CN112624759A - Lead hafnate antiferroelectric ceramic material and preparation method thereof - Google Patents
Lead hafnate antiferroelectric ceramic material and preparation method thereof Download PDFInfo
- Publication number
- CN112624759A CN112624759A CN202011530083.7A CN202011530083A CN112624759A CN 112624759 A CN112624759 A CN 112624759A CN 202011530083 A CN202011530083 A CN 202011530083A CN 112624759 A CN112624759 A CN 112624759A
- Authority
- CN
- China
- Prior art keywords
- powder
- sintering
- ceramic material
- antiferroelectric
- lead
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/64—Burning or sintering processes
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3296—Lead oxides, plumbates or oxide forming salts thereof, e.g. silver plumbate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6562—Heating rate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
- C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
- C04B2235/6567—Treatment time
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
- C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
Abstract
The invention discloses a lead hafnate antiferroelectric ceramic material and a preparation method thereof, belonging to the field of antiferroelectric ceramic materials. The preparation method of the invention combines the lead excess method and the three-layer crucible sintering method for preparation, and when the three-layer crucible sintering method is used for sintering, PbZrO3The buried material is heated and decomposed at high temperature to generate a large amount of oxygen molecules, so that local saturated vapor pressure is formed, evaporation-condensation mass transfer can be promoted at the initial stage of sintering, and the densification rate of a sintered product is accelerated; the aluminum oxide powder stably exists at the sintering temperature, and a sintering environment with uniform temperature is provided; the invention is sintered under the conditions of relatively rich oxygen and uniform temperature, the grain size of the sample obtained by sintering is uniform, and the microstructure is compact; and the control of lead excess and sintering conditions can accurately control the stoichiometric ratio of Pb and Hf in a sintered product to be closer to 1: 1. the invention has simple preparation process, lower cost and repeatabilityPreferably.
Description
Technical Field
The invention belongs to the field of antiferroelectric ceramic materials, and particularly relates to a lead hafnate antiferroelectric ceramic material and a preparation method thereof.
Background
With the progress of scientific technology, the dielectric material with high energy storage density has potential application value in the modern electronic technology, and particularly has irreplaceable application in the technical field of high-energy pulse power. Therefore, the development of a novel energy storage material with high energy storage density is urgent and becomes one of the hot spots of new materials and new technical researches. Common dielectric materials used for the energy storage capacitor comprise a linear dielectric material, a ferroelectric material, a relaxor ferroelectric material and an antiferroelectric material, and compared with other three dielectric materials, the antiferroelectric material shows the characteristics of near-zero residual polarization and high saturation polarization strength due to a special double-hysteresis loop, and has the characteristics of high energy storage density, high efficiency and the like. Most antiferroelectric energy storage ceramic materials reported at present have complex components and various element types, and mainly focus on lead zirconate (PbZrO) with mature preparation process and excellent energy storage performance3) A base antiferroelectric material. Similar lead hafnate (PbHfO)3) The antiferroelectric material has larger polarization intensity and higher critical electric field, so the antiferroelectric material has important application prospect in the field of high energy storage dielectric materials.
However, lead oxide is very easy to volatilize in the sintering process of the lead hafnate ceramic, the volatilization of the lead oxide causes deviation of the stoichiometric ratio of the ceramic material, and the sintered lead hafnate ceramic has poor compactness and poor electrical property, thereby seriously limiting the industrial application of the lead hafnate ceramic.
Disclosure of Invention
The invention aims to overcome the defect that the stoichiometric ratio of a lead hafnate antiferroelectric ceramic material is deviated due to the easy volatilization of PbO in the sintering process of the lead hafnate ceramic, and provides the lead hafnate antiferroelectric ceramic material and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
preparation method of lead hafnate antiferroelectric ceramic materialWhen the powder is weighed, the weight ratio of the powder to the powder is (1.04-1.05): 1 weighing PbO powder and HfO2Powder;
when sintering a green body made of powder, embedding the green body into a crucible containing powder with the same components as the green body, and embedding the crucible into a crucible containing PbZrO3Embedding the intermediate layer crucible into an outer layer crucible filled with aluminum oxide embedding materials;
and sintering in air at the sintering temperature of 1100-1200 ℃ for 4-6h to obtain the lead hafnate antiferroelectric ceramic material.
