CN115784717A - Strontium aluminate long afterglow luminescent ceramic and preparation method thereof - Google Patents
Strontium aluminate long afterglow luminescent ceramic and preparation method thereof Download PDFInfo
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Abstract
The invention provides a strontium aluminate long afterglow luminescent ceramic and a preparation method thereof, the structure is a rare earth element doped SrAlO structure, and the afterglow luminescent intensity can reach 7000mcd/m at most 2 The afterglow time can reach 30h at most>0.32mcd/m 2 ) The method comprises the steps of weighing raw material powder, mixing, ball milling, drying, sieving, calcining, forming and sintering to obtain the long afterglow luminescent ceramic. The ceramic prepared by the technical scheme of the invention has green, blue and red long-afterglow luminescence and certain emerald luster, can be used as energy-saving and environment-friendly scenes such as auxiliary illumination, night indication, high-end decoration and the like, and the ceramic synthesis method is a solid-phase reaction method, has low cost and simple operation and is suitable for large-size and large-batch industrial production.
Description
Technical Field
The invention relates to the field of ceramic materials, in particular to strontium aluminate long afterglow luminescent ceramic and a preparation method thereof.
Background
The long persistence luminescent material is a special material that emits visible light after absorbing light generated by the sun or artificial light source, and can continue to emit light for tens of minutes or even hours after excitation is stopped. The best performance is the aluminate long afterglow luminescent material activated by rare earth, and the rest glow time can reach more than tens of hours.
The development of the rare earth luminescent material goes through a sulfide matrix, a silicate matrix, a phosphate matrix, a borate matrix and an aluminate matrix, wherein the sulfide matrix and the alkaline earth aluminate matrix occupy important positions in the development history of the rare earth long afterglow luminescent material.
Since the 60's of the 19 th century, people have made a lot of detailed studies on long-afterglow luminescent materials. Sulfide luminescent materials are important long-afterglow luminescent materials, and are typically represented by Cu: znS. The Cu-ZnS long-afterglow luminescent material emitting green light realizes industrial production in the 40 th century and is widely applied. ZnS and later developed blue-emitting B 3+ (Ca, sr) S and red-emitting Eu 2+ Re (Ca, sr) S is the most representative of the first generation of long-lasting phosphors. However, the materials have their fatal drawbacks: the development of the method is limited by the poor afterglow intensity and time, unstable chemical properties, easy decomposition and the like. Although the residual glow intensity and afterglow time can be improved by adding radioactive substances such as Co, pm and the like, the practical application is greatly limited due to the pollution of the radioactive substances to the environment, and the afterglow intensity is gradually high, the afterglow time is long, and the chemical stability is goodAnd the non-radioactive recyclable alkaline earth aluminate matrix luminescent material.
Eu emitting green light 2+ ,Dy 3+ :SrAl 2 O 4 And blue light-emitting Eu 2+ ,Dy 3+ :SrAl 4 O 7 Because of the advantages of long time of remaining glow, good luminous effect and the like, the fluorescent lamp has been widely applied in a plurality of fields; eu-doped 2+ ,Dy 3+ Sr of 3 Al 2 O 6 The red long-afterglow luminescent material is the most common matrix material in the red long-afterglow luminescent materials, but the red long-afterglow luminescent material is a powder material in the current research, and no specific example exists for the preparation and the research of luminescent ceramics.
Patent CN103113097B adopts coprecipitation method to prepare strontium aluminate powder, and the reducing atmosphere calcination combines with reducing atmosphere pressureless sintering to prepare strontium aluminate ceramic, 2 examples are given, but no phase and performance characterization of ceramic is given, and no physical diagram of ceramic is given, and compared with the present invention, the preparation method has the advantages of large operation difficulty, difficult control, high cost, and unsuitability for large-scale and large-scale industrial production.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a strontium aluminate long afterglow luminescent ceramic which is bulk, adopts a solid phase reaction method, has small difficulty, is easy to control and low in cost, and is suitable for large-size and large-batch industrial production, and a preparation method thereof.
