CN114149262A - Reversible photochromic transparent ceramic and preparation method and application thereof - Google Patents
Reversible photochromic transparent ceramic and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of ceramic materials, in particular to reversible photochromic transparent ceramic and a preparation method and application thereof. The reversible photochromic transparent ceramic comprises the following chemical components: ba (A)xMgyBz)O3(ii) a Wherein A is selected from at least one of Zr, Sn, Ti and Hf; b is selected from at least one of Ta and Nb; 4x +2y +5z ═ mX is more than 0 and less than 1, y is more than 0 and less than 1, and z is more than 0 and less than 1. The reversible photochromic transparent ceramic has the characteristic of gray-brown reversible transformation. Ba (A)xMgyBz)O3The photochromic ceramic can change color under the irradiation condition of about 365nm and can restore the original shape under the irradiation or heating condition of about 450nm, and the reversible photochromic transparent ceramic has high color change contrast.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to reversible photochromic transparent ceramic and a preparation method and application thereof.
Background
Since the first report of Fritsche in 1867, photochromic materials have attracted attention for their potential applications in optical data storage, smart windows, optical switches, optical security labels, security camouflage, the coatings industry, and the like. In recent decades, the widely reported photochromic materials are mainly classified into three major classes, organic, inorganic and organic-inorganic hybrid materials. Compared with other systems, the inorganic photochromic material has the advantages of excellent mechanical strength, long cycle life, thermochemical stability and the like, and is the preferred material for optical devices. Currently, the more studied inorganic photochromic materials can be divided into three categories: (1) transition metal oxide (TiO)2、WO3、MoO3And Nb2O5) (ii) a (2) Strong oxide (BaMgSiO)4、Sr3YNa(PO4)3F and Sr2SnO4) (ii) a (3) Ferroelectric material ((K)0.5Nb0.5)NbO3,Na0.5Bi4.5Ti4O15And Na0.5Bi2.5Nb2O9). The ferroelectric ceramic material is well applied to the fields of optical data storage, optical switches, optical anti-counterfeiting labels and the like, and part of excellent results are reported.
However, the existing ceramic photochromic materials mainly focus on inorganic non-transparent materials, and photochromic inorganic transparent materials are rarely reported, especially the research in the field of intelligent windows is less, mainly due to the following aspects: (1) the intelligent window material needs to be a transparent material, and most of the existing photochromic ceramics are non-transparent ceramics; (2) the existing photochromic ceramics have low coloring contrast (>20 percent) and cannot meet the requirements of intelligent windows; (3) the existing photochromic ceramics are mainly recovered by a heating method, and have a plurality of inconveniences in practical application; (4) the photochromic response time of the existing photochromic ceramics is too long (20 seconds).
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide reversible photochromic transparent ceramic, and aims to solve the technical problems that photochromic ceramic in the prior art is non-transparent, slow in response and the like, and cannot be used in the field of intelligent windows and the like.
The second purpose of the invention is to provide a preparation method of the reversible photochromic transparent ceramic.
The third purpose of the invention is to provide the application of the reversible photochromic transparent ceramics in the fields of intelligent windows, optical storage or optical switches and the like.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
the reversible photochromic transparent ceramic comprises the following chemical components: ba (A)xMgyBz)O3;
Wherein A is selected from at least one of Zr, Sn, Ti and Hf; b is selected from at least one of Ta and Nb; 4x +2y +5z is 4, 0 < x < 1, 0 < y < 1, 0 < z < 1.
The reversible photochromic transparent ceramic has the characteristic of gray-brown reversible transformation. Ba (A)xMgyBz)O3The photochromic ceramic changes color under the irradiation condition of 365nm and can restore the original shape under the irradiation or heating condition of 450 nm.
In addition, the reversible photochromic transparent ceramic has high color change contrast which can reach 60 to 65 percent.
In an embodiment of the present invention, x is 0.04 to 0.25. Further, x is 0.1 to 0.2.
In an embodiment of the present invention, y is 0.25 to 0.35. Further, y is 0.25 to 0.3.
In a specific embodiment of the present invention, x is 0.16, y is 0.28, and z is 0.56.
