CN114804871B - Tungsten bronze-based photochromic ceramic material and preparation method thereof - Google Patents
Tungsten bronze-based photochromic ceramic material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of up-conversion luminescent materials, and provides a tungsten bronze-based photochromic ceramic material. The invention selects Ba with a square tungsten bronze structure 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6 O 30 As a base material, the material has the characteristic of good near infrared absorption property; by introducing a proper amount of molybdenum ions with variable valence property into the material and utilizing the variable valence property of the molybdenum ions to match with the action of the material matrix with the tetragonal tungsten bronze structure, a strong photochromic effect can be obtained within a few seconds under the irradiation of 405nm light, and the discoloration can be erased within a few seconds by heating. Thus, the material exhibits a fast color change effect. In addition, along with the rapid color change effect, the up-conversion luminous intensity of the material also shows the characteristic of rapid change under the alternating action of 405nm light irradiation and heating.
Description
Technical Field
The invention belongs to the technical field of up-conversion luminescent materials, and particularly relates to a tungsten bronze-based photochromic ceramic material and a preparation method thereof.
Background
Photochromic materials are materials that change color when excited by a light source. In the past, studies on photochromic materials have been mainly focused on organic substances, and many organic color-changing systems represented by fulgide systems, pyrans, spiropyran systems, diarylethylenes, schiff bases, anilide derivatives, and the like have been developed so far. However, the organic photochromic material has poor thermal stability, slow response, poor fatigue resistance, poor mechanical properties and environmental friendliness, and the bottleneck limits the wide application of the organic photochromic material in practice.
At present, photochromic materials prepared by using inorganic substances are widely concerned due to the advantages of good thermal stability, high mechanical strength, good oxidation resistance and the like. However, the inorganic photochromic material provided in the prior art has a slow color change speed, usually requires several minutes of light irradiation to have a strong color change effect, and requires several minutes of heating to recover. In addition, the use of photochromism to further achieve rapid control of up-conversion luminescence properties of materials has also been rarely reported.
Therefore, it is desired to provide an inorganic photochromic material having a high photochromic speed.
Disclosure of Invention
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention provides a tungsten bronze-based photochromic ceramic material, which has a chemical formula shown as a formula I
Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Formula I
In the formula I, 0<x is less than or equal to 0.2.
Preferably, x in said formula I is 0.006, 0.02, 0.04, 0.08 or 0.12.
The invention provides a preparation method of the tungsten bronze-based photochromic ceramic material, which comprises the following steps:
(1) Mixing BaCO 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 2 Ball milling is carried out after mixing to obtain a mixture; the mass ratio of the elements Ba, la, er, yb, ti, nb and Mo in the mixture is 4<x≤0.2；
(2) Pre-burning the mixture obtained in the step (1) to obtain a precursor;
(3) And (3) sintering the precursor obtained in the step (2) to obtain the tungsten bronze-based photochromic ceramic material.
Preferably, baCO in the step (1) 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 None of them had a purity of less than 99%.
Preferably, the ball milling medium of the ball milling in the step (1) comprises at least one of methanol, ethanol and propanol.
Preferably, after the ball milling in the step (1) is completed, the ball-milled product is sequentially dried and ground to obtain a material to be calcined.
Preferably, the pre-sintering temperature in the step (2) is 1250-1310 ℃, and the pre-sintering time is 6-10 h.
Preferably, after the pre-sintering in the step (2) is completed, the pre-sintered product is sequentially ground and pressed into sheets, so as to obtain a sintering precursor.
Preferably, the sintering temperature in the step (3) is 1330-1360 ℃, and the sintering time is 1-5 h.
Preferably, after the sintering in the step (3) is completed, polishing is performed on the sintered product to obtain the tungsten bronze-based photochromic ceramic material.