Further, the method comprises the following steps:
(1) mixing PbO powder and HfO2The powder is prepared from (1+ x): 1, weighing, mixing and then carrying out primary ball milling to obtain mixed powder;
wherein x is 0.04-0.05;
(2) drying, grinding and briquetting the mixed powder in sequence, and then preserving heat for 2-6 h at the temperature of 800-880 ℃ to obtain presintering powder;
(3) sequentially carrying out secondary ball milling, drying, grinding, granulating and sieving on the pre-sintered powder to obtain powder with uniform particles;
(4) standing the powder with uniform particles for 12-24 h, pressing the powder into a cylindrical blank, and keeping the temperature of the cylindrical blank at 500-600 ℃ for 2-5 h to obtain a primary sintered blank;
(5) embedding the primary sintered blank into a crucible containing powder with the same components as the blank, and embedding the crucible into a crucible containing PbZrO3Embedding the intermediate layer crucible into an outer layer crucible filled with aluminum oxide embedding materials, and sintering in air;
wherein the sintering condition is sintering at 1100-1200 ℃ for 4-6h, and furnace cooling.
Further, in the step (1) and the step (3), the ball milling medium is absolute ethyl alcohol, and the mass ratio of the material to the zirconium balls to the absolute ethyl alcohol is 1: 2: (0.5-1.5), and the ball milling time is 12-18 h.
Further, in the step (2) and the step (3), the drying temperature is 80-100 ℃.
Further, in the step (3), adding a polyvinyl alcohol aqueous solution for granulation, wherein the mass concentration of the polyvinyl alcohol aqueous solution is 5-10%;
the addition amount of the polyvinyl alcohol aqueous solution is 6-10% of the mass of the mixed powder.
Further, in the step (3), the sieve mesh number is 40 meshes and 80 meshes, and the material on the 80-mesh sieve is taken.
Further, in the step (4), pressing the blank into a cylindrical blank under the pressure of 200-500 MPa.
Further, the heating rate in the step (2) and the heating rate in the step (5) are both 3-5 ℃/min.
The lead hafnate antiferroelectric ceramic material prepared by the preparation method is provided.
Furthermore, the phase transition of the antiferroelectric and the ferroelectric can be carried out at room temperature, and a double ferroelectric hysteresis loop can be obtained.
Compared with the prior art, the invention has the following beneficial effects:
the preparation method of the lead hafnate antiferroelectric ceramic material adopts the combination of the lead excess method and the three-layer crucible sintering method for preparation, and when the three-layer crucible sintering method is used for sintering, PbZrO is prepared3The buried material is heated and decomposed at high temperature to generate a large amount of oxygen molecules, so that local saturated vapor pressure is formed, evaporation-condensation mass transfer can be promoted at the initial stage of sintering, and the densification rate of a sintered product is accelerated; meanwhile, the aluminum oxide powder on the outermost layer stably exists at the sintering temperature, so that a sintering environment with uniform temperature is provided; therefore, the sample sintered by the three-layer crucible sintering method is sintered under the conditions of relatively rich oxygen and uniform temperature, the grain size of the sample obtained by sintering is uniform, and the microstructure is compact; and the control of lead excess and sintering conditions can accurately control the stoichiometric ratio of Pb and Hf in a sintered product to be closer to 1: 1. the invention can effectively inhibit abnormal grain growth easily occurring in the high-temperature sintering process, and obtain uniform structure; the invention has simple preparation process, lower cost and better repeatability.
The lead hafnate antiferroelectric ceramic material has high density, high breakdown field strength and high energy storage density.
