CN115215641A - Photochromic ceramic, preparation method thereof and optical device - Google Patents
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Abstract
The application relates to the field of anti-counterfeiting ceramic materials, in particular to photochromic ceramic, a preparation method thereof and an optical device. A photochromic ceramic is Pr 3+ Doped BaMgSiO 4 . The photochromic ceramic provided by the application has the advantages of physical and chemical stability, quick photochromic response, large photochromic contrast and reversibility; and the photochromic ceramic has fluorescence, can be applied to double anti-counterfeiting, has high anti-counterfeiting precision and is not easy to copy. The application prepares Pr by a high-temperature solid-phase reaction method 3+ Doped BaMgSiO 4 The photochromic ceramic has simple preparation process, short period and simple and cheap raw materials, and is beneficial to industrial large-scale production. The optical device realizes double functions of photochromic anti-counterfeiting and fluorescent anti-counterfeiting by containing the photochromic ceramicThe anti-counterfeiting application has the advantages of large photochromic contrast, high response speed, reversible photochromic behavior, high anti-counterfeiting detection precision and difficult imitation.
Description
Technical Field
The application relates to the field of anti-counterfeiting ceramic materials, in particular to photochromic ceramic, a preparation method thereof and an optical device.
Background
In recent years, photochromic materials have great potential in anti-counterfeiting, information storage and optical switching devices. Photochromic materials can be classified into three major classes, organic, inorganic and organic-inorganic hybrid materials. Compared with organic photochromic materials, inorganic materials have stable physicochemical properties. However, the existing mainstream inorganic photochromic materials still have the defects of small photochromic contrast, low response efficiency, poor fatigue resistance and non-reversibility.
In photochromic material application, such as anti-counterfeiting application, rapid response, high contrast, reversible photochromic and the like are required, repeated detection can be realized, and anti-counterfeiting precision is high. However, most photochromic materials only have photochromic anti-counterfeiting single function and are easy to copy.
Disclosure of Invention
An object of an embodiment of the present application is to provide a photochromic ceramic, a method of preparing the same, and an optical device.
In a first aspect, the present application provides a photochromic ceramic, which is Pr 3+ Doped BaMgSiO 4 。
The photochromic ceramic provided by the application has physical and chemical stability, quick photochromic response, large photochromic contrast and reversibility; and the photochromic ceramic has fluorescence, can be applied to double anti-counterfeiting, has high anti-counterfeiting precision and is not easy to copy.
In other parts of this applicationIn the examples, pr is calculated in terms of molar ratio 3+ The doping amount of the catalyst is 0.1-5 percent.
In other embodiments of the present application, the photochromic ceramic is a sheet that is off-white in its original color.
In other embodiments of the present application, the photochromic ceramic is capable of changing color upon irradiation with ultraviolet light having a wavelength of 250nm to 365nm and then returning to the original color upon irradiation with blue light having a wavelength of 445nm to 455 nm.
In other embodiments of the present application, the photochromic ceramic is capable of changing to pink upon irradiation when the wavelength of the ultraviolet light is between 255nm and 265 nm.
In other embodiments of the present application, the photochromic ceramic is capable of fluorescing under ultraviolet radiation ranging from 270nm to 365 nm; after the irradiation is removed, the photochromic ceramic changes from the original off-white color to pink.
In other embodiments of the present application, the response time of the photochromic ceramic is: 71.6% of the maximum contrast can be reached in 3 seconds.
In other embodiments of the present application, the photochromic ceramic has a maximum discoloration contrast of 68.59%.
In a second aspect, the present application provides a method for preparing a photochromic ceramic, the method comprising:
uniformly mixing a barium source, a magnesium source, a silicon source and a praseodymium source, and calcining to obtain ceramic powder; and then pressing the ceramic powder into a sheet and sintering to obtain the photochromic ceramic sheet.
The application prepares Pr by a high-temperature solid-phase reaction method 3+ Doped BaMgSiO 4 The photochromic ceramic has simple preparation process, short period and simple and cheap raw materials, and is beneficial to industrial large-scale production.