The invention provides a tungsten bronze-based photochromic ceramic material, which has a chemical formula of Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Wherein, 0<x is less than or equal to 0.2. The invention selects Ba with a square tungsten bronze structure 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6 O 30 As a base material, the material has the characteristic of good near infrared absorption property; by introducing a proper amount of molybdenum ions with variable valence property into the material, and utilizing the characteristics of the molybdenum ions and the property with variable valence state to match the action of the material matrix with the tetragonal tungsten bronze structure, a strong photochromic effect can be obtained within seconds under the irradiation of 405nm light, and the discoloration can be erased within seconds by heating. Thus, the material exhibits a fast color change effect. In addition, along with the rapid color change effect, the up-conversion luminous intensity of the material also shows the characteristic of rapid change under the alternating action of 405nm light irradiation and heating. The experimental result shows that the material provided by the invention can realize coloring within 1 second under the irradiation of 405nm light,and the color fading is very rapid under the heating of 250 ℃, and the initial state can be basically recovered in only 1 second. Correspondingly, the upconversion luminescence intensity of the material under 980nm excitation also exhibits the same rapid change characteristic.
Drawings
FIG. 1 is an X-ray diffraction spectrum of the materials prepared in comparative example 1 and examples 1 to 5 of the present invention;
FIG. 2 is a photo of the photochromic material prepared in comparative example 1 and examples 1 to 5 of the present invention after being irradiated at 405nm for 30 seconds;
FIG. 3 is a reflectance spectrum of the materials prepared in comparative example 1 and examples 1 to 5 of the present invention before and after irradiation with light at 405nm for 120 seconds;
FIG. 4 is a graph of the reflectance of the material prepared in example 1 of the present invention as a function of time under 405nm light irradiation;
FIG. 5 is a graph showing the upconversion luminescence spectra of the material prepared in example 1 of the present invention in an irradiated state with a light irradiation time of 405nm of 120 seconds and heated at 250 ℃ for various times;
FIG. 6 is an up-converted luminescence spectrum at room temperature of materials prepared in comparative example 1 and examples 1 to 5 of the present invention;
FIG. 7 is a graph showing the reversibility of up-conversion luminescence of a material prepared in example 1 of the present invention under the alternate action of irradiation with light at 405nm for 120 seconds, heating at 250 ℃ for 10 seconds;
fig. 8 is a diagram of the application of the material prepared in example 1 of the present invention in the display of handwritten dual-mode (photochromic and up-conversion luminescence) information.
Detailed Description
The invention provides a tungsten bronze-based photochromic ceramic material, which has a chemical formula shown as a formula I
Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Formula I
In the formula I, 0<x is less than or equal to 0.2.
In the present invention, x in the formula I is preferably 0.006, 0.02, 0.04 or 0.08, more preferably 0.006. The invention limits the value of x in the range, the doping amount of Mo in the material is proper, the obtained material has good photochromic performance, and the regulating and controlling performance of photochromic on up-conversion luminescence is good.
The invention selects the Ba with a tetragonal tungsten bronze structure 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6 O 30 As a base material, the material has the characteristic of good near infrared absorption property; by introducing a proper amount of molybdenum ions with variable valence property into the material and utilizing the variable valence property of the molybdenum ions to match with the action of the material matrix with the tetragonal tungsten bronze structure, under the excitation of light, the photochromic capability of the material is greatly improved, the material is enabled to show a quick photochromic effect, and meanwhile, the photochromic function forms quick regulation and control on the up-conversion luminous intensity.
The invention provides a preparation method of the tungsten bronze-based photochromic ceramic material, which comprises the following steps:
(1) Mixing BaCO 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 Ball milling is carried out after mixing to obtain a mixture; the mass ratio of the elements Ba, la, er, yb, ti, nb and Mo in the mixture is 4<x≤0.2；
(2) Pre-burning the mixture obtained in the step (1) to obtain a precursor;
(3) And (3) sintering the precursor obtained in the step (2) to obtain the tungsten bronze-based photochromic ceramic material.
The invention uses BaCO 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 And ball milling is carried out after mixing to obtain a mixture.
