CN111153698A - Transparent ferroelectric ceramic material and preparation method and application thereof - Google Patents

Transparent ferroelectric ceramic material and preparation method and application thereof Download PDF

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CN111153698A
CN111153698A CN202010046966.4A CN202010046966A CN111153698A CN 111153698 A CN111153698 A CN 111153698A CN 202010046966 A CN202010046966 A CN 202010046966A CN 111153698 A CN111153698 A CN 111153698A
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sintering
raw material
treatment
ferroelectric ceramic
ball milling
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CN111153698B (en
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王�华
胡岗斌
刘浩男
许积文
汪江婷
曾卫东
王名昌
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Guilin University of Electronic Technology
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Abstract

The invention provides a transparent ferroelectric ceramic material and a preparation method and application thereof, belonging to the technical field of ceramic materials. The transparent ferroelectric ceramic material provided by the invention has a chemical composition shown in formula I: (1-x) K0.5Na0.5NbO3‑xSr(Yb0.5Ta0.5)O3The formula I, wherein x is 0.01-0.06. The invention provides a transparent ferroelectric ceramic material with K0.5Na0.5NbO3The (KNN) ferroelectric ceramic is used as a substrate, and a second component Sr (Yb) is dissolved in a solid solution0.5Ta0.5)O3Then, the ceramic material has transparent property; meanwhile, the solid solution ratio of the second component is regulated and controlled, so that the structure of the transparent ferroelectric ceramic material is compact, and the light transmittance of the transparent ferroelectric ceramic material is effectively improved. The invention providesThe transparent ferroelectric ceramic material has excellent light transmittance and ferroelectric properties.

Description

Transparent ferroelectric ceramic material and preparation method and application thereof
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a transparent ferroelectric ceramic material and a preparation method and application thereof.
Background
The ferroelectric ceramic has excellent dielectric, ferroelectric, piezoelectric, energy storing, thermoelectric and electrooptical effects, and may be used widely in various electronic functional devices. The transparent ferroelectric ceramic has the inherent advantages of transparent ceramics, and also has the multifunctional characteristics of ferroelectric, piezoelectric, photoelectric and the like. Lead-based transparent ferroelectric ceramic materials such as lead bismuth zirconate titanate ferroelectric ceramic (PBZT), lanthanum lead zirconate titanate ferroelectric ceramic (PLZT), lead lanthanum lead hafnate ferroelectric ceramic (PLHT), and the like, have been widely used in the production of electro-optical devices due to their excellent properties such as high photoelectric effect, fast response speed, low cost, and the like. However, the lead-based transparent ferroelectric ceramic contains heavy metal Pb, which is harmful to the environment and human body.
The lead-free transparent ferroelectric ceramic is safe and environment-friendly to the environment and human body, and is highly concerned by extensive researchers. Chinese patent application CN110041074A discloses an up-conversion luminescent transparent ferroelectric ceramic material (1-x) K0.5Na0.5NbO3-xSr(Yb0.5Nb0.5)O3-yM (wherein M is Er or Ho, x is 0.05-0.35, and y is 0.001-0.01), but the transmittance of the material is low, so that the application of the material is limited.
Disclosure of Invention
In view of this, the present invention provides a transparent ferroelectric ceramic material, and a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a transparent ferroelectric ceramic material, which has a chemical composition shown in formula I: (1-x)K0.5Na0.5NbO3-xSr(Yb0.5Ta0.5)O3The formula I, wherein x is 0.01-0.06.
The invention also provides a preparation method of the transparent ferroelectric ceramic material in the technical scheme, which comprises the following steps:
mixing a potassium raw material, a sodium raw material, a niobium raw material, a strontium raw material, an ytterbium raw material and a tantalum raw material according to the stoichiometric ratio of the transparent ferroelectric ceramic, and sequentially carrying out primary ball milling treatment and primary presintering treatment to obtain primary ceramic powder;
sequentially carrying out secondary ball milling treatment and secondary presintering treatment on the primary ceramic powder to obtain secondary ceramic powder;
and sequentially granulating, pressing and sintering the secondary ceramic powder to obtain the transparent ferroelectric ceramic material.
Preferably, the potassium raw material comprises one or more of potassium carbonate, potassium bicarbonate and potassium oxalate;
the sodium raw material comprises one or more of sodium carbonate, sodium bicarbonate and sodium oxalate;
the niobium raw material comprises niobium pentoxide;
the strontium raw material comprises strontium carbonate and/or strontium acetate;
the ytterbium raw material comprises ytterbium oxide;
the tantalum feedstock comprises tantalum oxide.
Preferably, the granularity of the mixed powder obtained by the primary ball milling treatment is 0.035-0.12 mm.
Preferably, the particle size of the mixed powder obtained by the secondary ball milling treatment is 0.03-0.08 mm.