The invention provides a strontium aluminate long afterglow luminescent ceramic, the structure of the long afterglow luminescent ceramic is a rare earth element doped SrAlO structure, the long afterglow luminescent ceramic is directly synthesized by a solid phase reaction method, and the afterglow luminescent intensity of the long afterglow luminescent ceramic can reach 7000mcd/m at most 2 The afterglow time can reach 30h at most>0.32mcd/m 2 )。
In one aspect of the present invention, a preparation method of the strontium aluminate long afterglow luminescent ceramic is provided, which comprises the following steps:
step 2, drying, sieving, calcining and molding the slurry to obtain a ceramic biscuit;
and 3, sintering the ceramic biscuit to finally obtain the long-afterglow luminescent ceramic.
Preferably: the chemical composition of the long-afterglow luminescent ceramic obtained in the step 1 comprises 75mol% -50mol% of SrO and 25mol% -50mol% of Al 2 O 3 。
Preferably: the rare earth element doped in the chemical composition of the long afterglow luminescent ceramic in the step 1 is Eu 2+ 、Eu 3+ 、Ce 3 + 、Dy 3+ 、Er 3+ 、Nd 3+ 、Tb 3+ 、Cr 3+ One or a combination of several of them.
Preferably: and step 1, after fully mixing, adding a sintering aid and a ball milling medium, and preparing powder suspension slurry by ball milling.
Preferably: the sintering aid is H 3 BO 3 、MgO、CaO、B 2 O 3 、SiO 2 、TEOS、LiF、NaF、MgF 2 、CaF 2 、AlF 3 One or a combination of several of them.
Preferably: the raw material powder in the step 1 comprises a SrO supply source and Al 2 O 3 The source of (1).
Preferably: the supply source of SrO is SrO and SrCO 3 Or Sr (OH) 2 Solid powder of said Al 2 O 3 Is provided by Al 2 O 3 And (3) solid powder.
Preferably: the forming mode in the step 2 is one or a combination of dry pressing, cold isostatic pressing, slip casting and tape casting.
Preferably: and the sintering in the step 3 is one or the combination of vacuum sintering, air pressure sintering, hot pressing sintering and hot isostatic pressing sintering (HIP).
The strontium aluminate long afterglow luminescent ceramic and the preparation method thereof have the following beneficial effects:
(1) The solid phase reaction method is used for directly synthesizing the block ceramic, the cost is low, the operation is simple, and the product is suitable for large-size and large-batch industrial production.
(2) The prepared long afterglow luminescent ceramic has green luminescent monoclinic phase and red luminescent cubic phase, and has certain transmittance.
(3) The prepared long-afterglow luminescent ceramic has certain emerald luster, and can be used as energy-saving and environment-friendly scenes such as auxiliary lighting, night indication, high-end decoration and the like.
Drawings
Other features, objects and advantages of the present invention will become more apparent upon reading of the following detailed description of non-limiting embodiments thereof, with reference to the accompanying drawings.
FIG. 1 is a flow chart of the preparation method of strontium aluminate long afterglow luminescent ceramic according to the embodiment of the present invention;
FIG. 2 is an XRD pattern (with Intensity as the ordinate) of a ceramic prepared according to example 1 of the present invention;
FIG. 3 is a photograph of a luminescent material object (from left to right, after excitation of the ceramic, after 5min, after 30min, after 1h and after 2 h) of the ceramic (diameter 13.5mm and thickness 2 mm) prepared in example 1 of the present invention;
FIG. 4 is a plot of afterglow performance of the ceramic prepared in example 1 of the present invention (Luminance on the ordinate and Time on the abscissa);
FIG. 5 is an XRD pattern (with Intensity as the ordinate) of a ceramic prepared according to example 2 of the present invention;
FIG. 6 is a photograph of a luminescent material object (from left to right, after excitation of the ceramic, after 5min, after 30min, after 1h and after 2 h) of the ceramic (diameter 13.5mm and thickness 2 mm) prepared in example 2 of the present invention;
FIG. 7 is a graph of afterglow performance of a ceramic prepared according to example 2 of the present invention (where luminence is the Luminance on the ordinate and Time on the abscissa);
FIG. 8 is a plot of afterglow performance of a ceramic prepared in accordance with example 3 of the present invention (Luminance on the ordinate, time on the abscissa);
FIG. 9 is a graph of afterglow performance of a ceramic prepared according to example 4 of the present invention (where luminence is plotted on the ordinate versus Time on the abscissa).
Detailed Description
Example embodiments will now be described more fully with reference to the accompanying drawings. Example embodiments may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of example embodiments to those skilled in the art. The same reference numerals in the drawings denote the same or similar structures, and thus, a repetitive description thereof will be omitted.
