CN111004031B - Optical storage material and preparation method thereof - Google Patents
Optical storage material and preparation method thereof Download PDFInfo
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Abstract
An optical storage material comprising the structure ABO3The perovskite lead-free ferroelectric ceramic material with the structure is characterized in that: the chemical formula of the lead-free ferroelectric ceramic material is Bi0.495‑xNa0.5TiO30.005Ho-xYb, wherein x is more than or equal to 0.005 and less than or equal to 0.05, by adding 0.005 mol content of rare earth element Ho in the A position3+And x mole content of a rare earth element Yb3+And thus optical storage of the material. The invention also discloses a preparation method of the optical storage material. Compared with the prior art, the invention can realize optical storage and has stable storage signals.
Description
Technical Field
The invention belongs to the technical field of optical storage materials, and particularly relates to an optical storage material and a preparation method thereof.
Background
Photochromic materials are materials that change color when irradiated by a light source. The traditional photochromic material mainly changes the structure of a light irradiation material, so that the color is changed, and comprises an inorganic photochromic material and an organic photochromic material, wherein the inorganic photochromic material mainly comprises tungsten oxide, bromide and the like and has no fluorescence luminescence property; although the organic photochromic material can emit light, it has poor thermal stability and corrosion resistance. These deficiencies limit their widespread use.
The traditional optical storage method is mainly characterized in that rare earth is added into a photochromic material, the luminous intensity of the luminescent material of the rare earth is obviously changed before and after light irradiation, and the two luminous intensities can be used as ' 0 ' 1 ' of information storage, so that the luminescent material can be used as an optical storage material, for example, documents [ J.Mater.chem.C,2017,5, 3838-. The absolute intensity of fluorescence is very sensitive to the surface roughness of the material, a detection system, an optical path and the like, which causes the storage signal to be very unstable.
ABO3Perovskite lead-free ferroelectric ceramics of type structure such as Na0.5Bi0.5TiO3Is a lead-free ferroelectric material with very stable physicochemical properties, and is generally considered as a potential material for replacing a lead-containing PZT piezoelectric material. Na (Na)0.5Bi0.5TiO3During the high-temperature sintering process, Na and Bi ions volatilize to form a plurality of inherent point defects, such as oxygen vacancy, Na/Bi vacancy, exciton and the like, and the defects have important influence on the electrical and fluorescent properties of the material. Due to the existence of the defects, defect energy levels are introduced between a conduction band and a valence band of the material, so that Na is introduced0.5Bi0.5TiO3Becoming a potential photochromic material. By using Na0.5Bi0.5TiO3The characteristics of (2) make it a certain significance for the optical storage material to be stable in storage signals.
Disclosure of Invention
The first technical problem to be solved by the present invention is to provide an optical storage material for improving the stability of stored signals by applying photochromic materials to optical storage, aiming at the current state of the prior art.
The second technical problem to be solved by the present invention is to provide a method for preparing the above optical storage material.
The technical scheme adopted by the invention for solving the first technical problem is as follows: an optical storage material comprising the structure ABO3The perovskite lead-free ferroelectric ceramic material with the structure is characterized in that: the chemical formula of the lead-free ferroelectric ceramic material is Bi0.495-xNa0.5TiO30.005Ho-xYb, wherein x is more than or equal to 0.005 and less than or equal to 0.05, by adding 0.005 mol content of rare earth element Ho in the A position3+And x mole content of a rare earth element Yb3+And thus optical storage of the material.
Further, said Bi0.495-xNa0.5TiO30.005Ho-xYb produces a visible 546 nm green light, a 656 nm red light, and an invisible 757 nm near-infrared light when excited by a 980nm wavelength laser.
Further, said Bi0.495-xNa0.5TiO30.005Ho-xYb material after 405nm light irradiation, and excited by 980nm light, the intensity I at 546 nm before irradiation546Intensity at 757 nm I757Ratio R betweenonGreater than the intensity I at 546 nm after irradiation546Intensity at 757 nm I757Ratio R betweenoffThe ratio is used as the storage signal.