In the present invention, the BaCO is 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 Required for providing tungsten bronze based photochromic ceramic materialElements, the oxides of which are selected for most of the desired elements in order to avoid the introduction of impurity elements. Among them, baO is very likely to absorb moisture and carbon dioxide in the air to generate barium carbonate, so Ba element is provided by its carbonate.
In the present invention, the ratio of the amounts of species of elements Ba, la, er, yb, ti, nb and Mo in the mixture is 4. The invention limits the value of x in the range, the doping amount of Mo in the material is more appropriate, and the obtained material has better photochromic performance.
In the present invention, the BaCO is 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 2 The purity of (2) is preferably 99% or more. The invention limits the purity of the material to the range, avoids the influence of impurities in the raw materials on the luminescence property of the material, and ensures that the obtained material has better up-conversion luminescence property.
In the present invention, the ball milling medium preferably comprises at least one of methanol, ethanol and propanol, more preferably ethanol. The invention selects the ethanol with relatively low toxicity as the ball milling medium, improves the dispersibility of the materials, and is beneficial to fully mixing oxide or carbonate powder. The invention utilizes ball milling to realize the full mixing of oxide or carbonate powder. The ball milling mode is not specially specified, and the solid-phase materials are uniformly mixed by adopting the ball milling mode well known by the technical personnel in the field.
After the ball milling is finished, the ball-milled materials are preferably dried and ground in sequence to obtain the materials to be calcined.
The drying operation is not particularly specified in the present invention, and the ball milling medium is removed by a drying method well known to those skilled in the art.
The grinding mode is not specially determined, and the dried material is easy to be agglomerated into blocks, so that the blocky material is ground into powder by adopting the grinding mode well known by the technical personnel in the field.
After the material to be calcined is obtained, the material to be calcined is presintered to obtain a sintering precursor.
In the present invention, the temperature of the pre-firing is preferably 1250 to 1310 ℃, more preferably 1300 ℃. The time for the calcination is preferably 6 to 10 hours, and more preferably 8 hours. In the present invention, the temperature raising means for the calcination is preferably a continuous temperature raising. In the present invention, the rate of temperature rise is preferably 2 to 5 ℃/min, more preferably 4 ℃/min. The invention can synthesize the transition crystalline phase in advance by pre-burning, thereby improving the speed of secondary burning; with CO formed by decomposition of carbonates 2 The gas is removed, so that cracking and deformation caused by excessive shrinkage during sintering can be avoided, and the residual of pores in the porcelain body during sintering can be reduced, which is beneficial to densifying sintering. According to the invention, the temperature, time and heating rate of the pre-sintering are controlled within the above ranges, and the obtained material has good photochromic performance.
After the presintering is finished, the presintering product is preferably mixed with ethanol, and then grinding and tabletting are sequentially carried out to obtain a sintering precursor.
In the invention, the ethanol can be used as a grinding medium on one hand, and is beneficial to the post-tabletting forming on the other hand.
The grinding mode is not specially specified in the invention, and the raw materials are agglomerated again in the pre-sintering process, so that the agglomerated materials are ground into powder by adopting the grinding mode well known by the technical personnel in the field.
The operation of the tabletting is not specially specified, and the ground material is pressed into the tablets.
In the present invention, the pressure of the tablet is preferably 6 to 20MPa, more preferably 10 to 15MPa. The invention controls the pressure of the tabletting in the range, and is beneficial to obtaining a sheet structure with a compact structure.
In the invention, the sintering temperature is preferably 1330-1360 ℃, and more preferably 1350 ℃; the sintering time is preferably 1 to 5 hours, more preferably 3 hours. According to the invention, the sintering temperature is controlled within the range, and the obtained material has good photochromic performance.
After sintering is finished, the sintered product is preferably cooled and then polished to obtain the tungsten bronze-based photochromic ceramic material.
The cooling mode is not specially specified, and the sintered product is cooled to the room temperature by adopting the cooling mode which is well known to the technical personnel in the field. In the embodiment of the invention, the temperature is preferably reduced to 550 ℃ at a cooling rate of 4 ℃/min, and then the temperature is reduced by adopting a natural cooling mode, and the cooling mode of the embodiment is favorable for rapidly reducing the temperature of the presintering product to room temperature.