In a third aspect, the present application provides an optical device comprising the aforementioned photochromic ceramic.
The optical device comprises the photochromic ceramic, so that photochromic anti-counterfeiting and fluorescent anti-counterfeiting are used as double anti-counterfeiting applications, the photochromic anti-counterfeiting optical device has the advantages of high photochromic contrast, high response speed and reversible photochromic behavior, and is high in anti-counterfeiting detection precision and difficult to copy.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
FIG. 1 shows BaMgSiO solid particles provided in example 1 of the present application 4 X-ray diffraction patterns of Pr photochromic ceramics;
FIG. 2 is a diagram of BaMgSiO solid particles provided in example 1 of the present application 4 A reflection spectrum and a real object graph of the Pr photochromic ceramic before and after photochromic at 265nm and 450nm (the picture is subjected to gray level processing, the circle on the left in the graph is the original color before the photochromic ceramic changes color and is grey white, and the circle on the right is pink after the photochromic ceramic changes color);
FIG. 3 is a diagram of BaMgSiO provided in example 1 of the present application 4 The photochromic contrast of Pr photochromic ceramic varies with the irradiation time;
FIG. 4 is a diagram of BaMgSiO provided in example 1 of the present application 4 Down-conversion excitation and emission spectrograms of Pr photochromic ceramics;
FIG. 5 is a diagram of BaMgSiO solid particles provided in example 1 of the present application 4 Emission spectra excited by Pr photochromic ceramics at 330nm before and after photochromism;
FIG. 6 is a graph showing the color change contrast Δ R of various photochromic ceramics provided in example 1 of the present application and comparative examples 1 to 4.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments.
Thus, the following detailed description of the embodiments of the present application is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments in the present application without making any creative effort belong to the protection scope of the present application.
The embodiment of the application provides a photochromic ceramic, wherein the photochromic ceramic is Pr 3+ Doped BaMgSiO 4 。
The photochromic ceramic is introduced with rare earth ions Pr 3+ Doping substrate material BaMgSiO 4 And a down-conversion anti-counterfeiting channel is added, and anti-counterfeiting precision is improved. The photochromic liquid crystal display has the advantages of large photochromic contrast, high response speed and reversible photochromic behavior, and can improve the information storage density and increase the storage efficiency if being used for information storage.
Further, in some embodiments of the present application, pr, in terms of mole ratio 3+ The doping amount of the catalyst is 0.1-5 percent.
Further alternatively, in some embodiments herein, pr, in terms of mole ratio, is 3+ The doping amount of the catalyst is 0.2-4.9%. Further alternatively, in some embodiments herein, pr, in terms of mole ratio, is 3+ The doping amount of the catalyst is 0.3-4.8%.
Illustratively, in terms of mole ratio, pr 3+ 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, 3.0%, 3.5%, 4.0%, or 4.5%.
As mentioned above, the photochromic ceramic has the general formula: baMgSiO 4 :xPr 3+ (x＝0.1％-5％)。
Further, in some embodiments herein, the photochromic ceramic is a platelet that is off-white in its original color.
Further, in some embodiments of the present application, the thickness of the photochromic ceramic sheet is in the range of 0.1mm to 50 mm.
Illustratively, the thickness of the above-described photochromic ceramic sheet is 0.5mm, 1mm, 5mm, 10mm, 15mm, 20mm, 25mm, 30mm, 35mm, 40mm, or 45mm.
Further, in some embodiments of the present application, the photochromic ceramic described above is capable of changing color upon irradiation with ultraviolet light having a wavelength of 250nm to 365nm and then returning to an original color upon irradiation with blue light having a wavelength of 445nm to 455 nm.
Further optionally, in some embodiments of the present application, the photochromic ceramic can change color after being irradiated by ultraviolet light with a wavelength of 255nm to 360nm, and then return to the original color after being irradiated by blue light with a wavelength of 446nm to 454 nm.