Excitation infrared light of 980nm to the Bi0.495-xNa0.5TiO3The storage signal of the 0.005Ho-xYb material has no effect. The optical storage material can stably store signals.
In the above scheme, the Bi0.495-xNa0.5TiO30.005Ho-xYb material is irradiated by 405nm light or sunlight, the color is changed from light yellow to gray, and Bi is excited by 980nm light0.495-xNa0.5TiO30.005Ho-xYb material emits a decrease in the intensity of visible light.
The Bi0.495-xNa0.5TiO30.005Ho-xYb material is irradiated by 405nm light or sunlight, and then heated to restore the color to light yellow, and Bi is excited by 980nm light0.495-xNa0.5TiO30.005Ho-xYb material emits visible light with restored intensity.
Excitation infrared light of 980nm to the Bi0.495-xNa0.5TiO3The color of the 0.005Ho-xYb material had no effect.
The technical scheme adopted by the invention for solving the second technical problem is as follows: a method for preparing an optical storage material as described above, characterized by comprising the steps of:
adopts Bi2O3，Na2CO3，TiO2，Yb2O3，Ho2O3Is used as a raw material and is Bi according to a chemical formula0.495-xNa0.5TiO30.005Ho-xYb, and weighing and proportioning the components according to the stoichiometric ratio of Na, Bi, Ti, Yb and Ho; then ball milling and mixing are carried out, and the ball milling and mixing are carried outVolume of raw materials in the synthesis: agate sphere volume: the volume ratio of the ball milling medium absolute ethyl alcohol is 1: 1-1.2: 1 to 1.5; drying and tabletting the raw materials subjected to ball milling for 2-15 hours, wherein the pressure of tabletting is 5-120 Mpa; keeping the temperature of the pressed green blank at 750-850 ℃ for 1-3 hours to synthesize the Bi with the perovskite structure0.495-xNa0.5TiO30.005Ho-xYb embryo body;
② preparing Bi obtained in the step I0.495-xNa0.5TiO30.005Ho-xYb grinding and ball milling for 5-12 hours, drying after ball milling to obtain Bi0.495-xNa0.5TiO30.005Ho-xYb drying the powder;
thirdly, Bi obtained in the step two0.495-xNa0.5TiO30.005Ho-xYb adding 3-5% polyvinyl alcohol water solution into the dried powder as a binder for granulation, wherein the volume of the polyvinyl alcohol water solution added per 10g of the dried powder is 1-2 ml; pressing the granulated powder under 100-200 MPa for sheet forming; then, preserving the heat at 650-800 ℃ for 2-4 hours to decompose the binder; then preserving the heat for 2-4 hours at 1050-1200 ℃, and finally obtaining the Bi ceramic wafer0.495-xNa0.5TiO30.005Ho-xYb lead-free ferroelectric ceramic material.
And in the step three, the binder is preferably granulated by fully mixing the dried powder and the polyvinyl alcohol aqueous solution in a mortar and then sieving the mixture through a 80-mesh sieve.
Compared with the prior art, the invention has the advantages that: before and after irradiation, Na0.5Bi0.5TiO3The reflectivity change of the material is highly dependent on the wavelength in the visible wavelength range. By reacting with Na0.5Bi0.5TiO3Adding rare earth ion Yb into the material3+And Ho3+Rare earth ion Ho3+In the sensitizer Yb3+Under the action of the light source, the light emitting of green light, red light and near infrared light can be realized, the change of the intensity ratio of the light after the ultraviolet light irradiation and before the irradiation is used as a signal, the optical storage can be realized, and the storage signal is stable.
The preparation method is simple, and all chemical reactions are carried out in the air; the cost of the required raw materials is low, and the prepared product has good stability in regulating and controlling the color and the luminous intensity, and is suitable for optical storage materials.