In a specific embodiment of the invention, the reversible photochromic transparent ceramic changes color under the irradiation of light of 250-400 nm, and recovers color under the irradiation of light of 450-700 nm or under the heating condition.
The invention also provides a preparation method of any one of the reversible photochromic transparent ceramics, which comprises the following steps:
mixing the Ba source, the A source, the Mg source and the B source with an auxiliary agent according to the chemical composition, grinding, and then carrying out calcination, molding and sintering treatment.
In a particular embodiment of the invention, the A source is selected from ZrO2、SnO2、TiO2And HfO2At least one of; the B source is selected from Ta2O5And Nb2O5At least one of; the Ba source is barium carbonate, and the Mg source is magnesium oxide.
In a specific embodiment of the invention, the conditions of the calcination include: the calcination temperature is 1000-1400 ℃, and the calcination time is 1-10 h.
In a specific embodiment of the present invention, the conditions of the sintering process include: the sintering temperature is 1300-1700 ℃, and the sintering time is 10-30 h.
The invention also provides application of any one of the reversible photochromic transparent ceramics in the fields of intelligent windows, optical storage or optical switches.
Compared with the prior art, the invention has the beneficial effects that:
(1) the reversible photochromic transparent ceramic has the characteristic of gray-brown reversible transformation; ba (A)xMgyBz)O3The photochromic ceramics can change and recover color under the irradiation of light with different wavelengths; the color-changing contrast is high and can reach 60 to 65 percent;
(2) the reversible photochromic transparent ceramic has the advantages of quick coloring/recovery response time and high stability, and has good application prospect in the fields of intelligent windows, optical storage or optical switch, and the like.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an X-ray diffraction pattern of a reversible photochromic ceramic provided in example 1 of the present invention;
FIG. 2 is an SEM topography of the reversible photochromic ceramic provided in example 1 of the present invention;
FIG. 3 is a graph of the diffuse reflectance spectrum of the reversible photochromic ceramic provided in example 1 of the present invention before and after 365nm irradiation;
FIG. 4 is a graph of the diffuse reflectance spectra of the reversible photochromic ceramic provided in example 1 of the present invention at 365nm for different periods of time;
FIG. 5 is a graph of maximum contrast of the reversible photochromic ceramic provided in example 1 of the present invention after 365nm irradiation as a function of time;
FIG. 6 is a graph of the diffuse reflectance spectra of the reversible photochromic ceramic provided in example 1 of the present invention after 365nm irradiation and after 450nm irradiation;
FIG. 7 is a diffuse reflectance spectrum and a diffuse reflectance spectrum before and after recovery of 365nm photochromic and 450nm of the reversible photochromic ceramic provided in example 1 of the present invention;
FIG. 8 is a diffuse reflectance spectrum and a real object chart of the reversible photochromic ceramic provided in example 1 of the present invention before and after 365nm photochromic and 300 ℃ thermal recovery;
FIG. 9 is a graph of the diffuse reflectance spectrum of the reversible photochromic ceramic provided in example 1 of the present invention at 365nm and 450nm in the photochromic cycle;
FIG. 10 is a pictorial representation of the 365nm photochromic and 450nm recovery process of the reversible photochromic ceramic provided in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The reversible photochromic transparent ceramic comprises the following chemical components: ba (A)xMgyBz)O3;
Wherein A is selected from at least one of Zr, Sn, Ti and Hf; b is selected from at least one of Ta and Nb; 4x +2y +5z is 4, 0 < x < 1, 0 < y < 1, 0 < z < 1.
The reversible photochromic transparent ceramic has the characteristic of gray-brown reversible transformation. Ba (A)xMgyBz)O3The photochromic ceramic can change color under the irradiation condition of 365nm and can restore to the original shape under the irradiation or heating condition of 450nm, and has stable recovery efficiency, and the recovery effect can reach 100 percent.
The photochromic ceramic in the prior art has low coloring contrast (more than 20 percent) and can not meet the requirements of the fields of intelligent windows and the like. The reversible photochromic transparent ceramic has high color change contrast which can reach 60 to 65 percent. In addition, the reversible photochromic transparent ceramic has quick response and the response time can reach 5 s.