Preferably, the temperature of the first-stage pre-sintering treatment and the second-stage pre-sintering treatment is 860-880 ℃ independently, and the time is 3-5 hours independently;
the heating rate of the temperature rising to the first-stage pre-sintering treatment temperature and the temperature rising to the second-stage pre-sintering treatment temperature is independently 3-5 ℃/min.
Preferably, polyvinyl alcohol is added during the granulation.
Preferably, the pressing pressure is 4-6 MPa.
Preferably, the sintering treatment comprises a first sintering and a second sintering which are sequentially performed;
the temperature of the first sintering is 600-700 ℃, and the time is 2-3 h;
the temperature of the second sintering is 1140-1200 ℃, and the time is 3-15 h.
The invention also provides application of the transparent ferroelectric ceramic material in the technical scheme or the transparent ferroelectric ceramic material prepared by the preparation method in the technical scheme as a photoelectric device.
The invention provides a transparent ferroelectric ceramic material, which has a chemical composition shown in formula I: (1-x) K0.5Na0.5NbO3-xSr(Yb0.5Ta0.5)O3The formula I, wherein x is 0.01-0.06. The invention provides a transparent ferroelectric ceramic material with K0.5Na0.5NbO3The (KNN) ferroelectric ceramic is used as a substrate, and a second component Sr (Yb) is dissolved in a solid solution0.5Ta0.5)O3Then, the ceramic material has transparent property; meanwhile, the solid solution ratio of the second component is regulated and controlled, so that the structure of the transparent ferroelectric ceramic material is compact, and the light transmittance of the transparent ferroelectric ceramic material is effectively improved.
Drawings
FIG. 1 is a schematic diagram of transparent ferroelectric ceramic materials prepared in examples 1-2 and comparative example 1;
FIG. 2 is a graph showing transmittance curves of the transparent ferroelectric ceramic materials prepared in examples 1 to 2 and comparative example 1;
FIG. 3 XRD spectra of the transparent ferroelectric ceramic materials prepared in examples 1-2 and comparative example 1;
FIG. 4 is a ferroelectric hysteresis loop plot of the transparent ferroelectric ceramic material prepared in example 1;
fig. 5 is a ferroelectric hysteresis loop diagram of the transparent ferroelectric ceramic material prepared in example 2.
Detailed Description
The invention provides a transparent ferroelectric ceramic material, which has a structural formula as follows: (1-x) K0.5Na0.5NbO3-xSr(Yb0.5Ta0.5)O3，x＝0.01～0.06。
In the invention, in the formula I, x is preferably 0.015 to 0.055, and is further preferably 0.02, 0.025, 0.03, 0.035, 0.04, 0.045 and 0.05.
The invention provides a transparent ferroelectric ceramic material with K0.5Na0.5NbO3The (KNN) ferroelectric ceramic is used as a substrate, and a second component Sr (Yb) is dissolved in a solid solution0.5Ta0.5)O3Then, the ceramic material has transparent property; meanwhile, the structure of the transparent ferroelectric ceramic material is compact by regulating the solid solution ratio of the second component, the light transmittance of the transparent ferroelectric ceramic material is effectively improved, and the transparent ferroelectric ceramic material has excellent ferroelectric property.
The invention provides a preparation method of the transparent ferroelectric ceramic material in the technical scheme, which comprises the following steps:
mixing a potassium raw material, a sodium raw material, a niobium raw material, a strontium raw material, an ytterbium raw material and a tantalum raw material according to the stoichiometric ratio of the transparent ferroelectric ceramic, and sequentially carrying out primary ball milling treatment and primary presintering treatment to obtain primary ceramic powder;
sequentially carrying out secondary ball milling treatment and secondary presintering treatment on the primary ceramic powder to obtain secondary ceramic powder;
and sequentially granulating, pressing and sintering the secondary ceramic powder to obtain the transparent ferroelectric ceramic material.
In the present invention, all the raw material components are commercially available products well known to those skilled in the art unless otherwise specified.
According to the stoichiometric ratio of the transparent ferroelectric ceramic, a potassium raw material, a sodium raw material, a niobium raw material, a strontium raw material, an ytterbium raw material and a tantalum raw material are mixed, and primary ball milling treatment and primary presintering treatment are sequentially carried out to obtain primary ceramic powder.
In the present invention, the potassium raw material preferably comprises one or more of potassium carbonate, potassium bicarbonate and potassium oxalate, more preferably comprises potassium carbonate, potassium bicarbonate or potassium oxalate, and most preferably is potassium carbonate. In the present invention, the sodium raw material preferably comprises one or more of sodium carbonate, sodium bicarbonate and sodium oxalate, more preferably comprises sodium carbonate, sodium bicarbonate or sodium oxalate, and most preferably is sodium carbonate. In the present invention, the niobium raw material preferably includes niobium pentoxide. In the present invention, the strontium raw material preferably includes strontium carbonate and/or strontium acetate, and more preferably strontium carbonate. In the present invention, the ytterbium raw material preferably includes ytterbium oxide. In the present invention, the tantalum raw material preferably includes tantalum oxide. In the embodiment of the present invention, potassium carbonate, sodium carbonate, niobium pentoxide, strontium carbonate, ytterbium oxide, and tantalum oxide are preferably used as raw materials.