Drawings
FIG. 1 shows Bi in the first embodiment of the present invention0.495-xNa0.5TiO30.005Ho-xYb material X-ray diffraction pattern;
FIG. 2 shows Bi in the first embodiment of the present invention0.495-xNa0.5TiO30.005Ho-xYb material by scanning electron microscopy;
FIG. 3 shows Bi in the first embodiment of the present invention0.495-xNa0.5TiO30.005Ho-xYb material before and after 405nm light irradiation;
FIG. 4 shows Bi in the first embodiment of the present invention0.495-xNa0.5TiO30.005Ho-xYb material reflection spectrum under 980nm light excitation;
FIG. 5 shows Bi in the second embodiment of the present invention0.495-xNa0.5TiO30.005Ho-xYb material X-ray diffraction pattern;
FIG. 6 shows Bi in the second embodiment of the present invention0.495-xNa0.5TiO30.005Ho-xYb material has a reflection spectrum under excitation of 980nm light before and after irradiation with 405nm light.
Detailed Description
The invention is described in further detail below with reference to the accompanying examples.
The first embodiment is as follows:
bi with the purity of 99.5 percent is adopted2O399.8% of Na2CO399.0% TiO299.9% of Yb2O399.9% Ho2O3As a raw material, according to Bi0.49Na0.5TiO3Weighing 0.005Ho-0.005Yb in a metering ratio, putting the weighed materials into a ball milling tank for mixing and ball milling, wherein the ball milling conditions are as follows: the volume ratio of the raw materials to the agate balls to the absolute ethyl alcohol of the ball-milling medium is equal to 1: 1: 1.5, ball-milling for 12 hours, and putting the ball-milled raw materials into an oven to be dried for 4 hours at the temperature of 80 ℃. Then, the dried raw material is processed at 20Mp by a tablet pressa, pressing the raw materials into green bodies with the diameter of 40mm, then putting the pressed green bodies into a KBF1400 box type furnace for presintering, preserving the temperature for 2 hours under the presintering condition of 800 ℃, then grinding the presintering blocky samples into powder, sieving the powder, carrying out ball milling on the powder for 12 hours, putting the powder into an oven for drying at 80 ℃ for 4 hours again, and obtaining the dried powder. Finally, grinding the dried powder according to the proportion of adding 1ml of binder (the binder is polyvinyl alcohol aqueous solution with the mass concentration of 3%) into 10g of powder, granulating, sieving for 3 times by using a 80-mesh sieve, pressing the ground powder into small pieces with the diameter of 10mm under the pressure of 150MPa, preserving the temperature at 650 ℃ for 2 hours to decompose the binder polyvinyl alcohol, and dissolving the polyvinyl alcohol in Al2O3And (3) laying mother powder on the gasket, covering the pressed small pieces with the mother powder, and sintering the small pieces in a box-type furnace under the sintering condition of 1200 ℃ for 4 hours.
Bi to be sintered0.49Na0.5TiO30.005Ho-0.005Yb ceramic, the results of which are shown in FIGS. 1-4. From FIG. 1, Bi can be seen0.49Na0.5TiO30.005Ho-0.005Yb material is pure perovskite structure. FIG. 2 shows Bi0.49Na0.5TiO30.005Ho-0.005Yb ceramic material has high compactness. Fig. 3 shows that the reflectance of the ceramic is significantly reduced after irradiation, and the emissivity change before and after irradiation is the largest near 600 nm without significant changes in the ultraviolet region and near infrared region, which shows that the reflectivity of the ceramic can be significantly changed by irradiation, and that such emissivity change has a large dependence on wavelength. FIG. 4 shows that the ceramic has 3 emission peaks at 546 nm, 656 nm and 757 nm.