In an embodiment of the present invention, x is 0.04 to 0.25. Further, x is 0.1 to 0.2.
As in various embodiments, x can be 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.11, 0.12, 0.13, 0.14, 0.15, 0.16, 0.17, 0.18, 0.19, 0.2, 0.21, 0.22, 0.23, 0.24, 0.25, and so forth.
In an embodiment of the present invention, y is 0.25 to 0.35. Further, y is 0.25 to 0.3.
As in various embodiments, y can be 0.25, 0.26, 0.27, 0.28, 0.29, 0.3, 0.31, 0.32, 0.33, 0.34, 0.35, and so forth.
In a specific embodiment of the invention, y: z is 1: 2.
In a specific embodiment of the present invention, x is 0.16, y is 0.28, and z is 0.56.
In a specific embodiment of the invention, the reversible photochromic transparent ceramic changes color under the irradiation of light of 250-400 nm, and recovers color under the irradiation of light of 450-700 nm or under the heating condition. Further, the heating temperature is 300-400 ℃, and the heating time is 30-60 s.
As in various embodiments, the reversible photochromic transparent ceramic may change color under illumination by light at 250nm, 260nm, 280nm, 300nm, 320nm, 340nm, 360nm, 380nm, 400nm, and the like; can change color under irradiation of light of 450nm, 460nm, 480nm, 500nm, 520nm, 540nm, 560nm, 580nm, 600nm, 620nm, 640nm, 660nm, 680nm, 700nm, etc.
The invention also provides a preparation method of any one of the reversible photochromic transparent ceramics, which comprises the following steps:
mixing the Ba source, the A source, the Mg source and the B source with an auxiliary agent according to the chemical composition, grinding, and then carrying out calcination, molding and sintering treatment.
In a particular embodiment of the invention, the A source is selected from ZrO2、SnO2、TiO2And HfO2At least one of; the B source is selected from Ta2O5And Nb2O5At least one of; the Ba source is barium carbonate, and the Mg source is magnesium oxide.
In a specific embodiment of the present invention, the auxiliary agents include a dispersant, a binder, and a sintering aid. In actual operation, the types and the use amounts of the dispersing agent, the binder and the sintering aid can be adjusted according to actual requirements, and the conventional aids can be selected to achieve corresponding conventional effects; the dispersing agent ensures the dispersion uniformity of the raw materials and avoids agglomeration; the binder ensures the composite molding of the raw materials in the ball milling process; the sintering aid improves the compactness of the product in the sintering process.
In a particular embodiment of the invention, the milling is ball milling. Further, the solvent adopted by the ball milling is ethanol. The materials are mixed and dispersed evenly by grinding.
In actual operation, the ground slurry is dried to obtain powder, and then the calcination is performed.
In a specific embodiment of the invention, the conditions of the calcination include: the calcination temperature is 1000-1400 ℃, and the calcination time is 1-10 h.
In a specific embodiment of the present invention, the conditions of the sintering process include: the sintering temperature is 1300-1700 ℃, and the sintering time is 10-30 h.
In a specific embodiment of the invention, the forming comprises tablet forming. The operation of the specific tabletting and forming can be adjusted according to the actual requirements.
The invention also provides application of any one of the reversible photochromic transparent ceramics in the fields of intelligent windows, optical storage or optical switches.
In practical application, the reversible photochromic transparent ceramic is discolored under illumination of 250-400 nm, is recovered under illumination of 450-700 nm or under heating condition, can be used for corresponding 0 and 1 in a computer, is applied to optical storage, can be applied to anti-counterfeiting marks, sensors, optical erasing, optical switches and the like, and has wide application prospect.
In actual operation, two light sources can be arranged to irradiate the reversible photochromic transparent ceramic, a light source of 250-400 nm is started firstly, and the ceramic is changed from brown to grey white based on the high light transmittance of the ceramic; then, a light source of 450-700 nm is started, and the ceramic is recovered to be brown from grey white based on the high light transmittance of the ceramic.