Drawings
FIG. 1 is a graph of lead weight loss at 1120 ℃ for different lead excesses;
FIG. 2 is SEM images of comparative examples and anti-ferroelectric ceramic samples of examples 1 to 3, wherein FIG. 2(a) is the SEM image of the comparative example, and FIGS. 2(b), 2(c) and 2(d) are the SEM images of examples 1 to 3;
FIG. 3 is an X-ray diffraction pattern of the ceramic materials prepared in examples 1-3;
FIG. 4 is a plot of the dielectric loss for comparative and example 1-3 antiferroelectric ceramic samples;
FIG. 5 is a graph of the dielectric temperature curves for the ceramic materials prepared in examples 1-3;
FIG. 6 is a hysteresis curve of antiferroelectric ceramic samples prepared in comparative example and examples 1-2 at a frequency of 10Hz at room temperature.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. 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.
It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.
The invention is described in further detail below with reference to the accompanying drawings:
example 1 (three-layer crucible sintering method for preparing PbHfO3Ceramic):
the chemical composition of the antiferroelectric ceramic is PbHfO3The method comprises the following steps:
(1) according to a molar ratio of 1.04: 1 weighing PbO powder and HfO2Powder, weighing the material, zircon ball stone and absolute ethyl alcohol according to the mass ratio of 1: 2: 1, ball milling for 15h after mixing, drying, grinding and briquetting in sequence after ball milling is finished, and preserving heat for 4h at 850 ℃ to obtain presintering powder;
(2) grinding the pre-sintered powder, and mixing the ground pre-sintered powder, the zirconium ball stone and the absolute ethyl alcohol according to a mass ratio of 1: 2: 1, mixing and then carrying out secondary ball milling for 15 hours; after drying, grinding and sieving by a 120-mesh sieve, and adding a polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder for granulation, wherein the mass concentration of the PVA is 5%; after granulation, respectively sieving the powder with a 40-mesh sieve and a 80-mesh sieve to obtain powder with uniform particles, standing for 15h, pressing the powder with uniform particles into a cylindrical blank under the pressure of 300MPa, placing the cylindrical blank in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving heat for 5h, and removing glue to obtain a primary sintered blank;
(3) embedding the primary sintered blank into a crucible containing powder with the same components as the blank, and embedding the crucible into a crucible containing PbZrO3Burying the intermediate layer crucible in an outer layer crucible filled with aluminum oxide buried material, sintering in air, heating to 1100 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to room temperature along with the furnace to obtain the lead hafnate antiferroelectric ceramic material;
(4) and (3) polishing the sintered ceramic material by using abrasive paper with different particle sizes to obtain a thin ceramic chip with a bright and smooth surface, uniformly coating silver electrode slurry on the front surface and the back surface of the sample, and carrying out heat preservation at 600 ℃ for 30min to burn silver to obtain the ceramic element. And carrying out electric hysteresis loop test and energy storage density calculation on the obtained energy storage ceramic element.
Example 2 (three-layer crucible sintering method for preparing PbHfO3Ceramic):
the chemical composition of the antiferroelectric ceramic is PbHfO3The method comprises the following steps:
(1) according to a molar ratio of 1.045: 1 weighing PbO powder and HfO2Powder, weighing the material, zircon ball stone and absolute ethyl alcohol according to the mass ratio of 1: 2: 1, ball milling for 15h after mixing, drying, grinding and briquetting in sequence after ball milling is finished, and preserving heat for 4h at 850 ℃ to obtain presintering powder;
(2) grinding the pre-sintered powder, and mixing the ground pre-sintered powder, the zirconium ball stone and the absolute ethyl alcohol according to a mass ratio of 1: 2: 1, mixing and then carrying out secondary ball milling for 15 hours; after drying, grinding and sieving by a 120-mesh sieve, and adding a polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder for granulation, wherein the mass concentration of the PVA is 5%; after granulation, respectively sieving the powder with a 40-mesh sieve and a 80-mesh sieve to obtain powder with uniform particles, standing for 15h, pressing the powder with uniform particles into a cylindrical blank under the pressure of 300MPa, placing the cylindrical blank in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving heat for 5h, and removing glue to obtain a primary sintered blank;
(3) embedding the primary sintered blank into a crucible containing powder with the same components as the blank, and embedding the crucible into a crucible containing PbZrO3Burying the intermediate layer crucible in an outer layer crucible filled with aluminum oxide buried material, sintering in air, heating to 1120 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to room temperature along with the furnace to obtain the lead hafnate antiferroelectric ceramic material;
(4) and (3) polishing the sintered ceramic material by using abrasive paper with different particle sizes to obtain a thin ceramic chip with a bright and smooth surface, uniformly coating silver electrode slurry on the front surface and the back surface of the sample, and carrying out heat preservation at 600 ℃ for 30min to burn silver to obtain the ceramic element. And carrying out electric hysteresis loop test and energy storage density calculation on the obtained energy storage ceramic element.