In the present invention, the purity of the potassium material, sodium material, niobium material, strontium material, ytterbium material and tantalum material is preferably not less than 99.5% independently. In the present invention, the purity of the potassium carbonate is preferably 99.5%, the purity of the sodium carbonate is preferably 99.8%, the purity of the niobium pentoxide is preferably 99.99%, the purity of the strontium carbonate is preferably 99.9%, and the purity of the tantalum oxide is preferably 99.99%.
In the invention, the balls for the primary ball milling treatment are preferably zirconium balls, and further preferably, the balls are firstly ball-milled by adopting mixed zirconium balls containing large zirconium balls and small zirconium balls, wherein the diameter of the large zirconium balls is preferably 7-8 mm, and the diameter of the small zirconium balls is preferably 4-5 mm; the mass ratio of the large zirconium balls to the small zirconium balls is preferably 1: (0.2-0.4). In the invention, the first-stage ball milling treatment is preferably wet ball milling; the medium for wet ball milling is preferably ethanol. In the invention, the rotation speed of the primary ball milling treatment is preferably 300-450 r/min, and is further preferably 350-410 r/min; the time of the primary ball milling treatment is preferably 20-28 h, and more preferably 24 h. The equipment adopted by the primary ball milling treatment is not particularly limited, and the ball milling equipment well known in the field can be adopted; in the embodiment of the present invention, the primary ball milling treatment is preferably performed in a tumbling ball mill. The zirconium balls with different grain diameters are subjected to wet ball milling, so that the dispersion effect of the raw materials can be further improved. In the invention, the granularity of the mixed powder obtained by the primary ball milling treatment is preferably less than or equal to 0.15mm, and is further preferably 0.035-0.12 mm.
After the first-stage ball milling treatment is finished, the first-stage ball milling powder obtained by the first-stage ball milling treatment is preferably dried and sieved in sequence. In the invention, the drying temperature is preferably 70-90 ℃, and the drying time is preferably 6-20 h; the invention can remove the organic solvent in the wet ball milling process by drying. In the present invention, the mesh number of the screen used for the sieving treatment is preferably 100 to 300 meshes, and more preferably 100 meshes. The dried first-stage ball-milling powder and the zirconium balls are preferably separated by sieving treatment.
In the invention, the temperature of the primary pre-sintering treatment is preferably 800-920 ℃, and more preferably 860-880 ℃. In the invention, the heating rate from room temperature to the first-stage pre-sintering treatment temperature is preferably 3-5 ℃/min, and more preferably 4 ℃/min; after the temperature is raised to the first-stage pre-sintering treatment temperature, the heat preservation time is preferably 2-10 hours, and more preferably 3-5 hours.
After the primary pre-sintering treatment is completed, the invention preferably cools the primary pre-sintering powder obtained by the primary pre-sintering treatment to obtain the primary ceramic powder. In the present invention, the cooling is preferably furnace cooling. In the invention, the primary ceramic powder is potassium sodium niobate-strontium tantalate-ytterbium acid ceramic powder.
After primary ceramic powder is obtained, sequentially carrying out secondary ball milling treatment and secondary presintering treatment on the primary ceramic powder to obtain secondary ceramic powder;
in the invention, the balls for the secondary ball milling treatment are preferably zirconium balls, and more preferably, the balls are firstly ball-milled by adopting mixed zirconium balls containing large zirconium balls and small zirconium balls, wherein the diameter of the large zirconium balls is preferably 7-8 mm, and the diameter of the small zirconium balls is preferably 4-5 mm; the mass ratio of the large zirconium balls to the small zirconium balls is preferably 1: (0.2-0.4). In the invention, the secondary ball milling treatment is preferably wet ball milling; the medium for wet ball milling is preferably ethanol. In the invention, the rotation speed of the secondary ball milling treatment is preferably 300-450 r/min, and is further preferably 350-410 r/min; the time of the secondary ball milling treatment is preferably 20-28 h, and more preferably 24 h. The equipment adopted by the secondary ball milling treatment is not particularly limited, and the ball milling equipment well known in the field can be adopted; in the embodiments of the present invention, the secondary ball milling treatment is preferably performed in a tumbling ball mill. The invention leads the crystal grains of the first-grade ceramic powder to be more refined through the second-grade ball milling treatment. In the invention, the particle size of the mixed powder obtained by the secondary ball milling treatment is preferably 0.03-0.08 mm, and more preferably 0.03-0.05 mm.
After the secondary ball milling treatment is finished, the secondary ball milling powder obtained by the secondary ball milling treatment is preferably dried and sieved in sequence. In the invention, the drying temperature is preferably 70-90 ℃, the drying time is preferably 6-20 h, and the organic solvent in the wet ball milling process can be removed through drying. In the present invention, the mesh number of the screen used for the sieving treatment is preferably 100 to 300 meshes, and more preferably 100 meshes. The invention preferably separates the dried second-stage ball-milling powder from the zirconium balls through screening treatment.