The polishing operation is not specially specified, and the sintered product is polished to be smooth and flat by adopting a polishing mode well known by the technical personnel in the field.
The preparation method of the tungsten bronze-based photochromic ceramic material is simple by adopting a high-temperature solid-phase reaction method, and the material of the obtained material has good photochromic performance.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
In the examples of the present invention, the raw materials and purities used were:
BaCO 3 (99％)、La 2 O 3 (99.9％)、Er 2 O 3 (99.9％)、Yb 2 O 3 (99.9％)、TiO 2 (99％)、Nb 2 O 5 (99.99%) and MoO 3 (99.5％)
In the examples of the present invention, the raw material sources used were:
BaCO 3 (Aladdin reagent (Shanghai) Co., ltd.), la 2 O 3 (Aladdin reagent (Shanghai) Co., ltd.) Er 2 O 3 (Aladdin reagent (Shanghai) Co., ltd.), yb 2 O 3 (Aladdin reagent (Shanghai) Co., ltd.), tiO 2 (Aladdin reagent (Shanghai) Co., ltd.), nb 2 O 5 (chemical reagents of national drug group Co., ltd.) and MoO 3 (Aladdin reagent (Shanghai) Co., ltd.).
Example 1
A tungsten bronze-based photochromic ceramic material with a chemical formula of Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Where x =0.006.
The preparation method comprises the following steps:
(1) According to the stoichiometric ratio of the chemical formula, baCO is respectively weighed by using an electronic balance with the precision of 0.0001g 3 (99％)、La 2 O 3 (99.9％)、Er 2 O 3 (99.9％)、Yb 2 O 3 (99.9％)、TiO 2 (99％)、Nb 2 O 5 (99.99%) and MoO 3 (99.5%) 3.5083g,1.3490g,0.0168g,0.0868g,1.4199g, 3.5055g and 0.0038g, respectively, and the raw materials are placed into a clean agate tank according to the chemical ratio and mixed to obtain a mixture. (ratio of the amounts of substances of elements Ba, la, er, yb, ti, nb, and Mo 4
(1) Absolute ethyl alcohol (99.7 mass percent) is used as a grinding medium, the mixture is ground in a planetary ball mill for 24 hours and uniformly mixed, the product is taken out of an agate tank, a 3ml suction pipe is used for sucking the product, the product is placed in a clean 250ml glass beaker, and then the glass beaker is placed in an oven for drying.
(2) And grinding the dried powder by using an agate mortar, then placing the powder into a corundum crucible, placing the corundum crucible into a muffle furnace, and continuously heating to 1300 ℃ for presintering for 8 hours, wherein the heating rate is 4 ℃/min.
(3) And putting the pre-sintered block into a clean mortar again, adding a proper amount of absolute ethyl alcohol (with the mass concentration of 99.7%) for grinding, putting 0.7g of ground powder into a 10MPa pressure to prepare a ceramic green sheet with the diameter of 13mm, bagging the rest samples for later use, putting the pressed samples into a muffle furnace, continuously heating to 1350 ℃ for sintering for 3 hours, cooling to 550 ℃ at the cooling rate of 4 ℃/min, then naturally cooling, taking the samples out of the muffle furnace, polishing and thinning the samples to 0.7mm through the surface of silicon carbide to obtain the tungsten bronze-based photochromic ceramic material.
Example 2
A tungsten bronze-based photochromic ceramic material with a chemical formula of Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Ceramic material, wherein x =0.02.
The preparation method was the same as in example 1 except that BaCO was weighed in step (1) using an electronic balance with an accuracy of 0.0001g 3 (99％)、La 2 O 3 (99.9％)、Er 2 O 3 (99.9％)、Yb 2 O 3 (99.9％)、TiO 2 (99％)、Nb 2 O 5 (99.99%) and MoO 3 (99.5%) were 3.5083g,1.3490g,0.0168g,0.0868g,1.4199g, 3.4973g, and 0.0127g, respectively. (ratio of the substances of the elements Ba, la, er, yb, ti, nb and Mo 4
Example 3
A tungsten bronze-based photochromic ceramic material with a chemical formula of Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Ceramic material, wherein x =0.04.
