavelength of less than 387nmOxidation reduction ability is reduced. The ultraviolet ray in the sunlight only accounts for 3% -5%, so the TiO in the sunlight2The photocatalytic efficiency of (2) is low.
The use of up-conversion luminescent materials to convert infrared or visible light into ultraviolet light is an enhancement of TiO2An efficient method of catalytic ability. However, many of the existing up-conversion luminescent materials have the disadvantages of poor reusability, low ultraviolet conversion efficiency and the like.
Disclosure of Invention
The invention aims to provide an up-conversion luminescent ceramic with good reusability and high ultraviolet light conversion efficiency and a preparation method thereof.
In a first aspect of the present invention, there is provided an upconversion luminescent ceramic having a chemical formula of mA · (1-x-y-z) Ln2O3·nMO2xPr yBi zRe, in which,
a is one or more selected from the group consisting of: li, Na, K, Rb, Cs;
ln is one or more selected from the group consisting of: sc, Y, La, Gd, Lu, Al, Ga, B;
m is one or more selected from the group consisting of: si, Ge, Sn, Ti, Zr, Hf;
re is one or more selected from the group consisting of: ce. Nd, Po, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb;
wherein m, n, x, y and z represent the mole fraction of corresponding elements, m is more than 0 and less than or equal to 0.8, n is more than or equal to 2 and less than or equal to 3, x is more than or equal to 0.0001 and less than or equal to 0.3, y is more than or equal to 0.0001 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and 0 is more than or equal to 1-x-y-z and less than.
In another preferred example, the value ranges of m, x, y and z are as follows: m is more than 0 and less than or equal to 0.5, n is more than or equal to 2 and less than or equal to 2.5, x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.3, and 0.2 is more than or equal to 1-x-y-z is less.
In another preferred embodiment, 0.1. ltoreq. m.ltoreq.0.3.
In another preferred embodiment, 2.2. ltoreq. n.ltoreq.2.4.
In another preferred embodiment, x is 0.001. ltoreq. x.ltoreq.0.15.
In another preferred embodiment, 0.001. ltoreq. y.ltoreq.0.15.
In another preferred embodiment, 0.3 < 1-x-y-z < 1.
In another preferred embodiment, 0.4 < 1-x-y-z < 1.
In another preferred embodiment, z is 0.001. ltoreq. z.ltoreq.0.15.
In another preferred embodiment, the luminescent ceramic is excited by light with a wavelength of 400nm to 980nm, preferably 420-800nm, more preferably 460-530 nm.
In another preferred embodiment, the conversion efficiency of the luminescent ceramic under the excitation of 480-500nm excitation light at 250-375nm is 0.0095% -0.032%.
In another preferred embodiment, the conversion efficiency of the luminescent ceramic under the excitation of 480-500nm excitation light at 250-375nm is 0.020-0.032%.
In another preferred embodiment, the conversion efficiency of the luminescent ceramic under the excitation of 480-500nm excitation light at 250-375nm is 0.025-0.032%.
In a second aspect of the present invention, there is provided a method for preparing an upconversion luminescent ceramic according to the first aspect of the present invention, comprising the steps of:
(1) providing raw materials, and performing ball milling, drying and firing in sequence to obtain powder;
(2) sequentially grinding, molding and cold isostatic pressing the powder to obtain a biscuit;
(3) and sintering the biscuit in a vacuum environment to obtain the luminescent ceramic.
In another preferred example, the raw material in step (1) is an oxide, fluoride, chloride, carbonate, borate, nitrate, oxalate or acetate containing the corresponding elements a, Ln, M, Pr, Bi and Re.
In another preferred example, in the ball milling process in step (1), the ball milling tank and the milling balls are made of polytetrafluoroethylene, the size of the milling balls is 3mm to 10mm, the ball milling medium is at least one of water, absolute ethyl alcohol, acetone and glycerol, the ball milling rotation speed is 100rad/min to 600rad/min, and the ball milling time is more than 2 hours (e.g., 2 to 48 hours, preferably 4 to 30 hours).