Example 3 (three-layer crucible sintering method for preparing PbHfO3Ceramic):
the chemical composition of the antiferroelectric ceramic is PbHfO3The method comprises the following steps:
(1) according to a molar ratio of 1.05: 1 weighing PbO powder and HfO2Powder, weighing the material, zircon ball stone and absolute ethyl alcohol according to the mass ratio of 1: 2: 1, ball milling for 15h after mixing, drying, grinding and briquetting in sequence after ball milling is finished, and preserving heat for 4h at 850 ℃ to obtain presintering powder;
(2) grinding the pre-sintered powder, and mixing the ground pre-sintered powder, the zirconium ball stone and the absolute ethyl alcohol according to a mass ratio of 1: 2: 1, mixing and then carrying out secondary ball milling for 15 hours; after drying, grinding and sieving by a 120-mesh sieve, and adding a polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder for granulation, wherein the mass concentration of the PVA is 5%; after granulation, respectively sieving the powder with a 40-mesh sieve and a 80-mesh sieve to obtain powder with uniform particles, standing for 15h, pressing the powder with uniform particles into a cylindrical blank under the pressure of 300MPa, placing the cylindrical blank in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving heat for 5h, and removing glue to obtain a primary sintered blank;
(3) embedding the primary sintered blank into a crucible containing powder with the same components as the blank, and embedding the crucible into a crucible containing PbZrO3Burying the intermediate layer crucible in an outer layer crucible filled with aluminum oxide buried material, sintering in air, heating to 1150 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to room temperature along with the furnace to obtain the lead hafnate antiferroelectric ceramic material;
(4) and (3) polishing the sintered ceramic material by using abrasive paper with different particle sizes to obtain a thin ceramic chip with a bright and smooth surface, uniformly coating silver electrode slurry on the front surface and the back surface of the sample, and carrying out heat preservation at 600 ℃ for 30min to burn silver to obtain the ceramic element. And carrying out electric hysteresis loop test and energy storage density calculation on the obtained energy storage ceramic element.