In the invention, the temperature of the secondary pre-sintering treatment is preferably 800-920 ℃, and more preferably 860-880 ℃. In the invention, the heating rate from room temperature to the secondary pre-sintering treatment temperature is preferably 3-5 ℃/min, and more preferably 4 ℃/min; after the temperature is raised to the temperature of the secondary pre-sintering treatment, the heat preservation time is preferably 2-10 hours, and more preferably 3-5 hours. According to the invention, through carrying out the secondary ball milling treatment and the secondary presintering treatment, raw materials which do not react completely in the primary presintering treatment react more completely to obtain secondary ceramic powder.
After the second-stage presintering treatment is finished, the second-stage presintering sample is preferably cooled to obtain second-stage ceramic powder. In the present invention, the cooling is preferably furnace cooling. In the invention, the secondary ceramic powder is potassium sodium niobate-strontium tantalate-ytterbium acid ceramic powder.
The method adopts primary presintering treatment and secondary presintering treatment to carry out sectional presintering, the primary presintering primarily synthesizes the main crystal phase of the material, so that the raw materials react to synthesize the designed ceramic component, and meanwhile, water and volatile impurities are removed, and the volume during subsequent sintering is reduced; on the basis, the secondary pre-burning can enable the raw materials which are not completely reacted in the primary pre-burning treatment to be more completely reacted.
After the secondary ceramic powder is obtained, the invention carries out granulation, pressing and sintering treatment on the secondary ceramic powder in sequence to obtain the transparent ferroelectric ceramic material.
In the present invention, polyvinyl alcohol is preferably added during the granulation; the polyvinyl alcohol is preferably used in the form of an aqueous polyvinyl alcohol solution, and the mass concentration of the aqueous polyvinyl alcohol solution is preferably 5% to 7%, and more preferably 6%. In the invention, the polyvinyl alcohol is preferably added in batches, more preferably added in 2-5 batches, and the mass of the polyvinyl alcohol added in each batch accounts for 20-50% of the total mass of the polyvinyl alcohol. And uniformly mixing the secondary ceramic powder and the polyvinyl alcohol after adding the polyvinyl alcohol in each batch, and then adding the polyvinyl alcohol again. The amount of polyvinyl alcohol added in the present invention is not particularly limited, and may be such that the secondary ceramic powder and polyvinyl alcohol are mixed and then assume a snowflake-like wet state, and specifically, the mass ratio of polyvinyl alcohol to secondary ceramic powder is preferably 0.0005 to 0.012:1, and more preferably 0.0007 to 0.01: 1.
The present invention does not require any particular process for granulation, and may be carried out by methods known to those skilled in the art. In the embodiment of the present invention, the granulation is preferably performed by grinding. According to the invention, by adding polyvinyl alcohol, the secondary ceramic powder can be more easily granulated in the granulation process.
After the granulation, the invention preferably carries out drying and sieving treatment on the granules obtained by the granulation in sequence. In the invention, the drying temperature is preferably 70-90 ℃, and the time is preferably 5-6 h; the present invention preferably enables the moisture in the granules obtained by granulation to be removed cleanly by the drying treatment. In the invention, the granularity of the raw material particles under the sieve obtained after the sieving treatment is preferably 0.03-0.08 mm, and more preferably 0.03-0.05 mm
In the present invention, the pressing pressure is preferably 4 to 8MPa, and more preferably 5 to 7 MPa. In the present invention, the pressing is preferably performed in a mold. The mold of the present invention is not particularly limited, and a mold known in the art may be used. In an embodiment of the invention, the mould is preferably a cylindrical mould; the diameter of the cylindrical die is preferably 8-9 mm. In the present invention, the pressing process preferably uses a tool or a mold to form the secondary ceramic powder into a green body having a certain shape, size and strength. The present invention does not require any particular pressing operation, and may employ pressing operations known to those skilled in the art.
In the present invention, the specific operation of the sintering treatment is preferably: and placing the pressed sheet on a zirconium plate padded with zirconium dioxide, then scattering secondary ceramic powder on the surface of the pressed sheet, reversely buckling the double crucibles, sealing by using the zirconium dioxide powder, and sintering. In the invention, the zirconium dioxide is preferably roasted before being paved on the zirconium plate; the roasting temperature is preferably 1250-1350 ℃, and more preferably 1300 ℃; the roasting time is preferably 1-4 h, and more preferably 2 h. In the invention, the granularity of the zirconium dioxide powder is preferably 0.03-0.12 mm. The invention preferably adopts the sintering method, which is favorable for creating a closed environment, increasing the element concentration atmosphere in the closed environment, reducing the volatilization of alkali metal potassium and sodium, simultaneously has better heat preservation effect and is favorable for preparing the transparent ferroelectric ceramic material.