In another preferred embodiment, the drying is carried out at 60-100 ℃ for 12-30 h; and/or
The burning is carried out for 2 to 10 hours at the temperature of 600 to 900 ℃; and/or
The cold isostatic pressing treatment is carried out at 100-500MPa, preferably 150-300 MPa.
In another preferred embodiment, the sintering is a two-stage sintering as follows: firstly, low-temperature sintering is carried out, and then high-temperature sintering is carried out.
In another preferred embodiment, the low temperature sintering is sintering at a first temperature for a first time;
the high-temperature sintering is sintering at a second temperature for a second time;
the first temperature is 1000-;
the second temperature is 1400-1900 deg.C (preferably 1400-1800 deg.C), and the second time is 1-15h (preferably 2-12 h).
In another preferred embodiment, the temperature rise rate during the sintering process is 1-10 ℃/min, preferably 3-8 ℃/min.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 is a graph showing the excitation spectra of luminescent ceramics 1 to 4 prepared in examples 1 to 4 of the present invention, wherein the emitted light has a wavelength of λem＝278nm。
FIG. 2 is a graph showing the excitation spectra of luminescent ceramics 1 to 4 prepared in examples 1 to 4 of the present invention, wherein the emitted light has a wavelength of λem＝315nm。
FIG. 3 is a graph showing emission spectra of luminescent ceramics 1 to 4 prepared in examples 1 to 4 of the present invention, in which the wavelength of excitation light is λex＝498nm。
Detailed Description
The inventor of the present invention has conducted extensive and intensive studies for a long time to prepare a highly recyclable luminescent ceramic by adjusting the composition of an upconversion luminescent ceramicAnd the up-conversion luminescent ceramic has high ultraviolet light conversion efficiency. The ceramic satisfies TiO2The application requirements of photocatalysis, ultraviolet sterilization, disinfection and the like, and has the advantages of direct recycling and high luminous efficiency of ultraviolet wave band. The preparation method of the ceramic has the advantages of low cost, simple process and contribution to large-scale popularization. On this basis, the inventors have completed the present invention.
Up-conversion luminescent ceramics
The invention provides an up-conversion luminescent ceramic. The chemical general formula of the luminescent ceramic is mA · (1-x-y-z) Ln2O3·nMO2xPr yBi zRe, in which,
a is at least one of Li, Na, K, Rb and Cs;
ln is at least one of Sc, Y, La, Gd, Lu, Al, Ga and B;
m is at least one of Si, Ge, Sn, Ti, Zr and Hf;
re is at least one of Ce, Nd, Po, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb;
wherein m, n, x, y and z represent the mole fraction of corresponding elements, m is more than 0 and less than or equal to 0.8, n is more than or equal to 2 and less than or equal to 3, x is more than or equal to 0.0001 and less than or equal to 0.3, y is more than or equal to 0.0001 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and 0 is more than or equal to 1-x-y-z and less than.
Preferably, the value ranges of m, n, x, y and z are as follows: m is more than 0 and less than or equal to 0.5, n is more than or equal to 2 and less than or equal to 2.5, x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.3, and 1-x-y-z is more than 0.2 and less than or equal. The preferred reasons are: within this range, the obtained upconversion luminescent ceramic is more excellent in properties.
The up-conversion luminescent ceramic has the following advantages:
first, with existing TiO2Compared with powder with the function of converting visible light into ultraviolet light, a glass fiber film and an active carbon composite film which are used for photocatalysis, the invention can directly use the up-conversion luminescent ceramic to carry out TiO2Photocatalysis, sterilization, disinfection and the like, the up-conversion luminescent ceramic can be directly recycled and repeatedly used for many times, and further the service life of the up-conversion functional material is prolonged.
Secondly, compared with the existing up-conversion luminescent ceramic, the up-conversion luminescent ceramic provided by the invention can realize higher conversion efficiency (such as 0.0095% -0.032%) from visible light to ultraviolet light by introducing extra luminescent ions to construct an electronic energy level bridge.