Comparative example:
preparation of PbHfO by common burying method3The ceramic comprises the following steps:
(1) according to a molar ratio of 1.045: 1 weighing PbO powder and HfO2Powder, weighing the material, zircon ball stone and absolute ethyl alcohol according to the mass ratio of 1: 2: 1, ball milling for 15h after mixing, drying, grinding and briquetting in sequence after ball milling is finished, and preserving heat for 4h at 850 ℃ to obtain presintering powder;
(2) grinding the pre-sintered powder, and mixing the ground pre-sintered powder, the zirconium ball stone and the absolute ethyl alcohol according to a mass ratio of 1: 2: 1, mixing and then carrying out secondary ball milling for 15 hours; after drying, grinding and sieving by a 120-mesh sieve, and adding a polyvinyl alcohol aqueous solution (PVA) accounting for 8% of the mass of the powder for granulation, wherein the mass concentration of the PVA is 5%; after granulation, respectively sieving the powder with a 40-mesh sieve and a 80-mesh sieve to obtain powder with uniform particles, standing for 15h, pressing the powder with uniform particles into a cylindrical blank under the pressure of 300MPa, placing the cylindrical blank in a muffle furnace, heating to 600 ℃ at the speed of 5 ℃/min, preserving heat for 5h, and removing glue to obtain a primary sintered blank;
(3) covering the primary sintered blank with powder with the same components, placing the primary sintered blank in an alumina crucible, heating to 1120 ℃ at a speed of 5 ℃/min, preserving heat for 4h, and naturally cooling to room temperature along with the furnace to obtain the lead hafnium antiferroelectric ceramic material;
(4) and (3) polishing the sintered ceramic material by using abrasive paper with different particle sizes to obtain a thin ceramic chip with a bright and smooth surface, uniformly coating silver electrode slurry on the front surface and the back surface of the sample, and carrying out heat preservation at 600 ℃ for 30min to burn silver to obtain the ceramic element. And carrying out electric hysteresis loop test and energy storage density calculation on the obtained energy storage ceramic element.
Referring to fig. 1, fig. 1 is a graph of lead weight loss at 1120 ℃ for different lead excesses, and a straight line in the graph represents PbHfO3Wherein the point where x is 0.045 in the figure corresponds to example 2, and at this time, the measured value is the same as the ideal stoichiometric ratio, illustrating that the volatilization of lead during high-temperature sintering can be compensated well by the control of the lead excess and the sintering conditions according to the operation of example 2, and the stoichiometric ratio of the material can be controlled more precisely.
Referring to FIG. 2, FIG. 2 is an SEM image of the antiferroelectric ceramic samples of comparative example and examples 1-3, from which it can be seen that the samples sintered using the triple-layer crucible sintering method have uniform grain size and dense microstructure due to the large amount of PbZrO3The buried material is heated and decomposed at high temperature to generate a large amount of oxygen molecules, so that local saturated vapor pressure is formed, evaporation-condensation mass transfer can be promoted at the initial stage of sintering, and the densification rate of a sintered product is accelerated. Meanwhile, the outermost layer of aluminum oxide powder can stably exist at the sintering temperature, so that a sintering environment with uniform temperature is provided. Thus, the three-layer crucible sintering method is relative to the sample sintering methodThe sintered ceramic is sintered under the conditions of oxygen enrichment and uniform temperature, so that higher compactness is obtained.
Referring to FIG. 3, FIG. 3 is an X-ray diffraction pattern of the ceramic materials prepared in examples 1-3, from which it can be seen that all of the ceramics are of a single orthorhombic phase structure, no secondary phase is formed, and excess Pb is present at the sintering temperature2+No second phase was introduced in the ceramic, indicating excess Pb2+The method can well compensate the volatilization of lead in the high-temperature sintering process, and can accurately control the stoichiometric ratio of the material.
Referring to fig. 4, fig. 4 is a graph showing dielectric loss curves at different frequencies at room temperature for antiferroelectric ceramic samples prepared in comparative examples and examples 1-3, and it can be seen that the samples obtained by sintering using the triple-layer crucible sintering method have smaller dielectric loss because the samples obtained by sintering using the triple-layer crucible sintering method have better compactness and thus lower dielectric loss.