The ceramic prepared in this example showed a significant decrease in luminous intensity after 3 minutes of 405nm light irradiation, and the modulation Δ R at 546 nm was calculatedt(ΔRt＝(R0–Rt)/R0×100(％)，R0The luminous intensity of the sample before irradiation, RtLuminous intensity of the sample after irradiation) reached 33%, modulation ratio deltar at 656 nmtReaches 18 percent, and the modulation rate delta R at 757 nanometerstReaching 13 percent. And at 98Intensity I at 546 nm before irradiation under excitation of 0nm light546Intensity at 757 nm I757Ratio R betweenonIntensity I at 546 nm after irradiation 29546Intensity at 757 nm I757Ratio R betweenoffThis ratio is used as a stored signal 23. And 980nm excitation infrared light has no influence on the storage signal.
Meanwhile, after the ceramic prepared in the embodiment is irradiated by 405nm light or sunlight, the color is changed from light yellow to gray, the color is restored to light yellow by heating at 200 ℃, and the intensity of the emitted visible light is restored under the excitation of 980nm light. The 980nm excitation infrared light has no effect on the color of the ceramic material.
Example two:
basically the same as the first embodiment except that the embodiment is based on Bi0.48Na0.5TiO30.005Ho-0.015Yb is weighed according to the metering ratio to prepare Bi0.48Na0.5TiO30.005Ho-0.015Yb ceramic.
Similarly, Bi obtained in this example was used0.48Na0.5TiO30.005Ho-0.015Yb ceramic was tested in relation to the test structure shown in FIGS. 5 and 6. FIG. 5 shows Bi0.48Na0.5TiO30.005Ho-0.015Yb material is pure perovskite structure. Fig. 6 shows that after irradiation with 405nm light, the ceramic exhibits a significant decrease in emission intensity at 546 nm and 656 nm, while the variation in emission intensity at 757 nm is small, specifically: the luminescence intensity at 546 nm was reduced to 66% before irradiation, the luminescence intensity at 656 nm was reduced to 71% before irradiation, and the luminescence intensity at 757 nm after irradiation was reduced to 76% before irradiation.
And intensity I at 546 nm before irradiation546Intensity at 757 nm I757Ratio R betweenon23, intensity I at 546 nm after irradiation546Intensity at 757 nm I757Ratio R betweenoffWith this ratio, the signal can be stored 19. I.e. intensity I at 546 nm before irradiation546And 757 nm positionStrength I of757Ratio R betweenonSpecific value of R after irradiationoffIs large. And 980nm excitation infrared light has no influence on the storage signal.
Similarly, the color of the ceramic prepared in the embodiment is changed from light yellow to gray after being irradiated by 405nm light or sunlight, the color is restored to light yellow by heating at 200 ℃, and the intensity of the emitted visible light is restored under the excitation of 980nm light. The 980nm excitation infrared light has no effect on the color of the ceramic material.
Example three:
basically the same as the first embodiment except that the embodiment is based on Bi0.485Na0.5TiO3Weighing 0.005Ho-0.01Yb in a ratio to obtain Bi0.485Na0.5TiO30.005Ho-0.01Yb ceramic. The prepared ceramic has a pure perovskite structure.
Bi obtained in this example0.485Na0.5TiO30.005Ho-0.01Yb ceramic was tested and found to decrease in intensity at 546 nm, 656 nm and 757 nm after 405nm light irradiation, but not at the same magnitude, specifically: the luminous intensity at 546 nm after irradiation was reduced to 64% before irradiation, and the luminous intensity at 757 nm after irradiation was reduced to 80% before irradiation. Intensity I at 546 nm before irradiation546Intensity at 757 nm I757Ratio R betweenonIntensity I at 546 nm after irradiation 26546Intensity at 757 nm I757Ratio R betweenoffWith this ratio, a signal can also be stored 20. And 980nm excitation infrared light has no influence on the storage signal.
Similarly, the color of the ceramic prepared in the embodiment is changed from light yellow to gray after being irradiated by 405nm light or sunlight, the color is restored to light yellow by heating at 200 ℃, and the intensity of the emitted visible light is restored under the excitation of 980nm light. The 980nm excitation infrared light has no effect on the color of the ceramic material.