In the embodiment of the invention, a strontium aluminate long afterglow luminescent ceramic and a preparation method thereof are provided, wherein the long afterglow luminescent ceramic has a structure of a rare earth element doped SrAlO structure and is directly synthesized by a solid phase reaction method.
The preparation method comprises the following steps:
(1) Weighing a certain amount of raw material powder, fully and uniformly mixing, adding a proper amount of sintering aid and ball milling medium, and preparing powder suspension slurry through ball milling;
preferably, the ceramic powder contains 75mol% -50mol% of SrO and 25mol% -50mol% of Al 2 O 3 Doping trace rare earth elements, and sintering aid and ball milling medium in a certain mass ratio.
SrO and Al with different proportions 2 O 3 The strontium aluminate generated by the reaction is the matrix material, and different luminescent colors depend on different matrix materials.
Preferably, the SrO is provided by SrO solid powder and SrCO 3 Or Sr (OH) 2 And strontium salt solid powder; al (aluminum) 2 O 3 Is provided with Al as a source 2 O 3 And (3) solid powder.
The rare earth element is used as activating ion and auxiliary activating ion, and can be Eu 2+ 、Eu 3+ 、Ce 3+ 、Dy 3+ 、Er 3+ 、Nd 3+ 、Tb 3+ 、Cr 3+ Which provides the source as the corresponding oxide solid powder.
And preferably the sintering aid is H 3 BO 3 、MgO、CaO、B 2 O 3 、SiO 2 、TEOS、LiF、NaF、MgF 2 、CaF 2 、AlF 3 One or a combination of several or no sintering aid is added. The ball milling medium is one or a combination of more of alumina ball mill, zirconia ball mill, methanol, ethanol, propanol, ultrapure water, deionized water and distilled water, and the solid phase content of the finally formed slurry is 40-60 vol%.
(2) Drying, sieving, calcining and molding the slurry to obtain a ceramic biscuit;
preferably, the drying temperature of the ball milling slurry is 50-100 ℃, and the drying time is 1-10 hours; the calcining temperature of the sieved powder is 200-1000 ℃, and the calcining time is 1-10 hours.
The preferred molding mode is one or a combination of several of dry pressing molding, cold isostatic pressing molding, slip casting molding and tape casting molding, the shape is circular, the diameter is 5-200 mm, and the thickness is 1-10 mm; square, 5-200 mm side length and 1-10 mm thickness.
(3) Sintering the ceramic biscuit by adopting a proper sintering process to finally obtain the long-afterglow luminescent ceramic.
And sintering the formed ceramic biscuit, wherein the sintering is preferably one or a combination of vacuum sintering, air pressure sintering, hot pressing sintering and hot isostatic pressing sintering (HIP).
The vacuum sintering comprises the following steps: the heat preservation temperature is 1300-1800 ℃, the heat preservation time is 0.1-50 hours, and the vacuum degree is better than 10-2Pa.
The air pressure sintering is as follows: the heat preservation temperature is 1300-1800 ℃, the heat preservation time is 0.1-50 hours, and the gas in the furnace is H 2 Or N 2 The pressure is 1-10 MPa.
The hot-pressing sintering comprises the following steps: the heat preservation temperature is 1300-1800 ℃, the heat preservation time is 0.1-50 hours, and the pressure applied to the ceramic blank is 50-200 MPa.
Hot isostatic pressing sintering (HIP) is: the heat preservation temperature is 1300-1800 ℃, the heat preservation time is 0.1-50 hours, the pressure is 50-250 MPa, and the gas is Ar or N 2 。
Solid phase for the examples of the present inventionThe strontium aluminate long afterglow luminescent ceramic prepared by the reaction method has high afterglow luminescent intensity which can reach 7000mcd/m 2 (ii) a Long afterglow time up to 30 h: (>0.32mcd/m 2 ) The other glow performance is superior to the ceramic reported at present, and the stability is superior to the powder reported at present.
In addition, the ceramic prepared by the embodiment of the invention has certain transmittance and certain emerald luster, and can widen the application of strontium aluminate ceramic in more fields. The strontium aluminate luminescent ceramic provided by the embodiment of the invention can be used for auxiliary lighting, night indication, high-end decoration and the like.
In addition, the preparation cost of the embodiment of the invention is low, the operation is simple, the control is easy, and the product is suitable for large-size and large-batch industrial production.