Referring to fig. 5, fig. 5 is a graph showing the dielectric constant versus temperature curves of the ceramic materials prepared in examples 1 to 3, and it can be seen that the temperature spectrum characteristics of all the samples are substantially identical, and two dielectric abnormal peaks are observed. Referring to fig. 6, fig. 6 is a hysteresis loop of antiferroelectric ceramic samples prepared in comparative example and example 1 at a frequency of 10Hz at room temperature, and it can be seen that the samples in example 1 realize antiferroelectric → ferroelectric phase transition of lead hafnate antiferroelectric ceramic at room temperature, resulting in a dual hysteresis loop; the measured breakdown electric field intensity is 230kV/cm, and the maximum polarization value is 47.33 mu C/cm2. The effective energy storage density calculated from the PE curve was 6.36J/cm3. In the comparison example, the sample obtained by the common burying burning method has poor compactness and low breakdown field intensity, and the hysteresis loop under the saturation condition cannot be measured.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. Lead hafnate counter-ironThe preparation method of the electroceramic material is characterized in that when powder is weighed, the powder is prepared according to the following molar ratio of (1.04-1.05): 1 weighing PbO powder and HfO2Powder;
when sintering a green body made of powder, embedding the green body into a crucible containing powder with the same components as the green body, and embedding the crucible into a crucible containing PbZrO3Embedding the intermediate layer crucible into an outer layer crucible filled with aluminum oxide embedding materials;
and sintering in air at the sintering temperature of 1100-1200 ℃ for 4-6h to obtain the lead hafnate antiferroelectric ceramic material.
2. The method of preparing a lead hafnate antiferroelectric ceramic material of claim 1, comprising the steps of:
(1) mixing PbO powder and HfO2The powder is prepared from (1+ x): 1, weighing, mixing and then carrying out primary ball milling to obtain mixed powder;
wherein x is 0.04-0.05;
(2) drying, grinding and briquetting the mixed powder in sequence, and then preserving heat for 2-6 h at the temperature of 800-880 ℃ to obtain presintering powder;
(3) sequentially carrying out secondary ball milling, drying, grinding, granulating and sieving on the pre-sintered powder to obtain powder with uniform particles;
(4) standing the powder with uniform particles for 12-24 h, pressing the powder into a cylindrical blank, and keeping the temperature of the cylindrical blank at 500-600 ℃ for 2-5 h to obtain a primary sintered blank;
(5) embedding the primary sintered blank into a crucible containing powder with the same components as the blank, and embedding the crucible into a crucible containing PbZrO3Embedding the intermediate layer crucible into an outer layer crucible filled with aluminum oxide embedding materials, and sintering in air;
wherein the sintering condition is sintering at 1100-1200 ℃ for 4-6h, and furnace cooling.
3. The method for preparing a lead hafnate antiferroelectric ceramic material according to claim 2, wherein in the step (1) and the step (3), the ball-milling media are absolute ethyl alcohol, and the mass ratio of the materials, the zirconium balls and the absolute ethyl alcohol is 1: 2: (0.5-1.5), and the ball milling time is 12-18 h.
4. The method for preparing a lead hafnate antiferroelectric ceramic material according to claim 2, wherein the drying temperature in step (2) and step (3) is 80-100 ℃.
5. The method for preparing a lead hafnate antiferroelectric ceramic material according to claim 2, wherein in the step (3), an aqueous solution of polyvinyl alcohol is added for granulation, and the mass concentration of the aqueous solution of polyvinyl alcohol is 5% to 10%;
the addition amount of the polyvinyl alcohol aqueous solution is 6-10% of the mass of the mixed powder.
6. The method for preparing a lead hafnate antiferroelectric ceramic material according to claim 2, wherein in step (3), the material is sieved to 40 mesh and 80 mesh, and the material is sieved to 80 mesh.
7. The method for preparing a lead hafnate antiferroelectric ceramic material according to claim 2, wherein in the step (4), the ceramic material is pressed into a cylindrical body at a pressure of 200 to 500 MPa.
8. The method for preparing a lead hafnate antiferroelectric ceramic material according to claim 2, wherein the temperature rise rate in step (2) and step (5) is 3-5 ℃/min.
9. An antiferroelectric lead hafnate ceramic material obtained by the method of preparation according to any one of claims 2 to 8.