Thirdly, the up-conversion luminescent ceramic can be effectively excited by light with the wavelength of 400 nm-980 nm, especially by visible light with the wavelength of 470nm-525nm, and the emission spectrum has higher quantum efficiency (such as 0.0095% -0.032%) in the ultraviolet light band of 250nm-375 nm.
The up-conversion ceramic can be directly excited by sunlight, or can be excited by blue light, green light, red light and infrared light LED chips or laser light sources, and the ultraviolet luminous efficiency is high (for example, 0.0095% -0.032%). Can be directly used in the natural environment of sunlight or used in photocatalysis, sterilization and disinfection devices which take blue light, green light, red light and infrared light LEDs or lasers as excitation sources, and has practical application value and commercial prospect.
Preparation method
The invention also provides a preparation method of the up-conversion luminescent ceramic. The method comprises the following steps:
s1, providing raw materials, and performing ball milling, drying and firing in sequence to obtain powder;
s2, sequentially grinding, molding and carrying out cold isostatic pressing treatment on the powder to obtain biscuit precast ceramics;
s3, sintering the biscuit in a vacuum environment to obtain ceramic;
in step S1, according to mA · (1-x-y-z) Ln2O3·nMO2The reaction raw materials were weighed out in a stoichiometric ratio of xPr. yBi. zRe. The raw materials of micron or nanometer scale with purity of more than 99 percent can be adopted without reprocessing, which can save cost and realize industrialization.
Preferably, the raw material is oxide, fluoride, chloride, carbonate, borate, nitrate, oxalate or acetate containing corresponding A, Ln, M, Pr, Bi and Re elements.
Mixing the prepared raw materials, putting the mixture into a ball milling tank, and carrying out ball milling on the mixture in a planetary ball mill to obtain slurry. In the ball milling process, the ball milling tank and the ball milling are all made of polytetrafluoroethylene products, the size of the ball milling is 3-10 mm, the ball milling medium is at least one of water, absolute ethyl alcohol, acetone and glycerol, the ball milling rotating speed is 100-600 rad/min, and the ball milling time is more than 2 hours.
The ground slurry can be dried by adopting a microwave drying or forced air drying oven to obtain dry powder with good uniformity.
And (3) burning the dried powder to remove some organic impurities introduced in the ball milling process. The burning temperature is 600-900 ℃, and the burning time is 2-10 hours.
In step S2, the burned powder is ground and sieved through a 100-300 mesh sieve. And then, molding the sieved powder by powder dry pressing, slip casting or gel casting, and finally carrying out cold isostatic pressing treatment under 50-300MPa to obtain a biscuit.
In step S3, the sintering temperature is 1200 to 1700 ℃, and the sintering time is 2 hours or more. Preferably, the sintering temperature is 1400-1700 ℃.
The upconversion luminescent ceramic obtained by the method can be effectively excited by 400-980 nm light, and the emission spectrum covers the ultraviolet light wave band of 250-375 nm. Therefore, the luminescent ceramic can be directly used in the natural environment of sunlight or applied to the application requirements of photocatalysis, sterilization and disinfection devices which take blue light, green light, red light and infrared light LEDs or lasers as excitation sources.
The preparation method of the up-conversion luminescent ceramic has the following advantages:
compared with the existing process of firstly preparing a nano precursor by a sol-gel liquid phase method and then preparing ceramic, the upconversion luminescent ceramic provided by the invention is prepared into the precursor by a solid phase method and then is prepared into the ceramic. The method for preparing the powder is simple, short in period, low in cost and suitable for large-scale production.
In addition, the raw materials are commercially available, the raw materials are easily available, the cost is low, the process is simple, and the obtained product has stable and reliable quality and is beneficial to industrial production.