In the present invention, the sintering treatment preferably includes a first sintering and a second sintering performed in this order. In the invention, the temperature of the first sintering is preferably 600-700 ℃, and more preferably 620-680 ℃; the heating rate from the room temperature to the first sintering temperature is preferably 0.5-1.5 ℃/min, and more preferably 0.4-0.8 ℃/min, and the heating rate is controlled within the range, so that the porosity is favorably reduced, and the density of the ceramic material structure is improved. In the invention, the heat preservation time after the temperature is raised to the first sintering temperature is preferably 2-3 h. In the present invention, the polyvinyl alcohol colloid can be excluded in the first sintering process.
In the invention, the temperature of the second sintering is preferably 1140-1200 ℃, more preferably 1170-1190 ℃, the heating rate of the second sintering temperature is preferably 1-2 ℃/min, and the heat preservation time after the second sintering temperature is preferably 3-15 h, more preferably 5-10 h. In the invention, in the second sintering process, substances of the ceramic material are mutually diffused at high temperature, so that the micro discrete particles form a continuous solid structure, the integral free energy of the ceramic sample is reduced, the strength is improved, and the main crystal phase is further formed. The equipment adopted by the sintering treatment is not particularly limited, and the sintering equipment well known in the field can be adopted; in an embodiment of the invention, the sintering process is preferably performed in a muffle furnace.
The invention adopts the first sintering mode and the second sintering mode, namely the mode of firstly sintering at low temperature and then sintering at high temperature, which is beneficial to reducing the porosity, improving the density of the ceramic material, and leading the micro discrete particles to form a continuous solid structure and further form a main crystal phase.
After the second sintering is completed, the present invention preferably performs a cooling process on the material obtained by the second sintering. In the present invention, the cooling includes programmed cooling and furnace cooling in sequence. In the invention, the cooling rate of the programmed cooling is preferably 1-2 ℃/min; the temperature after the programmed cooling is preferably 400-600 ℃, and the heat preservation time is preferably 0.5-1.0 h. In the present invention, the temperature after the furnace cooling is preferably room temperature. By adopting the cooling mode, the invention can prevent the excessive internal stress of the transparent ferroelectric ceramic material caused by the excessively high cooling rate, thereby avoiding the problem of the increase of the defects of the transparent ferroelectric ceramic material.
The invention also provides application of the transparent ferroelectric ceramic material in the technical scheme or the transparent ferroelectric ceramic material prepared by the method in the technical scheme as a photoelectric device.
In the present invention, the transparent ferroelectric ceramic material is preferably applied as an optoelectronic device to a memory element, an optical attenuator, an optical isolator and an optical switch.
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 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.
Example 1
0.99K0.5Na0.5NbO3-0.01Sr(Yb0.5Ta0.5)O3(0.99 KNN-0.01SYT for short)
(1) Preparing materials: weighing 3.4379g K2CO3(purity 99.5%), 2.6285g Na2CO3(purity 99.8%), 13.1589g Nb2O5(purity 99.99%) 0.1478g SrCO3(purity 99.9%), 0.0805gYb2O3(purity 99.99%) and 0.1105g Ta2O5(purity 99.99%) of the starting material.
(2) First-stage ball milling: putting the weighed raw materials into a ball milling tank with zirconium balls with the diameters of 4mm and 7mm respectively, adding 40mL of ethanol, and carrying out primary ball milling for 24h on a roller ball mill at the speed of 350r/min to obtain primary ball milling powder.
(3) Drying and sieving: and (3) placing the first-stage ball-milling powder in an oven, drying for 12h at 70 ℃ until the powder in the oven is volatilized and dried by alcohol, then drying for 5h at 90 ℃, and then sieving by a 100-mesh sieve to remove zirconium balls, wherein the part below the sieve is the first-stage ball-milling powder.
(4) First-stage pre-burning: and (3) placing the first-stage ball-milling powder in a crucible, heating to 860 ℃ at the heating rate of 4 ℃/min, preserving heat for 3 hours, and then cooling along with the furnace to obtain the first-stage ceramic powder.
(5) Secondary ball milling: putting the primary ceramic powder into a ball milling tank with zirconium balls with the diameters of 4mm and 7mm respectively, adding 40mL of ethanol, and performing primary ball milling for 24 hours on a roller ball mill at the speed of 350 r/min.
(6) Drying and sieving: and placing the mixed powder obtained by the first-stage ball milling in an oven, drying for 5 hours at the temperature of 90 ℃, and then sieving by a 100-mesh sieve to remove zirconium balls, wherein the part below the sieve is the second-stage ball milling powder.
(7) And (3) secondary pre-burning: and (3) placing the secondary ball-milling powder in a crucible, heating to 860 ℃ at the heating rate of 4 ℃/min, preserving heat for 3 hours, and then cooling along with the furnace to obtain secondary ceramic powder.