Illustratively, the photochromic ceramics described above are capable of changing color upon irradiation with ultraviolet light at wavelengths of 260nm, 262nm, 263nm, 264nm, 265nm, 266nm, 267nm, 268nm, 270nm, 280nm, 290nm, 300nm, 310nm, 320nm, 330nm, 340nm or 350nm, and then returning to the original color upon irradiation with blue light at wavelengths of 446nm, 447nm, 448nm, 449nm, 450nm, 451nm, 452nm, 453nm or 454 nm.
Further, in some embodiments of the present application, the photochromic ceramic is capable of changing to pink upon irradiation when the wavelength of the ultraviolet light is between 255nm and 265 nm.
Further, in some embodiments herein, the response time of the photochromic ceramic is: 71.6% of the maximum contrast can be reached in 3 seconds.
Response time (t) is a key parameter of photochromic materials, defined as the fraction of (1-1/e) or how much time is required to reach 63% of the maximum contrast of the photochromic.
Further, in some embodiments of the present application, the photochromic ceramic has a maximum discoloration contrast of 68.59%.
Further, in some embodiments of the present application, the photochromic ceramic is capable of fluorescing upon exposure to ultraviolet radiation ranging from 270nm to 365 nm; after the irradiation is removed, the photochromic ceramic changes from the original off-white color to pink.
Further optionally, in some embodiments of the present application, the photochromic ceramic is capable of fluorescing under ultraviolet radiation ranging from 271nm to 364 nm; after the irradiation is removed, the photochromic ceramic changes from the original off-white color to pink.
Further optionally, in some embodiments herein, the photochromic ceramic is capable of fluorescing when irradiated with ultraviolet light between 272nm and 363 nm; after the irradiation is removed, the photochromic ceramic changes from the original off-white color to pink.
Illustratively, the photochromic ceramic is capable of fluorescing upon ultraviolet 275nm, 280nm, 285nm, 290nm, 295nm, 300nm, 305nm, 310nm, 315nm, 320nm, 325nm, 330nm, 335nm, 340nm, 345nm, 350nm, 355nm, 360nm irradiation; after the irradiation is removed, the photochromic ceramic changes from the original off-white color to pink.
In some embodiments of the present application, the fluorescence is orange-yellow light.
The photochromic ceramic provided by the application has a photochromic range and a down-conversion fluorescence anti-counterfeiting dual anti-counterfeiting material, and can be applied to manufacturing high-security advanced optical anti-counterfeiting materials, high-density optical information storage materials, optical switches and the like.
Some embodiments of the present disclosure provide a method of preparing a photochromic ceramic, the method comprising:
uniformly mixing a barium source, a magnesium source, a silicon source and a praseodymium source, and calcining to obtain ceramic powder; and then pressing the ceramic powder into a sheet and sintering to obtain the photochromic ceramic sheet body.
Further, in some embodiments of the present application, the barium source is selected from barium salts, such as: baCO 3 And the like.
Further, in some embodiments of the present application, the magnesium source is selected from an oxide or a magnesium salt of magnesium, such as: magnesium oxide (MgO).
Further, in some embodiments of the present application, the silicon source is selected from an oxide or a salt of silicon, such as: silicon dioxide (SiO) 2 )。
Further, in some embodiments of the present application, the praseodymium source is selected from oxides of praseodymium, such as: praseodymium oxide (Pr) 6 O 11 )。
Further, in some embodiments of the present application, the step of uniformly mixing the barium source, the magnesium source, the silicon source, and the praseodymium source includes:
according to a molar ratio of Ba, mg, si and Pr of 1<m is less than or equal to 5.0 percent; further selecting m between 0.1% and 5.0%; barium carbonate(Ba 2 CO 3 ) Magnesium oxide (MgO), silicon dioxide (SiO) 2 ) Praseodymium oxide (Pr) 6 O 11 ) Accurately weighing, and then ball-milling uniformly.
Further, in some embodiments of the present application, during the ball milling, ethanol and a dispersant are further added to each raw material, and further optionally, the ball milling time is 20 to 30 hours, and further optionally, the ball milling time is 24 hours.