Compared with the prior art, the invention has the following main advantages:
(1) the up-conversion luminescent ceramic has very high ultraviolet light conversion efficiency, good reusability and long service life;
(2) the preparation method has the advantages of low cost, simple process and contribution to large-scale popularization.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
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. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
EXAMPLE 1 luminescent ceramic 1
A is Li, Ln is Y and Gd, M is Si and Ti, M is 0.01, n is 2, x is 0.0001, Y is 0.0001, z is 0, i.e. 0.01Li · 0.9998(Y · 0.9998)0.9Gd0.1)2O3·2(Si0.8Ti0.2)O2·0.0001Pr·0.0001Bi。
The preparation method of the luminescent ceramic 1 comprises the following steps:
with commercially available high purity Li2CO3、Y2O3、Gd2O3、SiO2、TiO2、Pr3O4、Bi2O3The mass of each oxide or carbonate is accurately weighed according to the above formula as a starting material. Taking 3mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in mass ratio: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and grinding the materials in a planetary ball mill by 300rad/min for 24 hours to obtain slurry after ball milling. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 600 ℃ for 2h to obtain powder 1.
Grinding the powder 1 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 1.
And (3) heating the biscuit 1 to 1200 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1700 ℃ at the speed of 5 ℃/min, preserving heat for 2h, and cooling along with the furnace to obtain the luminescent ceramic 1.
EXAMPLE 2 luminescent ceramic 2
A is Li, Ln is Y and Lu, M is Si and Zr, Re is Dy, M is 0.1, n is 2.2, x is 0.001, Y is 0.001, z is 0.001, i.e. 0.1Li · 0.997(Y is 0.1Li · 0.997)0.7Lu0.3)2O3·2.2(Si0.8Zr0.2)O2·0.001Pr·0.001Bi·0.001Dy。
The preparation method of the luminescent ceramic 2 comprises the following steps:
with commercially available high purity Li2CO3、Y2O3、Lu2O3、SiO2、ZrO2、Pr3O4、Bi2O3、Dy2O3The mass of each oxide or carbonate is accurately weighed according to the above formula as a starting material. Taking 3mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in mass ratio: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and carrying out ball milling in a planetary ball mill at the rotating speed of 300rad/min for 24 hours to obtain slurry. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 900 ℃ for 4h to obtain powder 2.
Grinding the powder 2 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 2.
And (3) heating the biscuit 2 to 1400 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1600 ℃ at the speed of 5 ℃/min, preserving heat for 5h, and cooling along with the furnace to obtain the luminescent ceramic 2.
EXAMPLE 3 luminescent ceramic 3
A is Na and K, Ln is La, M is Si and Hf, Re is Tb, M is 0.3, n is 2.4, x is 0.01, y is 0.1, z is 0.3, i.e. 0.3 (Na)0.5K0.5)·0.59La2O3·2.4(Si0.5Hf0.5)O2·0.01Pr·0.1Bi·0.3Tb。
The preparation method of the luminescent ceramic comprises the following steps:
as commercially available high purity Na2CO3、K2CO3、La2O3、SiO2、HfO2、Pr3O4、Bi2O3、Tb2O3The mass of each oxide or carbonate is accurately weighed according to the above formula as a starting material. Taking 3mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in mass ratio: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and ball milling for 24 hours in a planetary ball mill at the rotating speed of 600rad/min to obtain slurry. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 700 ℃ for 10h to obtain powder 3.
Grinding the powder 3 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 3.
And (3) heating the biscuit 3 to 1400 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1600 ℃ at the speed of 5 ℃/min, preserving heat for 10h, and cooling along with the furnace to obtain the luminescent ceramic 3.
EXAMPLE 4 luminescent ceramic 4
A is Li, Ln is Y, M is Si, Re is Tb, Er and Yb, M is 0.5, n is 2.5, x is 0.01, Y is 0.01, z is 0.5, i.e. 0.5Li · 0.48Y2O3·2.5SiO2·0.01Pr·0.01Bi·0.5(Tb0.8Er0.1Yb0.1)。
The preparation method of the luminescent ceramic 4 is as follows:
with commercially available high purity Li2O、Y2O3、SiO2、Pr3O4、Bi2O3、Tb2O3、Er2O3、Yb2O3The amount of each oxide was accurately weighed as above for the starting material. Taking 5mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in percentage by mass: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and ball milling for 24 hours in a planetary ball mill at the rotating speed of 600rad/min to obtain slurry. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 700 ℃ for 10h to obtain powder 4.