10. The lead hafnate antiferroelectric ceramic material of claim 9, wherein the antiferroelectric-ferroelectric phase transition is capable of undergoing at room temperature a double ferroelectric hysteresis loop.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011530083.7A CN112624759A (en) | 2020-12-22 | 2020-12-22 | Lead hafnate antiferroelectric ceramic material and preparation method thereof |
| CN202111572669.4A CN114149261B (en) | 2020-12-22 | 2021-12-21 | Lead hafnate antiferroelectric ceramic material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011530083.7A CN112624759A (en) | 2020-12-22 | 2020-12-22 | Lead hafnate antiferroelectric ceramic material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112624759A true CN112624759A (en) | 2021-04-09 |
Family
ID=75321059
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011530083.7A Pending CN112624759A (en) | 2020-12-22 | 2020-12-22 | Lead hafnate antiferroelectric ceramic material and preparation method thereof |
| CN202111572669.4A Active CN114149261B (en) | 2020-12-22 | 2021-12-21 | Lead hafnate antiferroelectric ceramic material and preparation method thereof |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111572669.4A Active CN114149261B (en) | 2020-12-22 | 2021-12-21 | Lead hafnate antiferroelectric ceramic material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN112624759A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115274298B (en) * | 2022-05-20 | 2023-10-03 | 沈阳工业大学 | Lead zirconate nano composite dielectric film and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848571A (en) * | 1994-08-09 | 1996-02-20 | Kobe Steel Ltd | Embedding powder for firing of alumina ceramics, its production and production of alumina ceramics using the same |
| CN107129301A (en) * | 2017-06-22 | 2017-09-05 | 重庆工商大学 | A kind of PLZT/ alumina composite ceramics material and preparation method thereof |
| CN107473743A (en) * | 2017-09-15 | 2017-12-15 | 西安交通大学 | A kind of lead base high-K capacitor dielectric material and preparation method thereof |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3216943A (en) * | 1963-01-15 | 1965-11-09 | Clevite Corp | Method of preparing lead titanate ferroelectric ceramics |
| WO2006134673A1 (en) * | 2005-06-14 | 2006-12-21 | Murata Manufacturing Co., Ltd | Process for producing ceramic sheet |
| US7497983B2 (en) * | 2006-08-18 | 2009-03-03 | Pentron Ceramics, Inc. | Coloring of ceramics by atmosphere control |
| JP5216319B2 (en) * | 2007-12-27 | 2013-06-19 | 株式会社アルバック | Method for producing lead zirconate titanate sintered body |
| JP2009231345A (en) * | 2008-03-19 | 2009-10-08 | Fujitsu Ltd | Ferroelectric material, ferroelectric capacitor, and semiconductor memory |
| US7783012B2 (en) * | 2008-09-15 | 2010-08-24 | General Electric Company | Apparatus for a surface graded x-ray tube insulator and method of assembling same |
| CN101445223A (en) * | 2008-12-19 | 2009-06-03 | 中国兵器工业第五二研究所 | Method for preparing low-oxygen high-alpha phase silicon nitride powder by auto-igniting synthesis |
| US8889030B2 (en) * | 2011-12-29 | 2014-11-18 | The Penn State Research Foundation | Pb(Hf,Ti)O3 based high performance polycrystalline piezoelectric materials |
| CN106699173B (en) * | 2017-01-19 | 2019-07-23 | 西安交通大学 | Antiferroelectric high energy storage ceramic material of one kind and preparation method thereof |
| CN109851344A (en) * | 2018-12-31 | 2019-06-07 | 天长市中德电子有限公司 | A kind of preparation process of high-performance nickel-zinc-ferrite material |
| CN111675533B (en) * | 2020-05-29 | 2022-06-17 | 北方民族大学 | High conductivity beta' -Al2O 3Method for preparing ceramic electrolyte |
-
2020
- 2020-12-22 CN CN202011530083.7A patent/CN112624759A/en active Pending
-
2021
- 2021-12-21 CN CN202111572669.4A patent/CN114149261B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0848571A (en) * | 1994-08-09 | 1996-02-20 | Kobe Steel Ltd | Embedding powder for firing of alumina ceramics, its production and production of alumina ceramics using the same |
| CN107129301A (en) * | 2017-06-22 | 2017-09-05 | 重庆工商大学 | A kind of PLZT/ alumina composite ceramics material and preparation method thereof |