The invention is described below in specific examples:
example 1:
a preparation method (low-temperature vacuum sintering) of strontium aluminate long afterglow luminescent ceramic comprises the following steps:
adopting strontium carbonate (SrCO) 3 ) Alumina (Al) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material, according to (Sr) 0.97 Eu 0.01 Dy 0.02 )Al 2 O 4 Chemical composition, accurately weighing 37.60g of four raw material powders respectively, and adding 0.11g of H 3 BO 3 30ml of absolute ethyl alcohol are put into a ball milling tank, 188g of ball mill is added for ball milling, the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And (3) after ball milling, blowing dry, drying in a 70 ℃ oven for 2 hours, drying, sieving by using a 200-mesh sieve, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace after sieving, keeping the temperature for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under 30MPa by using a phi 18mm mould for tabletting, cooling under 250MPa for 3 minutes and the like, thus obtaining the ceramic biscuit.
Putting the biscuit into a vacuum sintering furnace for presintering, wherein the sintering conditions are as follows: the heat preservation temperature is 1300 ℃, the heat preservation time is 3 hours, and the vacuum sintering furnace is arranged inThe vacuum degree of the vacuum is better than 1 multiplied by 10 -3 Pa. Finally polishing the two sides of the sample to 2mm thickness to obtain Eu 2+ ,Dy 3+ :SrAl 2 O 4 Green long afterglow luminescent ceramic.
Example 2
A preparation method (high-temperature vacuum sintering) of strontium aluminate long afterglow luminescent ceramic comprises the following steps:
adopting strontium carbonate (SrCO) 3 ) Alumina (Al) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material, according to (Sr) 0.97 Eu 0.01 Dy 0.02 )Al 2 O 4 Chemical composition, accurately weighing 37.60g of four raw material powders respectively, and adding 0.11g of H 3 BO 3 And 30ml of absolute ethyl alcohol are put into a ball milling tank, 188g of ball mill is added for ball milling, the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And (3) after ball milling, blowing dry, drying in a 70 ℃ oven for 2 hours, drying, sieving by using a 200-mesh sieve, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace after sieving, keeping the temperature for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under 30MPa by using a phi 18mm mould for tabletting, cooling under 250MPa for 3 minutes and the like, thus obtaining the ceramic biscuit.
Pre-sintering the biscuit in a vacuum sintering furnace under the following sintering conditions: the heat preservation temperature is 1600 ℃, the heat preservation time is 3 hours, and the vacuum degree in the vacuum sintering furnace is superior to 1 multiplied by 10 -3 Pa. Finally polishing the two sides of the sample to 2mm thickness to obtain Eu 2+ ,Dy 3+ :SrAl 2 O 4 Green long afterglow luminescent ceramic.
Example 3
A preparation method of strontium aluminate long afterglow luminescent ceramic (low temperature vacuum sintering combined with high temperature HIP) comprises the following steps:
adopting strontium carbonate (SrCO) 3 ) Alumina (Al) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material, according to (Sr) 0.97 Eu 0.01 Dy 0.02 )Al 2 O 4 Chemical composition, accurately weighing 37.60g of four raw material powders respectively, and adding 0.11g of H 3 BO 3 And 30ml of absolute ethyl alcohol are put into a ball milling tank, 188g of ball mill is added for ball milling, the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And (3) after ball milling, blowing dry, drying in a 70 ℃ oven for 2 hours, drying, sieving by using a 200-mesh sieve, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace after sieving, keeping the temperature for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under 30MPa by using a phi 18mm mould for tabletting, cooling under 250MPa for 3 minutes and the like, thus obtaining the ceramic biscuit.
Pre-sintering the biscuit in a vacuum sintering furnace under the following sintering conditions: the heat preservation temperature is 1300 ℃, the heat preservation time is 3 hours, and the vacuum degree in the vacuum sintering furnace is superior to 1 multiplied by 10 -3 Pa, then placing the pre-sintered ceramic into a hot isostatic pressing furnace for sintering, wherein the sintering conditions are as follows: the heat preservation temperature is 1600 ℃, the heat preservation time is 3 hours, the pressure is 200MPa, the gas is Ar, and finally the double surfaces of the sample are polished to the thickness of 2mm to obtain Eu 2+ ,Dy 3+ :SrAl 2 O 4 Green long afterglow luminescent ceramic.