The preparation method was the same as in example 1 except that BaCO was weighed in step (1) using an electronic balance with an accuracy of 0.0001g 3 (99％)、La 2 O 3 (99.9％)、Er 2 O 3 (99.9％)、Yb 2 O 3 (99.9％)、TiO 2 (99％)、Nb 2 O 5 (99.99%) and MoO 3 (99.5%) were 3.5083g,1.3490g,0.0168g,0.0868g,1.4199g, 3.4856g, and 0.0255g, respectively. (ratio of the amounts of substances of elements Ba, la, er, yb, ti, nb and Mo 4
Example 4
Tungsten blueCopper-based photochromic ceramic material having the chemical formula Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Ceramic material, wherein x =0.08.
The preparation method was the same as in example 1 except that BaCO was weighed in step (1) using an electronic balance with an accuracy of 0.0001g 3 (99％)、La 2 O 3 (99.9％)、Er 2 O 3 (99.9％)、Yb 2 O 3 (99.9％)、TiO 2 (99％)、Nb 2 O 5 (99.99%) and MoO 3 (99.5%) were 3.5083g,1.3490g,0.0168g,0.0868g,1.4199g, 3.4623g, and 0.0509g, respectively. (ratio of the substances of the elements Ba, la, er, yb, ti, nb and Mo 4
Example 5
A tungsten bronze-based photochromic ceramic material with a chemical formula of Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Ceramic material, wherein x =0.12.
The preparation method was the same as in example 1 except that BaCO was weighed in step (1) using an electronic balance with an accuracy of 0.0001g 3 (99％)、La 2 O 3 (99.9％)、Er 2 O 3 (99.9％)、Yb 2 O 3 (99.9％)、TiO 2 (99％)、Nb 2 O 5 (99.99%) and MoO 3 (99.5%) were 3.5083g,1.3490g,0.0168g,0.0868g,1.4199g, 3.4389g, and 0.0764g, respectively. (ratio of the amounts of substances of elements Ba, la, er, yb, ti, nb and Mo 4
Comparative example 1
A tungsten bronze-based photochromic ceramic material with a chemical formula of Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Ceramic material, wherein x =0.
The preparation method was the same as in example 1 except that BaCO was weighed in step (1) using an electronic balance with an accuracy of 0.0001g, respectively 3 (99％)、La 2 O 3 (99.9％)、Er 2 O 3 (99.9％)、Yb 2 O 3 (99.9％)、TiO 2 (99％)、Nb 2 O 5 (99.99%) and MoO 3 (99.5%) were 3.5083g,1.3490g,0.0168g,0.0868g,1.4199g,3.5090g and 0g, respectively. (ratio of the amounts of substances of the elements Ba, la, er, yb, ti and Nb 4
Application example 1
Application of the material prepared in example 1 to a handwritten, dual-mode (photochromic and up-converting luminescent) information display prototype.
The material prepared in example 1 was irradiated with light at 405nm for 1s (corresponding to the handwriting in the drawing), and then heated for 1s for recovery; the effect is shown in fig. 8. In fig. 8, the CAUC is the area discolored by 405nm light irradiation, and the other parts are the areas not irradiated by 405nm light, and the CAUC disappears after heating. This shows that the material provided by the present invention can change color rapidly under 405nm light irradiation, and information can be encoded on the surface of the sample by using the color change effect, such as CAUC (Black) shown in FIG. 8, and the information can be erased by heating.
Or, the material prepared in the example 1 is subjected to light excitation under 980nm light, and a sample emits green light to form a green background; on the basis, when the film is irradiated by 405nm light, the luminous intensity of the irradiated path is reduced, the visual effect is darkened, and the effect graph is shown in figure 8. The CAUC pattern displayed on a green background can be seen in FIG. 8. This means that information can also be written on the surface of the sample by this effect.