| CN107473743A (en) * | 2017-09-15 | 2017-12-15 | 西安交通大学 | A kind of lead base high-K capacitor dielectric material and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| WEI JING ET AL.: "Excellent Energy Storage and Charge-discharge Performances in PbHfO3 Antiferroelectric Ceramics", 《JOURNAL OF THE EUROPEAN CERAMIC SOCIETY》 * |
| 杜海清: "《工业陶瓷》", 31 December 1989, 湖南大学出版社 * |
| 王迎军: "《新型材料科学与技术-无机材料卷》", 31 October 2016, 华南理工大学出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114149261A (en) | 2022-03-08 |
| CN114149261B (en) | 2023-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108439981B (en) | Silver niobate-based antiferroelectric material with wide temperature zone dielectric stability and high energy storage density and preparation method thereof | |
| CN113999004B (en) | Leadless high energy storage density ceramic material and preparation method thereof | |
| CN108424122B (en) | Preparation method of lead-free antiferroelectric ceramic material with wide temperature stability and high energy storage density | |
| CN111548156A (en) | Silver niobate-based lead-free antiferroelectric ceramic material with high energy storage density and temperature stability and preparation method thereof | |
| CN107759215A (en) | The method for preparing huge dielectric constant low-loss ceramic capacitor | |
| CN114621004B (en) | High-entropy ceramic material with high energy storage density and preparation method thereof | |
| CN110451955A (en) | Unleaded relaxation ferroelectric energy storage ceramic of bismuth sodium titanate-barium titanate base and preparation method thereof | |
| CN111574212A (en) | Low-temperature sintered low-dielectric microwave ceramic material and preparation method thereof | |
| CN107473732B (en) | Strontium titanate-based ceramic material with high energy storage density and low dielectric loss and preparation method thereof | |
| CN108863348A (en) | A kind of dielectric ceramic material and preparation method thereof of ultra-wide temperature stability | |
| CN114149261B (en) | Lead hafnate antiferroelectric ceramic material and preparation method thereof | |
| CN112341192B (en) | High-energy-storage-density sodium bismuth titanate-based lead-free dielectric material and preparation method thereof | |
| CN113511893B (en) | BNT-based high-energy-density ceramic with three-layer structure and preparation method thereof | |
| CN108863349A (en) | A kind of barium titanate-based lead-free height Jie temperature-stable ceramic material and preparation method thereof | |
| CN113480310A (en) | High-density and high-dielectric-constant tantalum pentoxide-based ceramic and preparation method thereof | |
| CN109320236B (en) | Composite material with high energy storage density and charge-discharge performance and preparation method thereof | |
| CN117229056A (en) | High-dielectric aluminum-doped perovskite structure high-entropy microwave dielectric ceramic and preparation method thereof | |
| CN112430084A (en) | NBT-BT-based relaxation ferroelectric ceramic thin film material with high electric field strength resistance and high energy storage density and preparation method thereof | |
| CN111732430A (en) | Sm and Eu co-doped CaBi8Ti7O27Preparation method of ceramic, product and application thereof | |
| CN111732431B (en) | High-electric-strength titanium oxide-based medium powder with core-shell structure and preparation method and application thereof | |
| CN113149644A (en) | Low-temperature sintered lead antimonate manganese-lead zirconate titanate low-dielectric-loss piezoelectric ceramic and preparation method thereof | |
| CN109516800A (en) | A kind of high energy-storage property media ceramic, preparation method and applications | |
| CN111499374B (en) | Ceramic dielectric material for capacitor and preparation method thereof | |
| CN109503153A (en) | A kind of high energy-storage property media ceramic, preparation method and applications | |
| CN114560695B (en) | Preparation method of composite ceramic material with high energy storage density and high energy storage efficiency |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20210409 |