Grinding the powder 4 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 4.
And (3) heating the biscuit 4 to 1200 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1400 ℃ at the speed of 5 ℃/min, preserving heat for 10h, and cooling along with the furnace to obtain the luminescent ceramic 4.
EXAMPLE 5 luminescent ceramic 5
A is Li, Ln is Y and Al, M is Si, Re is Sm, M is 0.8, n is 2.4, x is 0.01, Y is 0.3, z is 0.01, i.e. 0.8Li · 0.68(Y is 0.8Li · 0.68)0.8Al0.2)2O3·2.4SiO2·0.01Pr·0.3Bi·0.01Sm。
The preparation method of the luminescent ceramic 5 comprises the following steps:
with commercially available high purity Li2O、Y2O3、Al2O3、SiO2、Pr3O4、Bi2O3、Sm2O3The amount of each oxide was accurately weighed as above for the starting material. Taking 5mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in percentage by mass: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and grinding the balls in a planetary ball mill at a rotating speed of 600rad/minSlurry was obtained after 24 hours of milling. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 700 ℃ for 10h to obtain powder 5.
Grinding the powder 5 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 5.
And (3) heating the biscuit 5 to 1300 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1500 ℃ at the speed of 5 ℃/min, preserving heat for 10h, and cooling along with the furnace to obtain the luminescent ceramic 5.
EXAMPLE 6 luminescent ceramic 6
A is Li, Ln is Sc and Lu, M is Si, Re is Eu, M is 0.1, n is 2.4, x is 0.01, y is 0.5, z is 0.01, i.e. 0.1Li · 0.48 (Sc)0.5Lu0.5)2O3·2.4SiO2·0.01Pr·0.5Bi·0.01Eu。
The preparation method of the luminescent ceramic 6 comprises the following steps:
with commercially available high purity Li2CO3、Sc2O3、Lu2O3、SiO2、Pr3O4、Bi2O3、Eu2O3The mass of each oxide or carbonate is accurately weighed according to the above formula as a starting material. Taking 5mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in percentage by mass: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and ball milling for 24 hours in a planetary ball mill at the rotating speed of 600rad/min to obtain slurry. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 700 ℃ for 10h to obtain powder 6.
Grinding the powder 6 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 6.
And heating the biscuit 6 to 1400 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1600 ℃ at the speed of 5 ℃/min, preserving heat for 10h, and cooling along with the furnace to obtain the luminescent ceramic 6.
EXAMPLE 7 luminescent ceramic 7
A is Li, Ln is Y, M is Si, Re is Nd, M is 0.1, n is 2.4, x is 0.2, Y is 0.01, z is 0.01, i.e. 0.1Li · 0.78Y2O3·2.4SiO2·0.2Pr·0.01Bi·0.01Nd。
The preparation method of the luminescent ceramic 7 comprises the following steps:
with commercially available high purity Li2O、Y2O3、SiO2、Pr3O4、Bi2O3、Nd2O3The amount of each oxide was accurately weighed as above for the starting material. Taking 5mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in percentage by mass: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and ball milling for 24 hours in a planetary ball mill at the rotating speed of 600rad/min to obtain slurry. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 700 ℃ for 10h to obtain powder 7.
Grinding the powder 7 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 7.
And heating the biscuit 7 to 1300 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1600 ℃ at the speed of 5 ℃/min, preserving heat for 10h, and cooling along with the furnace to obtain the luminescent ceramic 7.