(8) And (3) granulation: adding 20g of secondary ceramic powder and 0.2g of 7 wt% polyvinyl alcohol aqueous solution into the mixture for 4 times, grinding the mixture by using a mortar after the polyvinyl alcohol aqueous solution is added each time to enable the powder and the polyvinyl alcohol to be uniformly mixed, and finally stopping adding the polyvinyl alcohol after the ground powder is in a snowflake-shaped wet state, wherein the adding amount of the polyvinyl alcohol aqueous solution is 0.2 g.
(9) Drying and sieving: and (3) placing the sample obtained by granulation in an oven, drying for 6 hours at 90 ℃ to completely dry the powder, and sieving by a 100-mesh sieve, wherein the raw material of the part under the sieve is dry powder.
(10) Tabletting: 0.4g of the dried powder was put into a cylindrical mold having a radius of 9mm, and compression-molded under a pressure of 4MPa to obtain a tablet.
(11) Sintering treatment: placing the pressed sheet on a zirconium plate padded with zirconium dioxide (burned at 1300 ℃ for 2h), scattering a little secondary ceramic powder on the pressed sheet, reversing the double crucibles, sealing by using the zirconium dioxide powder, then placing the pressed sheet in a muffle furnace, heating to 600 ℃ at the speed of 0.5 ℃/min, preserving heat for 2h to remove polyvinyl alcohol, heating to 1180 ℃ at the speed of 1 ℃/min, preserving heat for 3h, cooling to 600 ℃ at the speed of 1 ℃/min, preserving heat for 0.5h, and cooling with the furnace to obtain the transparent ferroelectric ceramic material with the temperature of 0.99K0.5Na0.5NbO3-0.01Sr(Yb0.5Ta0.5)O3。
Example 2
0.98K0.5Na0.5NbO3-0.02Sr(Yb0.5Ta0.5)O3(0.98 KNN-0.02SYT for short)
(1) Preparing materials: weighing 3.4032g K2CO3(purity 99.5%), 2.6020g Na2CO3(purity 99.8%), 13.0260gNb2O5(purity 99.99%) 0.2956g SrCO3(purity 99.9%), 0.1611gYb2O3(pure)Degree 99.99%) and 0.2209g Ta2O5(purity 99.99%) of the starting material.
(2) First-stage ball milling: putting the weighed raw materials into a ball milling tank with zirconium balls with the diameters of 5mm and 7mm respectively, adding 40mL of ethanol, carrying out primary ball milling for 24h on a roller ball mill at the speed of 400r/min, and taking primary ball milling powder as the undersize part.
(3) Drying and sieving: and (3) placing the first-stage ball-milling powder in an oven, drying for 12h at 70 ℃ until the powder in the oven is volatilized and dried by alcohol, then drying for 5h at 90 ℃, and then sieving by a 100-mesh sieve to remove zirconium balls, wherein the part below the sieve is the first-stage ball-milling powder.
(4) First-stage pre-burning: and (3) placing the first-stage ball-milling powder in a crucible, heating to 860 ℃ at the heating rate of 4 ℃/min, preserving heat for 3 hours, and then cooling along with the furnace to obtain the first-stage ceramic powder.
(5) Secondary ball milling: putting the primary ceramic powder into a ball milling tank with zirconium balls with the diameters of 5mm and 8mm respectively, adding 40mL of ethanol, and performing primary ball milling for 24 hours on a roller ball mill at the speed of 400 r/min.
(6) Drying and sieving: and (3) placing the mixed powder obtained by the first-stage ball milling in a drying oven, drying for 15h at 70 ℃, then drying for 5h at 90 ℃, sieving by a 100-mesh sieve to remove zirconium balls, wherein the part below the sieve is the second-stage ball milling powder.
(7) And (3) secondary pre-burning: and (3) placing the secondary ball-milling powder in a crucible, heating to 860 ℃ at the heating rate of 4 ℃/min, preserving heat for 3 hours, and then cooling along with the furnace to obtain secondary ceramic powder.
(8) And (3) granulation: adding 20g of secondary ceramic powder and 0.2g of 7 wt% polyvinyl alcohol aqueous solution into the mixture for 4 times, grinding the mixture by using a mortar after the polyvinyl alcohol aqueous solution is added each time to enable the powder and the polyvinyl alcohol to be uniformly mixed, and finally stopping adding the polyvinyl alcohol after the ground powder is in a snowflake-shaped wet state, wherein the adding amount of the polyvinyl alcohol aqueous solution is 0.2 g.
(9) Drying and sieving: and (3) placing the sample obtained by granulation in an oven, drying for 6 hours at 90 ℃ to completely dry the powder, and sieving by a 100-mesh sieve, wherein the raw material of the part under the sieve is dry powder.
(10) Tabletting: 0.4g of the dried powder was put into a cylindrical mold having a radius of 8mm, and compression-molded under a pressure of 4MPa to obtain a tablet.