Example 1
The embodiment provides a preparation method of a reversible photochromic transparent ceramic, which comprises the following steps:
(1) according to Ba (Zr)0.16Mg0.28Ta0.56)O3Is measured by the stoichiometry ofBaCO3、ZrO2、MgO、Ta2O5(the molar ratio of Ba, Zr, Mg and Ta is 1: 0.16: 0.28: 0.56) to obtain mixed powder, and 0.5 percent, 1 percent and 0.5 percent of dispersant oleic acid, binder polyvinyl butyral and sintering aid ethyl orthosilicate which are based on the mass of the mixed powder are respectively added to obtain mixed materials; then adding ethanol which is 1.2 times of the mass of the mixed materials, and mixing the materials according to a ball-to-material ratio of 1: and 3, adding zirconia balls (the weight ratio of the big balls to the small balls is 1: 1, the size of the big balls is 10mm, and the size of the small balls is 5mm), putting all the zirconia balls into a polytetrafluoroethylene ball milling tank, and performing ball milling treatment for 24 hours to obtain mixed slurry.
(2) Then, absorbing the slurry and drying in a drying oven at 50 ℃; and grinding the dried powder, then placing the powder into a closed alumina crucible, and calcining the powder for 2 hours in a box-type furnace at 1300 ℃ in air atmosphere to obtain the powder.
(3) And (3) pre-pressing the powder obtained by calcining in the step (2) at the pressure of 3MPa by using a dry press, then placing the powder into a cold isostatic press, and maintaining the pressure at 200MPa for 2min to obtain a biscuit. Sintering the biscuit at 1500 ℃ for 10h in the industrial oxygen atmosphere to obtain the reversible photochromic transparent ceramic Ba (Zr)0.16Mg0.28Ta0.56)O3。
Example 2
This example provides a reversible photochromic transparent ceramic Ba (Sn)0.16Mg0.28Ta0.56)O3With reference to example 1, except that ZrO in step (1) was used2Replacement by SnO2。
Example 3
This example provides a reversible photochromic transparent ceramic Ba (Ti)0.16Mg0.28Ta0.56)O3With reference to example 1, except that ZrO in step (1) was used2Substituted by TiO2。
Example 4
This example provides a reversible photochromic transparent ceramic Ba (Hf)0.16Mg0.28Ta0.56)O3The specific procedure is as in example 1, except thatZrO in step (1)2Replacement is HfO2。
Example 5
This example provides a reversible photochromic transparent ceramic Ba (Zr)0.16Mg0.28Nb0.56)O3With reference to example 1, except that Ta in step (1) is used2O5Substituted by Nb2O5。
Example 6
This example provides a method for preparing a reversible photochromic transparent ceramic, the specific steps of which are described in reference to example 1, except that the ceramic of this example has a chemical composition of Ba (Zr)xMgyTaz)O3Wherein x is 0.04, y is 0.32, and z is 0.64; in the step (3), the sintering temperature is 1680 ℃.
Example 7
This example provides a method for preparing a reversible photochromic transparent ceramic, the specific steps of which are described in reference to example 1, except that the ceramic of this example has a chemical composition of Ba (Zr)xMgyTaz)O3Where x is 0.08, y: z is 1: 2, 4x +2y +5z is 4(y ≈ 0.307, z ≈ 0.613); in the step (3), the sintering temperature is 1680 ℃.
Example 8
This example provides a method for preparing a reversible photochromic transparent ceramic, the specific steps of which are described in reference to example 1, except that the ceramic of this example has a chemical composition of Ba (Zr)xMgyTaz)O3Wherein x is 0.12, y: z is 1: 2, 4x +2y +5z is 4(y ≈ 0.293, z ≈ 0.587); in the step (3), the sintering temperature is 1680 ℃.
Experimental example 1
FIG. 1 is an X-ray diffraction pattern of a reversible photochromic ceramic provided in example 1 of the present invention. Fig. 2 is an SEM topography of the reversible photochromic ceramic provided in example 1 of the present invention.