The materials prepared in examples 1 to 5 and comparative example 1 were subjected to X-ray diffraction, and the results are shown in fig. 1. It can be seen from fig. 1 that with the doping of the element Mo, the peak position of the diffraction peak of the material does not change significantly, but the relative intensity of the diffraction peak is changed. Therefore, mo does not change the inherent crystal structure of the material, but can effectively improve the photochromic effect of the material.
The materials prepared in examples 1 to 5 and comparative example 1 were irradiated with light at 405nm for 30 seconds, in which the black crown region was discolored by the irradiation of light at 405nm, and the other portions wereRegions not irradiated by 405nm light; the photochromic picture is shown in figure 2. As can be seen from FIG. 2, a Mo-doped tetragonal tungsten bronze material (Ba) 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6 O 30 ) The photochromic intensity under 405nm light is firstly enhanced and then weakened, which shows that the doping amount of Mo is in a certain range, and the photochromic effect of the material can be effectively improved.
The materials prepared in examples 1 to 5 and comparative example 1 were irradiated at 405nm for 120 seconds to obtain front and rear reflectance spectra, as shown in FIG. 3. As can be seen from FIG. 3, after irradiation, the reflectivity generally decreases, and with the addition of Mo, the difference between the reflection spectrum value after irradiation and the reflection spectrum value before irradiation is larger, which further illustrates that the introduction of Mo ions can effectively improve the photochromic effect of the material.
The reflectance change of the material prepared in example 1 was measured at 405nm for 120s, as shown in FIG. 4. As can be seen from fig. 4, the reflectance continuously decreases as the illumination time increases. This is because the degree of photon reaction increases and thus the photochromic effect is better.
After the material prepared in example 1 is irradiated for 120s under 405nm light, the material is heated and recovered at 250 ℃ for different time periods, and the effect graph is shown in fig. 5. As can be seen from fig. 5, when heated for 1s, it can be restored to a level almost equivalent to that of heating for 10 s; the material provided by the invention can be quickly recovered under the heating condition.
The materials prepared in examples 1 to 5 and comparative example 1 were directly subjected to the up-conversion luminescence test (without being subjected to the light irradiation treatment), and the test results are shown in fig. 6. It can be seen from fig. 6 that the upconversion luminescence intensity first increases and then decreases as the Mo doping amount increases, and the intensity is highest when the Mo doping amount x =0.006.
The material prepared in example 1 was irradiated with light at 405nm for 120 seconds and then heated at 250 c for 10 seconds, so that the irradiation and heating were alternately performed, and the measured percentage difference between the upconversion luminescence intensity and the initial upconversion luminescence intensity of the material was shown in fig. 7. As can be seen from fig. 7, after 10 cycles when the Mo doping amount x =0.006, the control of the upconversion luminescence intensity is maintained around 50%, without significant change; when the Mo doping amount x =0.008 is 10 times of circulation, the up-conversion luminescence intensity is kept about 37% and is not obviously changed; this demonstrates that the material provided by the present invention has good reversibility.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The tungsten bronze-based photochromic ceramic material is characterized by having a chemical formula shown as formula I
Ba 4 La 1.88 Er 0.02 Yb 0.1 Ti 4 Nb 6-x Mo x O 30 Formula I
X in the formula I is 0.006, 0.02, 0.04, 0.08 or 0.12.
2. A method of making a tungsten bronze based photochromic ceramic material according to claim 1 comprising the steps of:
(1) Mixing BaCO 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 Ball milling is carried out after mixing to obtain a mixture; the mass ratio of the elements Ba, la, er, yb, ti, nb and Mo in the mixture is 4 (6-x) x, wherein x is 0.006, 0.02, 0.04, 0.08 or 0.12;
(2) Pre-burning the mixture obtained in the step (1) to obtain a precursor;
(3) And (3) sintering the precursor obtained in the step (2) to obtain the tungsten bronze-based photochromic ceramic material.