Illustratively, a proper amount of ethanol and a dispersant are added to all weighed raw materials, and the mixture is placed in a ball milling tank and ball milled for 24 hours.
Further, in some embodiments of the present application, the ball milled homogeneous blend is dried.
Illustratively, in some embodiments of the present application, the ball-milled slurry is transferred to a glass dish and dried in an oven.
Further, in some embodiments herein, calcining comprises:
and calcining the uniformly mixed and dried raw material mixture at 800-1000 ℃ for 2-4 h.
Further optionally, calcining the uniformly mixed and dried raw material mixture at 810-950 ℃ for 2.5-3.5 h.
Illustratively, the raw material mixture obtained by uniformly mixing and drying is calcined at 820 ℃, 850 ℃, 880 ℃, 900 ℃, 920 ℃ or 940 ℃ for 2.5h, 2.8h, 3h, 3.2h or 3.4h.
Further, in some embodiments of the present application, pressing the ceramic powder into a tablet comprises:
and grinding and sieving the calcined powder, pressing into a biscuit by adopting dry pressing, and then cooling for 60-240 s at 240Mpa in a cold isostatic press.
By sieving the ceramic powder obtained by calcination, the oversize or undersize particles and possible impurities are removed, so that the subsequent crystallinity can be improved.
Further optionally, the calcined powder is ground, sieved, pressed into a biscuit by dry pressing, and then cooled at 240MPa for 70-230 s in a cold isostatic press. Illustratively, the calcined good powder is ground, sieved, pressed into a biscuit using dry compaction, and then cold-pressed at 240MPa for 70s-230s in a cold isostatic press.
Further, in some embodiments of the present application, the step of sintering comprises:
sintering the pressed flaky bodies at 1200-1400 ℃ for 1-5 h.
Further optionally, the step of sintering comprises:
sintering the pressed tablet body at 1250-1350 ℃ for 1.5-4.5 h.
Illustratively, the aforementioned compressed tablet bodies are sintered at 1260 ℃, 1280 ℃, 1300 ℃, 1320 ℃, or 1340 ℃ for 1.5h, 2h, 2.5h, 3h, 3.5h, or 4h.
In some embodiments of the present application, the formed biscuit is placed into a tube furnace to prepare Pr by sintering at 1200-1400 ℃ for 1-5h with 5% nitrogen-hydrogen mixed gas 3+ Doped BaMgSiO 4 Photochromic ceramics.
The application prepares Pr by a high-temperature solid-phase reaction method 3+ Doped BaMgSiO 4 The photochromic ceramic has simple preparation process, short period and simple and cheap raw materials, and is beneficial to industrial large-scale production.
Some embodiments of the present application provide an optical device comprising a photochromic ceramic as provided in any of the preceding embodiments.
The optical device comprises the photochromic ceramic, so that photochromic anti-counterfeiting and fluorescent anti-counterfeiting are used as dual anti-counterfeiting applications, the photochromic anti-counterfeiting and fluorescent anti-counterfeiting optical device has the advantages of high photochromic contrast, high response speed and reversible photochromic behavior, and is high in anti-counterfeiting detection precision and difficult to imitate.
The scheme of the present application is further described in detail below with reference to examples:
example 1
Providing a photochromic ceramic, which is prepared according to the following steps:
(a) Weighing: weighing BaCO at molar ratio of Ba, mg, si and Pr of 1: 0.02 3 、MgO、SiO 2 And Pr 6 O 11 Mixing the powder with ethanol and oleic acid to obtainTo a mixture;
(b) Ball milling: adding ethanol and ball-milling medium zirconium oxide balls into the mixture obtained in the step (a), mixing, placing in an agate ball-milling tank, and ball-milling for 24 hours; wherein the mass ratio of ethanol to the mixture is 1.2: 1, the pellet/pellet ratio is 1: 3, and the ratio of the large pellet to the small pellet is 1: 1. And transferring the slurry subjected to ball milling to a glass culture dish, and drying in an oven at 60 ℃.