(11) Sintering treatment: placing the pressed sheet on a zirconium plate padded with zirconium dioxide (burned at 1300 ℃ for 2h), scattering a little secondary ceramic powder on the pressed sheet, reversing the double crucibles, sealing by using the zirconium dioxide powder, then placing the pressed sheet in a muffle furnace, raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, preserving the heat for 2h to remove polyvinyl alcohol, raising the temperature to 1180 ℃ at the speed of 1 ℃/min, preserving the heat for 3h, lowering the temperature to 600 ℃ at the speed of 1 ℃/min, preserving the heat for 0.5h, and cooling with the furnace to obtain the transparent ferroelectric ceramic material 0.98K0.5Na0.5NbO3-0.02Sr(Yb0.5Ta0.5)O3。
Comparative example 1
0.85K0.5Na0.5NbO3-0.15Sr(Yb0.5Nb0.5)O3(abbreviated as 0.85KNN-0.15SYN)
(1) Preparing materials: weighing 2.9472g K2CO3(purity 99.5%), 2.2570g Na2CO3(purity 99.8%), 12.2945gNb2O5(purity 99.99%) 2.2162g SrCO3(purity 99.9%) and 1.4782gYb2O3(purity 99.95%) of the starting material.
(2) First-stage ball milling: putting the weighed raw materials into a ball milling tank with zirconium balls with the diameters of 4mm and 7mm respectively, adding 40mL of ethanol, and carrying out primary ball milling for 24h on a roller ball mill at the speed of 350r/min to obtain primary ball milling powder.
(3) Drying and sieving: and (3) placing the first-stage ball-milling powder in an oven, drying for 12h at 70 ℃ until the powder in the oven is volatilized and dried by alcohol, then drying for 5h at 90 ℃, and then sieving by a 100-mesh sieve to remove zirconium balls, wherein the part below the sieve is the first-stage ball-milling powder.
(4) First-stage pre-burning: and (3) placing the first-stage ball-milling powder in a crucible, heating to 850 ℃ at the heating rate of 4 ℃/min, preserving the heat for 5 hours, and then cooling along with the furnace to obtain the first-stage ceramic powder.
(5) Secondary ball milling: putting the first-stage ceramic powder into a ball milling tank with zirconium balls with the diameters of 4mm and 7mm respectively, adding 40mL of ethanol, and carrying out first-stage ball milling for 24h on a roller ball mill at the speed of 400 r/min.
(6) Drying and sieving: and placing the mixed powder obtained by the first-stage ball milling in an oven, drying for 5 hours at the temperature of 90 ℃, and then sieving by a 100-mesh sieve to remove zirconium balls, wherein the part below the sieve is the second-stage ball milling powder.
(7) And (3) secondary pre-burning: and (3) placing the secondary ball-milling powder in a crucible, heating to 950 ℃ at the heating rate of 4 ℃/min, preserving the heat for 5 hours, and then cooling along with the furnace to obtain secondary ceramic powder.
(8) And (3) granulation: adding 20g of secondary ceramic powder and 0.2g of 7 wt% polyvinyl alcohol aqueous solution into the mixture for 4 times, grinding the mixture by using a mortar after the polyvinyl alcohol aqueous solution is added each time to enable the powder and the polyvinyl alcohol to be uniformly mixed, and finally stopping adding the polyvinyl alcohol after the ground powder is in a snowflake-shaped wet state, wherein the adding amount of the polyvinyl alcohol aqueous solution is 0.2 g.
(9) Drying and sieving: and (3) placing the sample obtained by granulation in an oven, drying for 6 hours at 90 ℃ to completely dry the powder, and sieving by a 100-mesh sieve, wherein the raw material of the part under the sieve is dry powder.
(10) Tabletting: 0.4g of the dried powder was put into a cylindrical mold having a radius of 9mm, and compression-molded under a pressure of 4MPa to obtain a tablet.
(11) Sintering treatment: placing the pressed sheet on a zirconium plate padded with zirconium dioxide (burned at 1300 ℃ for 2h), scattering a little secondary ceramic powder on the pressed sheet, reversing the double crucibles, sealing by using the zirconium dioxide powder, then placing the pressed sheet in a muffle furnace, raising the temperature to 600 ℃ at the speed of 0.5 ℃/min, preserving the heat for 2h to remove polyvinyl alcohol, raising the temperature to 1260 ℃ at the speed of 1 ℃/min, preserving the heat for 5h, lowering the temperature to 600 ℃ at the speed of 1 ℃/min, preserving the heat for 0.5h, and cooling with the furnace to obtain the transparent ferroelectric ceramic material with the temperature of 0.85K0.5Na0.5NbO3-0.15Sr(Yb0.5Nb0.5)O3。
Performance testing
The transparent ferroelectric ceramic materials prepared in examples 1 to 2 and comparative example 1 were polished to a thickness of about 0.3mm, a sample object diagram is shown in fig. 1, and a transmittance diagram of the polished transparent ferroelectric ceramic material is shown in fig. 2 and table 1.