3. The method of claim 2, wherein the BaCO in step (1) 3 、La 2 O 3 、Er 2 O 3 、Yb 2 O 3 、Nb 2 O 5 、MoO 3 And TiO 2 Is not less than 99%.
4. The method of claim 2, wherein the ball milling media ball milled in step (1) comprises at least one of methanol, ethanol, and propanol.
5. The method according to claim 2, wherein after the ball milling in the step (1) is completed, the ball-milled product is sequentially dried and ground to obtain the material to be calcined.
6. The method of claim 2, wherein the pre-sintering in the step (2) is performed at a temperature of 1250-1310 ℃ for 6-10 hours.
7. The method according to claim 2, wherein after the pre-sintering in step (2) is completed, the pre-sintered product is sequentially subjected to grinding and tabletting to obtain a sintering precursor.
8. The method as claimed in claim 2, wherein the sintering temperature in the step (3) is 1330-1360 ℃ and the sintering time is 1-5 h.
9. The method according to claim 2, wherein after the sintering in the step (3) is completed, the sintered product is polished to obtain a tungsten bronze based photochromic ceramic material.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090017251A (en) * | 2007-08-14 | 2009-02-18 | 주식회사 엘지화학 | Photochromic composition and product produced by the same |
| JP2014047307A (en) * | 2012-08-31 | 2014-03-17 | National Institute Of Advanced Industrial & Technology | Photochromic material, and method of reversible change of absorption spectrum of photochromic material |
| CN105016728A (en) * | 2014-04-23 | 2015-11-04 | 中国民航大学 | Rear earth doped non-fullness tungsten bronze luminescence ferroelectric material and preparation method thereof |
| CN106478096A (en) * | 2015-08-31 | 2017-03-08 | 中国民航大学 | A kind of rare earth base novel non-full of type tungsten bronze ferroelectric material and preparation method thereof |
| CN107345134A (en) * | 2016-05-05 | 2017-11-14 | 中国民航大学 | A kind of rear-earth-doped tungsten bronze fluorescence temperature detection material of high sensitivity |
| CN114181701A (en) * | 2020-09-14 | 2022-03-15 | 中国民航大学 | Rare earth doped up-conversion luminescence regulation and control material |
| CN114394833A (en) * | 2022-01-07 | 2022-04-26 | 电子科技大学 | Tungsten bronze structure high energy storage density and power density lead-free energy storage dielectric ceramic material |
-
2022
- 2022-05-18 CN CN202210543468.XA patent/CN114804871B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20090017251A (en) * | 2007-08-14 | 2009-02-18 | 주식회사 엘지화학 | Photochromic composition and product produced by the same |
| JP2014047307A (en) * | 2012-08-31 | 2014-03-17 | National Institute Of Advanced Industrial & Technology | Photochromic material, and method of reversible change of absorption spectrum of photochromic material |
| CN105016728A (en) * | 2014-04-23 | 2015-11-04 | 中国民航大学 | Rear earth doped non-fullness tungsten bronze luminescence ferroelectric material and preparation method thereof |
| CN106478096A (en) * | 2015-08-31 | 2017-03-08 | 中国民航大学 | A kind of rare earth base novel non-full of type tungsten bronze ferroelectric material and preparation method thereof |
| CN107345134A (en) * | 2016-05-05 | 2017-11-14 | 中国民航大学 | A kind of rear-earth-doped tungsten bronze fluorescence temperature detection material of high sensitivity |
| CN114181701A (en) * | 2020-09-14 | 2022-03-15 | 中国民航大学 | Rare earth doped up-conversion luminescence regulation and control material |
| CN114394833A (en) * | 2022-01-07 | 2022-04-26 | 电子科技大学 | Tungsten bronze structure high energy storage density and power density lead-free energy storage dielectric ceramic material |
Non-Patent Citations (1)
| Title |
|---|
| 钨青铜陶瓷Sr_(0.6)Ba_(0.4)Nb_2O_6的合成、结构与介电性能;郑兴华等;《山东陶瓷》;20050830(第04期);第3-5页 * |
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