EXAMPLE 8 luminescent ceramic 8
A is Li, Ln is Y, M is Si, Re is Nd, M is 0.3, n is 3, x is 0.3, Y is 0.15, z is 0.15, i.e. 0.3Li · 0.4Y2O3·3SiO2·0.3Pr·0.15Bi·0.15Nd。
The preparation method of the luminescent ceramic 8 comprises the following steps:
with commercially available high purity Li2O、Y2O3、SiO2、Pr3O4、Bi2O3、Nd2O3The amount of each oxide was accurately weighed as above for the starting material. Weighing the reaction raw materials and adding 5mm of polytetrafluoroethyleneThe alkene ball is a grinding ball, the absolute ethyl alcohol is a ball milling medium, and the ball is prepared from the following components in percentage by mass: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and ball milling for 24 hours in a planetary ball mill at the rotating speed of 600rad/min to obtain slurry. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 700 ℃ for 10h to obtain powder 8.
Grinding the powder 8 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 8.
And heating the biscuit 8 to 1300 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1500 ℃ at the speed of 5 ℃/min, preserving heat for 10h, and cooling along with the furnace to obtain the luminescent ceramic 8.
EXAMPLE 9 luminescent ceramic 9
A is Li, Ln is Y, M is Si, Re is Nd, M is 0.2, n is 2.3, x is 0.1, Y is 0.01, z is 0.01, i.e. 0.2Li · 0.88Y2O3·2.3SiO2·0.1Pr·0.01Bi·0.01Nd。
The preparation method of the luminescent ceramic 9 is as follows:
with commercially available high purity Li2O、Y2O3、SiO2、Pr3O4、Bi2O3、Nd2O3The amount of each oxide was accurately weighed as above for the starting material. Taking 5mm polytetrafluoroethylene balls as grinding balls and absolute ethyl alcohol as a ball milling medium, and mixing the raw materials in percentage by mass: material preparation: medium 10: 1: 2, putting the weighed reaction raw materials, grinding balls and a medium into a polytetrafluoroethylene ball milling tank, and ball milling for 24 hours in a planetary ball mill at the rotating speed of 600rad/min to obtain slurry. Drying the slurry in a forced air drying oven at 85 ℃ for 24h, and then burning at 700 ℃ for 10h to obtain powder 9.
Grinding the powder 9 in a corundum crucible, sieving the powder by a 200-mesh sieve, performing dry pressing in a steel mould with the diameter of 50mm, and performing cold isostatic pressing treatment under 200MPa to obtain a biscuit 9.
And heating the biscuit 9 to 1300 ℃ at the speed of 5 ℃/min in a vacuum atmosphere, preserving heat for 2h, heating to 1600 ℃ at the speed of 5 ℃/min, preserving heat for 10h, and cooling along with the furnace to obtain the luminescent ceramic 9.
Performance testing
In the present invention, excitation and emission spectra were obtained by testing with an F4600 spectrometer manufactured by hitachi, japan, and quantum efficiency was obtained with a QE2100 quantum efficiency tester manufactured by tsukamur, japan.
FIGS. 1 and 2 show excitation spectra of luminescent ceramics 1-4 obtained in examples 1-4, wherein 278nm is monitored in FIG. 1, 315nm is monitored in FIG. 2, the excitation spectrum ranges from 400nm to 525nm, the optimal excitation range covers the blue light and green light regions from 470nm to 525nm, and the excitation peak ranges from 488nm to 498 nm.
FIG. 3 shows the emission spectra of luminescent ceramics 1 to 4 obtained in examples 1 to 4, which covers ultraviolet light of 250nm to 375nm under excitation of visible light of 498nm wavelength. The ultraviolet light emission peak is near 278nm and 315nm, and the UVC emission peak position at 283nm has higher emission intensity, and the ultraviolet light in the UVC (200nm-280nm) wave band has better sterilization effect, and can kill bacteria within 1 s.
The excitation spectrum of luminescent ceramic 5-9 is substantially as shown in FIGS. 1 and 2, and the emission spectrum of luminescent ceramic 5-9 is substantially as shown in FIG. 3.