Example four:
bi with the purity of 99.5 percent is adopted2O399.8% of Na2CO399.0% of TiO299.9% of Yb2O399.9% Ho2O3As a raw material, according to Bi0.445Na0.5TiO3Weighing 0.005Ho-0.05Yb in a metering ratio, putting the weighed materials into a ball milling tank, and mixing and ball milling the materials under the ball milling conditions: the volume ratio of the raw materials to the agate balls to the absolute ethyl alcohol of the ball-milling medium is equal to 1: 1.2: 1, ball-milling the raw materials for 15 hours, and putting the ball-milled raw materials into an oven to be dried for 4 hours at the temperature of 80 ℃. Then, pressing the dried raw materials into raw material blanks with the diameter of 40mm by a tablet machine under the pressure of 120Mpa, then putting the pressed raw blanks into a KBF1400 box type furnace for presintering, preserving the presintering condition for 1 hour at the temperature of 850 ℃, then crushing the presintering blocky samples, grinding the samples into powder, sieving the powder, carrying out ball milling for 5 hours, putting the powder into an oven for drying at the temperature of 80 ℃ for 4 hours again, and obtaining the dried powder. Finally, grinding the dried powder according to the proportion of 10g of powder and 2ml of binder (the binder is polyvinyl alcohol aqueous solution with the mass concentration of 5 percent), granulating, sieving for 3 times by using a 80-mesh sieve, pressing the ground powder into small pieces with the diameter of 10mm under the pressure of 100MPa, preserving the temperature at 700 ℃ for 3 hours to decompose the binder polyvinyl alcohol, and dissolving the polyvinyl alcohol in Al2O3Laying mother powder on the gasket, covering the pressed small pieces with the mother powder, sintering the small pieces in a box-type furnace under the sintering condition of 1050 ℃ for 2 hours, and finally obtaining the ceramic piece which is Bi0.445Na0.5TiO30.005Ho-0.05Yb lead-free ferroelectric ceramic material.
Example five:
bi with the purity of 99.5 percent is adopted2O399.8% of Na2CO399.0% TiO299.9% of Yb2O399.9% Ho2O3As a raw material, according to Bi0.47Na0.5TiO3Weighing 0.005Ho-0.025Yb in a metering ratio, and putting the weighed materials into a ball milling tank for mixing and ball milling, wherein the ball milling conditions are as follows: the volume ratio of the raw materials to the agate balls to the absolute ethyl alcohol of the ball-milling medium is equal to 1: 1.1: 1.2, ball-milling the raw materials for 2 hours, and putting the ball-milled raw materials into an oven to be dried for 4 hours at the temperature of 80 ℃. Then, the dried raw materials are pressedPressing the raw material into a raw blank with the diameter of 40mm by a sheet machine under the pressure of 5Mpa, then presintering the pressed raw blank in a KBF1400 box type furnace under the presintering condition of 750 ℃ for 3 hours, then grinding the presintering block sample into powder, sieving, ball-milling the powder for 9 hours, and putting the powder into an oven to dry for 4 hours at the temperature of 80 ℃ again to obtain the dried powder. Finally, grinding the dried powder according to the proportion of 10g of powder and 1.5ml of binder (the binder is polyvinyl alcohol aqueous solution with the mass concentration of 4%), granulating, sieving for 3 times by using a 80-mesh sieve, pressing the ground powder into small pieces with the diameter of 10mm under 200MPa, preserving the temperature at 800 ℃ for 4 hours to decompose the binder polyvinyl alcohol, and dissolving the polyvinyl alcohol in Al2O3Laying mother powder on the gasket, covering the pressed small pieces with the mother powder, sintering in a box furnace under the sintering condition of 1100 ℃ for 3 hours to finally obtain the Bi ceramic chip0.47Na0.5TiO30.005Ho-0.025Yb lead-free ferroelectric ceramic material.