FIG. 3 is a graph of the diffuse reflectance spectrum of the reversible photochromic ceramic provided in example 1 of the present invention before and after 365nm irradiation; FIG. 4 shows the irradiation of 365nm of the reversible photochromic ceramic provided in example 1 of the present inventionDiffuse reflectance spectra at different times; FIG. 5 is a graph of the maximum contrast of the reversible photochromic ceramic provided in example 1 of the present invention after 365nm irradiation as a function of time. As can be seen from the figure, the reversible photochromic ceramic of the present invention has the characteristics of fast response time and high contrast of change. Wherein the maximum contrast Δ R is calculated as: initial reflectance R0Subtracting the reflectivity R after irradiation1Then divided by the initial reflectivity R0The concrete formula is expressed as: Δ R ═ R0-R1)/R0。
FIG. 6 is a graph of the diffuse reflectance spectra of the reversible photochromic ceramic provided in example 1 of the present invention after 365nm irradiation and after 450nm irradiation; fig. 7 is a diffuse reflectance spectrum and a diffuse reflectance spectrum of the reversible photochromic ceramic before and after 365nm photochromic and 450nm recovery according to embodiment 1 of the present invention. As can be seen from the figure, after the reversible photochromic ceramic is irradiated at 365nm, the diffuse reflection is changed, and the color is changed from grey white to brown; after 450nm irradiation, the original diffuse reflection is restored and the color is restored from brown to off-white.
Fig. 8 is a diffuse reflectance spectrum and a diffuse reflectance spectrum of the reversible photochromic ceramic provided in example 1 of the present invention before and after 365nm photochromic and 300 ℃ thermal recovery. As can be seen from the figure, after the reversible photochromic ceramic is irradiated at 365nm, the diffuse reflection is changed, and the color is changed from grey white to brown; after heat treatment at 300 ℃ for 30s, the original diffuse reflection is restored and the color is restored from brown to off-white.
FIG. 9 shows the reflection spectrum of the reversible photochromic ceramic provided in example 1 of the present invention at 365nm and 450nm in the photochromic cycle; wherein figure 9 is an irradiation treatment 60 s.
Fig. 10 is a physical diagram of the reversible photochromic ceramic provided in embodiment 1 of the present invention after 365nm photochromic and 450nm recovery processing (the rest positions are shaded, and only the mark "2" is left), which illustrates that the reversible photochromic material provided in embodiment 1 of the present invention can store information.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The reversible photochromic transparent ceramic is characterized by comprising the following chemical components: ba (A)xMgyBz)O3;
Wherein A is selected from at least one of Zr, Sn, Ti and Hf; b is selected from at least one of Ta and Nb; 4x +2y +5z is 4, 0 < x < 1, 0 < y < 1, 0 < z < 1.
2. The reversible photochromic transparent ceramic of claim 1 wherein x is 0.04 to 0.25;
preferably, x is 0.1 to 0.2.
3. The reversible photochromic transparent ceramic of claim 1 wherein y is 0.25 to 0.35;
preferably, y is 0.25 to 0.3.
4. The reversible photochromic transparent ceramic of claim 1 wherein x is 0.16, y is 0.28 and z is 0.56.
5. The reversible photochromic transparent ceramic of claim 1 wherein the reversible photochromic transparent ceramic changes color under 250 to 400nm light irradiation and recovers color under 450 to 700nm light irradiation or under heating.
6. A method for preparing a reversible photochromic transparent ceramic according to any one of claims 1 to 5 comprising the following steps:
mixing the Ba source, the A source, the Mg source and the B source with an auxiliary agent according to the chemical composition, grinding, and then carrying out calcination, molding and sintering treatment.
7. The method for preparing a reversible photochromic transparent ceramic according to claim 6 wherein the A source is selected from ZrO2、SnO2、TiO2And HfO2At least one of; the B source is selected from Ta2O5And Nb2O5At least one of; the Ba source is barium carbonate, and the Mg source is magnesium oxide.
8. The method for preparing a reversible photochromic transparent ceramic according to claim 6, wherein the conditions of the calcination comprise: the calcination temperature is 1000-1400 ℃, and the calcination time is 1-10 h.
9. The method for preparing a reversible photochromic transparent ceramic according to claim 6, wherein the conditions of the sintering treatment comprise: the sintering temperature is 1300-1700 ℃, and the sintering time is 10-30 h.
10. Use of the reversible photochromic transparent ceramic according to any one of claims 1 to 5 in the field of smart windows, optical storage or optical switches.
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