Example 4
Preparation method of strontium aluminate long afterglow luminescent ceramic (high addition amount H) 3 BO 3 ) The method comprises the following steps:
adopting strontium carbonate (SrCO) 3 ) Alumina (Al) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material, according to (Sr) 0.97 Eu 0.01 Dy 0.02 )Al 2 O 4 Chemical composition, accurately weighing the four raw material powders respectively, wherein the total weight of the four raw material powders is 37.60g, and adding 0.38g of H 3 BO 3 30ml of absolute ethyl alcohol are put into a ball milling tank, 188g of ball mill is added for ball milling, the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And after ball milling, blowing to dry, putting into a 70 ℃ oven for drying for 2 hours, after drying, sieving by using a 200-mesh screen, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace, preserving heat for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under the pressure of 30MPa by using a phi 18mm mould for tabletting and carrying out cooling at the pressure of 250MPa for 3 minutes and the like to obtain the ceramic biscuit.
Pre-sintering the biscuit in a vacuum sintering furnace under the following sintering conditions: the heat preservation temperature is 1600 ℃, the heat preservation time is 3 hours, and the vacuum degree in the vacuum sintering furnace is superior to 1 multiplied by 10 -3 Pa. Finally, polishing the two sides of the sample to 2mm thick to obtain Eu 2+ ,Dy 3+ :SrAl 2 O 4 Green long afterglow luminescent ceramic.
Example 5
A preparation method of strontium aluminate long afterglow luminescent ceramic (raw material SrO) comprises the following steps:
strontium oxide (SrO) and aluminum oxide (Al) are adopted 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material according to (Sr) 0.97 Eu 0.01 Dy0 .02 )Al 2 O 4 Chemical composition, accurately weighing 37.43g of four raw material powders respectively, adding 1.87g of H 3 BO 3 30ml of absolute ethyl alcohol are put into a ball milling tank, 188g of ball mill is added for ball milling, the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And after ball milling, blowing to dry, putting into a 70 ℃ oven for drying for 2 hours, after drying, sieving by using a 200-mesh screen, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace, preserving heat for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under the pressure of 30MPa by using a phi 18mm mould for tabletting and carrying out cooling at the pressure of 250MPa for 3 minutes and the like to obtain the ceramic biscuit.
Putting the biscuit into a vacuum sintering furnace for presintering, wherein the sintering conditions are as follows: the heat preservation temperature is 1300 ℃, the heat preservation time is 3 hours, and the vacuum degree in the vacuum sintering furnace is superior to 1 multiplied by 10 -3 Pa. Finally polishing the two sides of the sample to 2mm thickness to obtain Eu 2+ ,Dy 3+ :SrAl 2 O 4 Green long afterglow luminescent ceramic.
Example 6
A preparation method of strontium aluminate long afterglow luminescent ceramic (supplementing Al element) comprises the following steps:
by using strontium carbonate(SrCO 3 ) Aluminum oxide (Al) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material according to (Sr) 0.97 Eu 0.01 Dy 0.02 ) 0.9 Al 2 O 4 The chemical composition is that 35.37g of four raw material powder is accurately weighed respectively, 30ml of absolute ethyl alcohol is added, the mixture is placed into a ball milling tank, 188g of ball mill is added, and ball milling is carried out, wherein the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And (3) after ball milling, blowing dry, drying in a 70 ℃ oven for 2 hours, drying, sieving by using a 200-mesh sieve, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace after sieving, keeping the temperature for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under 30MPa by using a phi 18mm mould for tabletting, cooling under 250MPa for 3 minutes and the like, thus obtaining the ceramic biscuit.
Putting the biscuit into a vacuum sintering furnace for presintering, wherein the sintering conditions are as follows: the heat preservation temperature is 1600 ℃, the heat preservation time is 3 hours, and the vacuum degree in the vacuum sintering furnace is superior to 1 multiplied by 10 -3 Pa. Finally polishing the two sides of the sample to 2mm thickness to obtain Eu 2+ ,Dy 3+ :SrAl 2 O 4 Green long afterglow luminescent ceramic.