(c) And (3) calcining: and (c) grinding the dried material in the step (b) in an agate mortar, placing the ground material in a sealed alumina crucible, and calcining the ground material in a box-type furnace at 1000 ℃ for 4 hours.
(d) Tabletting: and (d) regrinding the calcined material in the step (c), pre-pressing the powder into slices by using a tablet press under the pressure of 3MPa, wrapping the slices, placing the slices in a cold isostatic press, and maintaining the pressure for 2min under the pressure of 200MPa to obtain the ceramic wafer.
(e) And (3) sintering: putting the biscuit obtained in the step (d) into a tubular furnace, introducing 5% of nitrogen and hydrogen, mixing, sintering at 1350 ℃ for 2h, cooling to room temperature, and taking out to obtain Pr-doped BaMgSiO 4 Photochromic ceramics: baMgSiO 4 2% of Pr. The doping amount of Pr in the ceramic is 2 percent in molar ratio.
Example 2
A photochromic ceramic was provided, the same procedure as in example 1, except that: (a) The molar ratio of Ba, mg, si and Pr in the steps is 1: 0.001. The prepared photochromic ceramic comprises the following components: baMgSiO 4 0.1% Pr, in a molar ratio, the amount of Pr doped in the ceramic being 0.1%.
Example 3
A photochromic ceramic was provided, the same procedure as in example 1, except that: (a) The molar ratio of Ba, mg, si and Pr in the steps is 1: 0.05. The prepared photochromic ceramic comprises the following components: baMgSiO 4 5% Pr, in a molar ratio, the amount of Pr doped in the ceramic is 5%.
Comparative example 1
A photochromic ceramic was provided, the same procedure as in example 1, except that: (a) In the step, pr is not doped, and the photochromic ceramic BaMgSiO is prepared 4 。
Comparative example 2
A photochromic ceramic was provided, the same procedure as in example 1, except that: and (a) replacing the doped element Pr with Eu in the step. Then the photochromic ceramic BaMgSiO is prepared 4 :Eu。
Comparative example 3
A photochromic ceramic was provided, the same procedure as in example 1, except that: and (a) replacing the doping element Pr with Bi in the step. The photochromic ceramic BaMgSiO is prepared 4 :Bi。
Comparative example 4
A photochromic ceramic was provided, the same procedure as in example 1, except that: and (a) replacing the doping element Pr by Nd in the step. The photochromic ceramic BaMgSiO is prepared 4 :Nd。
Experimental example 1
The photochromic ceramics obtained in example 1 were examined by X-ray diffraction.
The X-ray diffraction pattern is shown in figure 1. It can be seen from FIG. 1 that the Pr-doped ceramic prepared is of Fm-3m structure.
Experimental example 2
The photochromic ceramic prepared in example 1 was examined by an ultraviolet spectrophotometer.
The results of the detection are shown in FIG. 2.
FIG. 2 shows BaMgSiO solid particles provided in example 1 of the present invention 4 Pr photochromic ceramic photochromic spectrum. As can be seen from the figure, the simultaneous irradiation of ultraviolet ray 265nm for 1s changes the ceramic coloring from the original grey white color to pink color, and the response speed is clearly visible to naked eyes; the sample can be bleached by irradiation of visible light of 450nm, the reversibility is good, and the color change contrast delta R can reach 68.59%.
Thus, the BaMgSiO provided by the application 4 Pr photochromic ceramics have reversible photochromic properties.
The photochromic ceramics obtained in example 1 and comparative examples 1 to 4 were compared in terms of color change contrast Δ R, as shown in fig. 6.
The method for calculating the color-changing contrast delta R comprises the following steps: Δ R = (R0-R1)/R0, and R0 and R1 are reflectance of the photochromic material before and after irradiation, respectively.
As can be seen from FIG. 6, baMgSiO produced by the present application 4 Pr photochromic ceramic is greater than the photochromic contrast DeltaR of the photochromic ceramics obtained in comparative examples 1-4.
Thus, the BaMgSiO provided by the application 4 The Pr photochromic ceramic has high color change contrast delta R.