By the test of quantum efficiency tester, the luminescent ceramic obtained in examples 1-9 has a luminescent efficiency of 0.0095% -0.032% in the ultraviolet light band of 250-375nm under the excitation of visible light (such as light with a wavelength of 480-500 nm), wherein the luminescent efficiency of luminescent ceramic 1 obtained in example 1 is 0.0095%, the luminescent efficiency of luminescent ceramic 2-4 obtained in examples 2-4 is 0.020% -0.025%, and the luminescent efficiency of luminescent ceramic 5-9 obtained in examples 5-9 is 0.025% -0.032%. This shows that the luminescent ceramic provided by the invention has higher ultraviolet light conversion efficiency under the excitation of visible light, so that the luminescent ceramic can be directly applied to the natural environment of sunlight.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.

Claims (10)

1. An up-conversion luminescent ceramic, which is characterized in that the chemical formula of the luminescent ceramic is mA · (1-x-y-z) Ln2O3·nMO2xPr yBi zRe, in which,
a is one or more selected from the group consisting of: li, Na, K, Rb, Cs;
ln is one or more selected from the group consisting of: sc, Y, La, Gd, Lu, Al, Ga, B;
m is one or more selected from the group consisting of: si, Ge, Sn, Ti, Zr, Hf;
re is one or more selected from the group consisting of: ce. Nd, Po, Sm, Eu, Tb, Dy, Ho, Er, Tm and Yb;
wherein m, n, x, y and z represent the mole fraction of corresponding elements, m is more than 0 and less than or equal to 0.8, n is more than or equal to 2 and less than or equal to 3, x is more than or equal to 0.0001 and less than or equal to 0.3, y is more than or equal to 0.0001 and less than or equal to 0.5, z is more than or equal to 0 and less than or equal to 0.5, and 0 is more than or equal to 1-x-y-z and less than.
2. The upconversion luminescent ceramic according to claim 1, wherein m, x, y, and z have values in the range of: m is more than 0 and less than or equal to 0.5, n is more than or equal to 2 and less than or equal to 2.5, x is more than or equal to 0.0001 and less than or equal to 0.2, y is more than or equal to 0.0001 and less than or equal to 0.3, z is more than or equal to 0 and less than or equal to 0.3, and 0.2 is more than or equal to 1-x-y-z is less.
3. The upconversion luminescent ceramic according to claim 1, wherein 0.001. ltoreq. z.ltoreq.0.15.
4. The upconversion luminescent ceramic according to claim 1, wherein the luminescent ceramic is excited by light having a wavelength of 400nm to 980 nm.
5. The upconversion luminescent ceramic according to claim 1, wherein the luminescent ceramic has an ultraviolet light conversion efficiency of 0.0095% to 0.032% at 250-375nm under excitation of excitation light at 480-500 nm.
6. The upconversion luminescent ceramic according to claim 1, wherein the luminescent ceramic has an ultraviolet light conversion efficiency of 0.020% to 0.032% at 250-375nm under excitation of excitation light at 480-500 nm.
7. A method for preparing the upconversion luminescent ceramic according to any one of claims 1 to 6, comprising the steps of:
(1) providing raw materials, and performing ball milling, drying and firing in sequence to obtain powder;
(2) sequentially grinding, molding and cold isostatic pressing the powder to obtain a biscuit;
(3) and sintering the biscuit in a vacuum environment to obtain the luminescent ceramic.
8. The method for preparing an upconversion luminescent ceramic according to claim 7, wherein the drying is performed at 60-100 ℃ for 12-30 h; and/or
The burning is carried out for 2 to 10 hours at the temperature of 600 to 900 ℃; and/or
The cold isostatic pressing treatment is carried out at 100-500 MPa.
9. The method of claim 7, wherein the sintering is a two-step sintering as follows: firstly, low-temperature sintering is carried out, and then high-temperature sintering is carried out.
10. The method of making an upconversion luminescent ceramic according to claim 9, wherein the low temperature sintering is sintering at a first temperature for a first time;
the high-temperature sintering is sintering at a second temperature for a second time;
the first temperature is 1000-1400 ℃, and the first time is 1-5 h;
the second temperature is 1400-1900 ℃, and the second time is 1-15 h.
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