Example 7
A preparation method of strontium aluminate long afterglow luminescent ceramic (doped with rare earth elements with different atomic percentages) comprises the following steps:
using strontium carbonate (SrCO) 3 ) Aluminum oxide (Al) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material according to (Sr) 0.96 Eu 0.02 Dy 0.02 )Al 2 O 4 Chemical composition, accurately weighing 37.64g of four raw material powders respectively, and adding 0.11g of H 3 BO 3 30ml of absolute ethyl alcohol are put into a ball milling tank, 188g of ball mill is added for ball milling, the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And after ball milling, blowing to dry, putting into a 70 ℃ oven for drying for 2 hours, after drying, sieving by using a 200-mesh screen, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace, preserving heat for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under the pressure of 30MPa by using a phi 18mm mould for tabletting and carrying out cooling at the pressure of 250MPa for 3 minutes and the like to obtain the ceramic biscuit.
Putting the biscuit into a vacuum sintering furnace for presintering, wherein the sintering conditions are as follows: the heat preservation temperature is 1600 ℃, the heat preservation time is 3 hours, and the vacuum degree in the vacuum sintering furnace is better than 1 multiplied by 10 -3 Pa. Finally polishing the two sides of the sample to 2mm thickness to obtain Eu 2+ ,Dy 3+ :SrAl 2 O 4 Green long afterglow luminescent ceramic.
Example 8
A preparation method (red light) of strontium aluminate long afterglow luminescent ceramic comprises the following steps:
adopting strontium carbonate (SrCO) 3 ) Alumina (Al) 2 O 3 ) Europium oxide (Eu) 2 O 3 ) Dysprosium oxide (Dy) 2 O 3 ) As a raw material, according to (Sr) 0.95 Eu 0.02 Dy 0.03 ) 3 Al 2 O 6 Chemical composition, accurately weighing 38.50g of four raw material powders respectively, and adding 0.39g of H 3 BO 3 30ml of absolute ethyl alcohol are put into a ball milling tank, 188g of ball mill is added for ball milling, the rotating speed of the ball mill is 130r/min, and the time is 12 hours.
And after ball milling, blowing to dry, putting into a 70 ℃ oven for drying for 2 hours, after drying, sieving by using a 200-mesh screen, heating to 800 ℃ at the speed of 5 ℃/min in a muffle furnace, preserving heat for 4 hours, cooling to 50 ℃, taking out the powder, carrying out uniaxial pressing on the powder under the pressure of 30MPa by using a phi 18mm mould for tabletting and carrying out cooling at the pressure of 250MPa for 3 minutes and the like to obtain the ceramic biscuit.
Putting the biscuit into a vacuum sintering furnace for presintering, wherein the sintering conditions are as follows: the heat preservation temperature is 1400 ℃, the heat preservation time is 3 hours, and the vacuum degree in the vacuum sintering furnace is superior to 1 multiplied by 10 -3 Pa. Finally polishing the two sides of the sample to 2mm thickness to obtain Eu 2+ ,Dy 3+ :Sr 3 Al 2 O 6 Red long afterglow luminescent ceramics.
In conclusion, the strontium aluminate long afterglow luminescent ceramic and the preparation method thereof provided by the embodiment of the invention have green, blue and red long afterglow luminescence, have certain emerald luster, can be used as energy-saving and environment-friendly scenes such as auxiliary illumination, night indication, high-end decoration and the like, and the synthesis method of the ceramic is a solid phase reaction method, has low cost and simple operation, and is suitable for large-size and large-scale industrial production.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.
Claims (10)
1. The strontium aluminate long afterglow luminescent ceramic is characterized in that the structure of the long afterglow luminescent ceramic is a rare earth element doped SrAlO structure, the long afterglow luminescent ceramic is directly synthesized by a solid phase reaction method, and the afterglow luminescent intensity of the long afterglow luminescent ceramic can reach 7000mcd/m at most 2 The afterglow time can reach 30h at most>0.32mcd/m 2 )。
2. The preparation method of the strontium aluminate long afterglow luminescent ceramic according to claim 1, comprising the following steps:
step 1, weighing raw material powder according to the chemical composition of the long afterglow luminescent ceramic, fully and uniformly mixing the raw material powder and the long afterglow luminescent ceramic, and preparing powder suspension slurry through ball milling;
step 2, drying, sieving, calcining and molding the slurry to obtain a ceramic biscuit;
and 3, sintering the ceramic biscuit to finally obtain the long-afterglow luminescent ceramic.