Claims (3)
1. An optical storage material comprising the structure ABO3The perovskite lead-free ferroelectric ceramic material with the structure is characterized in that: the chemical formula of the lead-free ferroelectric ceramic material is Bi0.495-xNa0.5TiO30.005Ho-xYb, wherein x is more than or equal to 0.005 and less than 0.05, by adding 0.005 mol content of rare earth element Ho in the A position3+And x mole content of a rare earth element Yb3+Further realizing optical storage of the material;
the Bi0.495-xNa0.5TiO30.005Ho-xYb material under the excitation of 980nm wavelength laser, producing visible 546 nm green light, 656 nm red light and invisible 757 nm near infrared light;
the Bi0.495-xNa0.5TiO30.005Ho-xYb material after 405nm light irradiation, and excited by 980nm light, the intensity I at 546 nm before irradiation546Intensity at 757 nm I757Ratio R betweenonGreater than the intensity I at 546 nm after irradiation546Intensity at 757 nm I757Ratio R betweenoffUsing the ratio asTo store the signal;
excitation infrared light of 980nm to the Bi0.495-xNa0.5TiO30.005Ho-xYb material has no effect on the storage signal;
the Bi0.495-xNa0.5TiO30.005Ho-xYb material is irradiated by 405nm light or sunlight, the color is changed from light yellow to gray, and Bi is excited by 980nm light0.495-xNa0.5TiO30.005Ho-xYb material emits a decrease in the intensity of visible light;
excitation infrared light of 980nm to the Bi0.495-xNa0.5TiO30.005Ho-xYb has no influence on the color of the material;
the preparation method of the optical storage material comprises the following steps:
adopts Bi2O3，Na2CO3，TiO2，Yb2O3，Ho2O3Is used as a raw material and is Bi according to a chemical formula0.495-xNa0.5TiO30.005Ho-xYb, and weighing and proportioning the components according to the stoichiometric ratio of Na, Bi, Ti, Yb and Ho; then ball-milling and mixing are carried out, wherein the volume of the raw materials in the ball-milling and mixing process is as follows: agate sphere volume: the volume ratio of the ball milling medium absolute ethyl alcohol is 1: 1-1.2: 1 to 1.5; drying and tabletting the raw materials subjected to ball milling for 2-15 hours, wherein the pressure of tabletting is 5-120 Mpa; keeping the temperature of the pressed green blank at 750-850 ℃ for 1-3 hours to synthesize the Bi with the perovskite structure0.495-xNa0.5TiO30.005Ho-xYb embryo body;
② preparing Bi obtained in the step I0.495-xNa0.5TiO30.005Ho-xYb grinding and ball milling for 5-12 hours, drying after ball milling to obtain Bi0.495-xNa0.5TiO30.005Ho-xYb drying the powder;
thirdly, Bi obtained in the step two0.495-xNa0.5TiO30.005Ho-xYb adding 3-5% polyvinyl alcohol water solution into the dried powder as a binder for granulation, wherein the volume of the polyvinyl alcohol water solution added per 10g of the dried powder is 1-2 ml; after granulationThe powder is pressed into sheets under 100-200 MPa for molding; then, preserving the heat at 650-800 ℃ for 2-4 hours to decompose the binder; then preserving the heat for 2-4 hours at 1050-1200 ℃, and finally obtaining the Bi ceramic wafer0.495-xNa0.5TiO30.005Ho-xYb lead-free ferroelectric ceramic material.
2. An optical storage material as claimed in claim 1, wherein: the Bi0.495-xNa0.5TiO30.005Ho-xYb material is irradiated by 405nm light or sunlight, and then heated to restore the color to light yellow, and Bi is excited by 980nm light0.495-xNa0.5TiO30.005Ho-xYb material emits visible light with restored intensity.
3. An optical storage material as claimed in claim 1, wherein: and the binder granulation in the step III is to fully mix the dried powder and the polyvinyl alcohol aqueous solution in a mortar and then pass through a 80-mesh sieve.
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