Experimental example 3
The response time of the photochromic ceramic provided in example 1 was examined. The results are shown in FIG. 3.
FIG. 3 is a diagram of BaMgSiO provided in example 1 of the present application 4 The variation of the Pr photochromic ceramic contrast with the irradiation time, the response time (t) is a key parameter of photochromic materials and is defined as the fraction (1-1/e) or how much time is required to reach 63% of the maximum contrast of the photochromic. As can be seen from FIG. 3, baMgSiO of the present application 4 The Pr photochromic ceramic can reach 71.6 percent of the maximum contrast within 3 seconds, and the response speed is extremely high.
Experimental example 4
The fluorescence of the photochromic ceramics provided in example 1 was examined. The results are shown in FIG. 4.
FIG. 4 is a BaMgSiO solid provided in example 1 of the present application 4 A down-conversion excitation and emission spectrum of Pr photochromic ceramics. As can be seen from the figure, baMgSiO provided in example 1 of the present application 4 Pr photochromic ceramic has a certain fluorescence emission under 330nm excitation, showing 600nm orange-yellow light.
Experimental example 5
The photochromic ceramics provided in example 1 were examined for their properties before and after discoloration. The results are shown in FIG. 5.
FIG. 5 is a diagram of BaMgSiO provided in example 1 of the present application 4 Pr emission spectra excited at 330nm before and after photochromism. As can be seen from the graph, the fluorescence intensity Δ Rl was reduced by 79.1% in comparison with the fluorescence emission spectrum of the ceramic before and after the irradiation of the ultraviolet ray 265 nm. The method for calculating the fluorescence intensity delta Rl comprises the following steps: Δ Rl = (Rl 0-Rl 1)/Rl 0, where Rl0 and Rl1 are fluorescence intensities of the photochromic material before and after irradiation, respectively. ByThis specification, baMgSiO provided by the present application 4 Pr photochromic ceramics have a high fluorescence intensity contrast.
In conclusion, the BaMgSiO provided by the application 4 Pr photochromic ceramics, which has the photochromic behavior of large contrast, fast response and reversibility; the anti-counterfeiting paper integrates fluorescence anti-counterfeiting, can realize double anti-counterfeiting, and solves the problems of high cost, poor confidentiality and the like of the existing anti-counterfeiting technology.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. The photochromic ceramic is characterized in that the photochromic ceramic is Pr 3+ Doped BaMgSiO 4 。
2. The photochromic ceramic of claim 1 wherein,
in terms of molar ratio, the Pr 3+ The doping amount of the catalyst is 0.1-5 percent.
3. The photochromic ceramic of claim 1 wherein,
the photochromic ceramic is a sheet body with the original grey color.
4. The photochromic ceramic of any one of claims 1 to 3 wherein,
the photochromic ceramic can change color after being irradiated by ultraviolet rays with the wavelength of 250nm-365nm and then restore to the original color after being irradiated by blue light with the wavelength of 445nm-455 nm.
5. The photochromic ceramic of claim 4 wherein,
when the wavelength of the ultraviolet light is 255nm-265nm, the photochromic ceramic can turn pink after being irradiated.
6. The photochromic ceramic of claim 1 wherein,
the photochromic ceramic can emit fluorescence under the irradiation of ultraviolet rays of 270nm to 365 nm; upon removal of the irradiation, the photochromic ceramic changes from an original off-white color to a pink color.
7. The photochromic ceramic of claim 1 wherein,
the response time of the photochromic ceramic is: 71.6% of the maximum contrast can be reached in 3 seconds.
8. The photochromic ceramic of claim 1 wherein,
the photochromic ceramic has a maximum discoloration contrast of 68.59%.
9. The method for preparing a photochromic ceramic according to any one of claims 1 to 8, comprising:
uniformly mixing a barium source, a magnesium source, a silicon source and a praseodymium source, and calcining to obtain ceramic powder; and then pressing the ceramic powder into a sheet and sintering to obtain the photochromic ceramic sheet body.
10. An optical device comprising the photochromic ceramic of any one of claims 1 to 8.
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