3. The preparation method of the strontium aluminate long afterglow luminescent ceramic according to claim 2, characterized in that: the chemical composition of the long-afterglow luminescent ceramic obtained in the step 1 comprises 75mol% -50mol% of SrO and 25mol% -50mol% of Al 2 O 3 。
4. The method for preparing strontium aluminate long afterglow luminescent ceramics according to claim 2, wherein: the rare earth element doped in the chemical composition of the long afterglow luminescent ceramic in the step 1 is Eu 2+ 、Eu 3+ 、Ce 3+ 、Dy 3+ 、Er 3+ 、Nd 3+ 、Tb 3+ 、Cr 3+ One or a combination of several of them.
5. The preparation method of the strontium aluminate long afterglow luminescent ceramic according to claim 2, characterized in that: the step 1 also comprises the steps of adding a sintering aid and a ball milling medium, and preparing powder suspension slurry through ball milling.
6. The preparation method of the strontium aluminate long afterglow luminescent ceramic according to claim 5, characterized in that: the sintering aid is H 3 BO 3 、MgO、CaO、B 2 O 3 、SiO 2 、TEOS、LiF、NaF、MgF 2 、CaF 2 、AlF 3 One or a combination of several of them.
7. The method for preparing strontium aluminate long afterglow luminescent ceramics according to claim 2, wherein: the raw material powder in step 1 comprises a SrO supply source and Al 2 O 3 The source of (1).
8. The preparation method of the strontium aluminate long afterglow luminescent ceramic of claim 7, wherein: the supply source of SrO is SrO solid powder and SrCO 3 Or Sr (OH) 2 Solid powder of said Al 2 O 3 Is provided with Al as a source 2 O 3 And (3) solid powder.
9. The preparation method of the strontium aluminate long afterglow luminescent ceramic according to claim 2, characterized in that: the forming mode in the step 2 is one or a combination of dry pressing, cold isostatic pressing, slip casting and tape casting.
10. The preparation method of the strontium aluminate long afterglow luminescent ceramic according to claim 2, characterized in that: and the sintering in the step 3 is one or the combination of vacuum sintering, air pressure sintering, hot pressing sintering and hot isostatic pressing sintering (HIP).
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036833A (en) * | 1996-07-17 | 1998-02-10 | Nec Kansai Ltd | Production of light-transmitting long-afterglow phosphor |
| CN102876326A (en) * | 2012-10-24 | 2013-01-16 | 淮海工学院 | Composite-substrate red long-afterglow luminescent material and preparation method thereof |
| CN103113097A (en) * | 2013-01-20 | 2013-05-22 | 河北联合大学 | Synthetic method of europium and dysprosium ion co-doped strontium aluminate transparent ceramic |
| CN106866132A (en) * | 2017-01-13 | 2017-06-20 | 南京工业大学 | It is a kind of for fluorescence ceramics for illuminating or showing and preparation method thereof |
| CN107523294A (en) * | 2017-09-09 | 2017-12-29 | 华北理工大学 | A kind of preparation method of the cellular porous material with long-persistence luminous function |
-
2022
- 2022-12-08 CN CN202211572866.0A patent/CN115784717A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1036833A (en) * | 1996-07-17 | 1998-02-10 | Nec Kansai Ltd | Production of light-transmitting long-afterglow phosphor |
| CN102876326A (en) * | 2012-10-24 | 2013-01-16 | 淮海工学院 | Composite-substrate red long-afterglow luminescent material and preparation method thereof |
| CN103113097A (en) * | 2013-01-20 | 2013-05-22 | 河北联合大学 | Synthetic method of europium and dysprosium ion co-doped strontium aluminate transparent ceramic |
| CN106866132A (en) * | 2017-01-13 | 2017-06-20 | 南京工业大学 | It is a kind of for fluorescence ceramics for illuminating or showing and preparation method thereof |
| CN107523294A (en) * | 2017-09-09 | 2017-12-29 | 华北理工大学 | A kind of preparation method of the cellular porous material with long-persistence luminous function |
Non-Patent Citations (2)
| Title |
|---|
| LEI YANG ET AL.: "The decay model of Eu2+ and Eu2+, Dy3+ substituted SrAl2O4 prepared by high temperature solid phase method", 《JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS》, vol. 124, pages 151 - 156, XP085522864, DOI: 10.1016/j.jpcs.2018.09.022 * |
| 李江等: "固态照明/显示用荧光陶瓷研究进展", 《发光学报》, vol. 42, no. 5, pages 580 - 604 * |
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