TABLE 1 transmittance of transparent ferroelectric ceramic material under 400-1100 nm light
Figure BDA0002369763900000121
As can be seen from fig. 1 to 2 and table 1, the transparent ferroelectric ceramic materials prepared in examples 1 and 2 of the present invention have transparency, and the transparency of the transparent ferroelectric ceramic material prepared in the present invention is superior to that of the transparent ferroelectric ceramic material prepared in comparative example 1. To explain, with K0.5Na0.5NbO3(KNN) ferroelectric ceramic as matrix, mixed with solid solution of Sr (Yb)0.5Nb0.5)O3Compared with the obtained transparent ferroelectric ceramic (comparative example 1), the solid-solution Sr (Yb) of the invention0.5Ta0.5)O3The obtained transparent ferroelectric ceramic material has better transparency.
The XRD patterns of the transparent ferroelectric ceramic materials prepared in example 1, example 2 and comparative example 1 of the present invention are shown in fig. 3. As can be seen from fig. 3, the XRD spectrogram peak positions of the transparent ferroelectric ceramic materials prepared in examples 1-2 and comparative example 1 of the present invention substantially coincide with the diffraction peak on the PDF standard card, which can indicate that the obtained ceramic materials have a perovskite structure; then, the prepared sample can be judged to be of a pseudo-cubic structure according to the fact that the diffraction peak of (200) (around 46 ℃) is a single peak. Therefore, the transparent ferroelectric ceramic material obtained by the invention has a pseudo cubic phase perovskite structure, and no second phase is generated.
The P-E curves of 0.99KNN-0.01SYT prepared in example 1 under different electric fields are shown in FIG. 4, Pr increases with increasing electric field, and Pmax is 11.77 μ C/cm at E60 kV/cm2，Pr＝1.87μC/cm2，Ec＝10.17kV。
The P-E curves at different electric fields of the transparent ferroelectric ceramic material prepared in example 2 are shown in fig. 5. As can be seen from fig. 5, Pr increases with increasing electric field, and when E is 60kV/cm, Pmax is 6.59 μ C/cm2，Pr＝1.39μC/cm2，Ec＝13.79kV。
As can be seen from FIGS. 4 and 5, the transparent ferroelectric ceramic material prepared by the present invention has ferroelectric properties, which exhibit relatively fine hysteresis loops, showing relaxation-like behavior, and is accompanied by the second component Sr (Yb)0.5Nb0.5)O3The content is increased, the saturation polarization intensity and the residual polarization intensity are reduced, and the coercive field is increased.
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 (10)

1. A transparent ferroelectric ceramic material, characterized in that it has a chemical composition according to formula I: (1-x) K0.5Na0.5NbO3-xSr(Yb0.5Ta0.5)O3The formula I, wherein x is 0.01-0.06.
2. A method for preparing a transparent ferroelectric ceramic material according to claim 1, comprising the steps of:
mixing a potassium raw material, a sodium raw material, a niobium raw material, a strontium raw material, an ytterbium raw material and a tantalum raw material according to the stoichiometric ratio of the transparent ferroelectric ceramic, and sequentially carrying out primary ball milling treatment and primary presintering treatment to obtain primary ceramic powder;
sequentially carrying out secondary ball milling treatment and secondary presintering treatment on the primary ceramic powder to obtain secondary ceramic powder;
and sequentially granulating, pressing and sintering the secondary ceramic powder to obtain the transparent ferroelectric ceramic material.
3. The preparation method of claim 2, wherein the potassium raw material comprises one or more of potassium carbonate, potassium bicarbonate and potassium oxalate;
the sodium raw material comprises one or more of sodium carbonate, sodium bicarbonate and sodium oxalate;
the niobium raw material comprises niobium pentoxide;
the strontium raw material comprises strontium carbonate and/or strontium acetate;
the ytterbium raw material comprises ytterbium oxide;
the tantalum feedstock comprises tantalum oxide.
4. The preparation method of claim 2, wherein the particle size of the mixed powder obtained by the primary ball milling treatment is 0.035-0.12 mm.
5. The preparation method of claim 2, wherein the particle size of the mixed powder obtained by the secondary ball milling treatment is 0.03-0.08 mm.
6. The preparation method according to claim 2, wherein the temperature of the primary pre-sintering treatment and the temperature of the secondary pre-sintering treatment are 860 to 880 ℃ independently, and the time is 3 to 5 hours independently;
the heating rate of the temperature rising to the first-stage pre-sintering treatment temperature and the temperature rising to the second-stage pre-sintering treatment temperature is independently 3-5 ℃/min.
7. The method according to claim 2, wherein polyvinyl alcohol is added during the granulation.
8. The method according to claim 2, wherein the pressure for pressing is 4 to 6 MPa.
9. The production method according to claim 2, wherein the sintering process includes a first sintering and a second sintering that are performed in this order;
the temperature of the first sintering is 600-700 ℃, and the time is 2-3 h;
the temperature of the second sintering is 1140-1200 ℃, and the time is 3-15 h.
10. Use of the transparent ferroelectric ceramic material according to claim 1 or the transparent ferroelectric ceramic material prepared by the preparation method according to any one of claims 2 to 9 as a photovoltaic device.
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