CN112209711A - Zirconium-titanium-tin lead niobate thick film ceramic and preparation method and application thereof - Google Patents
Zirconium-titanium-tin lead niobate thick film ceramic and preparation method and application thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 78
- FUVJKXSEOCHILY-UHFFFAOYSA-N [Pb].[Sn].[Ti].[Zr] Chemical compound [Pb].[Sn].[Ti].[Zr] FUVJKXSEOCHILY-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 34
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000000498 ball milling Methods 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011812 mixed powder Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 35
- 238000005266 casting Methods 0.000 claims description 22
- 238000005057 refrigeration Methods 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 238000007873 sieving Methods 0.000 claims description 9
- 229910052451 lead zirconate titanate Inorganic materials 0.000 claims description 8
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 5
- 239000003292 glue Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
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- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- FGKRRBWIHMRUCR-UHFFFAOYSA-N [Sn].[Ti].[Zr] Chemical compound [Sn].[Ti].[Zr] FGKRRBWIHMRUCR-UHFFFAOYSA-N 0.000 claims 2
- 239000010936 titanium Substances 0.000 claims 1
- 239000003989 dielectric material Substances 0.000 abstract description 5
- 238000010345 tape casting Methods 0.000 abstract description 2
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
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- 238000001000 micrograph Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical group [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
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- 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
- C04B35/49—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 containing also titanium oxides or titanates
- C04B35/491—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 containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT
- C04B35/493—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 containing also titanium oxides or titanates based on lead zirconates and lead titanates, e.g. PZT containing also other lead compounds
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- C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
- C04B35/638—Removal thereof
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
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Abstract
The invention belongs to the technical field of dielectric materials, and discloses a zirconium-titanium-tin lead niobate thick-film ceramic and a preparation method and application thereof. The molecular formula of the thick film ceramic is PbxNby(ZrnSnmTiv)zO3Wherein x is 0.9-0.99, y is 0-0.02, n is 0.1-1.5, m is 0-1.5, v is 0-0.15, and z is 0.9-1; according to the stoichiometric ratio, PbO and ZrO are added2、SnO2、TiO2、Nb2O5Ball milling and mixing, drying at 60-80 ℃, pre-sintering the sieved ceramic powder at 950-1000 ℃, performing secondary ball milling, drying the mixed powder at 60-80 ℃, adding the obtained ceramic powder into the dispersed ceramic powderPreparing ceramic slurry by using an agent, a binder and a mixed solution; the ceramic slurry is subjected to tape casting to obtain a thick film green body, then the thick film green body is subjected to binder removal at 400-600 ℃, and the thick film green body is sintered at 1250-1300 ℃. The thick film has the advantages of small size and good compatibility with integrated circuits.
Description
Technical Field
The invention belongs to the technical field of dielectric materials, and particularly relates to a zirconium-titanium-tin-lead niobate thick-film ceramic and a preparation method and application thereof.
Background
The traditional refrigeration mode is realized based on a vapor compression technology, and a gas-liquid refrigeration mode which takes Freon as a refrigerant is adopted, so once the Freon enters the atmosphere, the ozone layer can be damaged, and not only are environmental problems brought, but also the human health is threatened. The refrigeration problem is related to industrial production and many aspects of people's life, and the importance of the refrigeration problem is self-evident. At present, the electrocaloric effect based on polar materials is a new method for realizing solid state refrigeration, and the principle of the electrocaloric effect is that the polarization state in the polar dielectric materials is changed due to the change of an external electric field, so that the generated adiabatic temperature change or isothermal entropy change is generated.
Compared with the traditional refrigeration mode, the electric card effect has the advantages of higher energy conversion efficiency, lower cost, small application size, higher working reliability, more important no environmental pollution and the like in the solid-state refrigeration technology, so the electric card effect has development prospect in the field of small-size solid-state refrigeration devices. The current electric card materials are mainly divided into five types: ceramic blocks, thin films, polymers, ceramic and polymer matrix composites, and multilayer ceramic thick films. For ceramic block materials, the electrical card performance of the materials is severely limited due to the fact that the ceramic block materials have more defects and lower breakdown electric fields. The ceramic film material has the advantages of reduced thickness, greatly reduced defects, improved breakdown property, and improved electric card performance. However, the total volume of the film is small, the heat absorption capacity is small, and the substrate is needed, so that the requirement of refrigeration cannot be met. The polymer has good breakdown characteristic and high electric card performance, but the external voltage required by the polymer is too high, so the polymer is difficult to apply to actual refrigeration and is particularly dangerous. The thick film ceramic has the advantages of small size, good compatibility with an integrated circuit, relatively high breakdown electric field and the like, and has great significance for realizing refrigeration of microelectronic devices such as the integrated circuit and the like by utilizing the electric card effect of a thick film material. Therefore, how to optimize the electrocaloric effect of the thick film to realize high-efficiency refrigeration becomes a scientific problem which needs to be solved urgently. Among ceramic dielectric materials, antiferroelectric materials are a particular class of dielectric materials. In antiferroelectric materials (AFEs), adjacent dipoles with the same strength in the crystal structure are initially aligned in parallel in opposite directions, resulting in zero overall spontaneous polarization. However, these initially antiparallel arranged dipoles can induce an Antiferroelectric (AFE) to Ferroelectric (FE) phase transition by an electric field, and the electric dipoles are forced to align parallel along the direction of the external electric field, thereby achieving a large polarized FE state. Then, once the external electric field is removed, the induced FE phase can revert back to the original AFE phase, thereby creating a P-E double hysteresis loop. Antiferroelectric materials have outstanding advantages in energy storage, and electric card refrigeration of the antiferroelectric materials is receiving more and more attention of researchers.
Disclosure of Invention
In order to solve the defects in the prior art, the invention mainly aims to provide the lead zirconate titanate tin niobate thick-film ceramic.
The invention also aims to provide a preparation method of the zirconium-titanium-tin-lead niobate thick film ceramic.
The invention also aims to provide application of the zirconium-titanium-tin-lead niobate thick-film ceramic.
The purpose of the invention is realized by the following technical scheme:
the zirconium-titanium-tin lead niobate thick film ceramic has the molecular formula of PbxNby(ZrnSnmTiv)zO3Wherein x is 0.9-0.99, y is 0-0.02, n is 0.1-1.5, m is 0-1.5, v is 0-0.15, and z is 0.9-1; the thick film ceramic is prepared by mixing PbO and ZrO according to stoichiometric ratio2、SnO2、TiO2、Nb2O5Adding ethanolBall milling and mixing, drying and sieving to obtain ceramic powder; pre-sintering ceramic powder at 950-1000 ℃, then adding ethanol, carrying out secondary ball milling, drying and sieving mixed powder, adding a dispersing agent, a binder and a mixed solution into the obtained ceramic powder, and obtaining casting slurry; and drying the casting slurry on a casting machine, discharging the glue of a casting-molded green body at 400-600 ℃, and sintering at 1250-1300 ℃ to obtain the casting-molded green body.
Preferably, the dispersant is polyoxyethylene ether; the binder is more than one of polyvinyl butyral, polyvinyl alcohol or acrylic resin.
Preferably, the mixed solution is ethanol and acetone,
more preferably, the mass ratio of ethanol to acetone is 1: (1-5).
Preferably, the ceramic powder, the dispersant, the binder: the mass ratio of the mixed solution is (40-50): (0.9-1.2): (4-6): (40-50).
Preferably, the drying temperature is 60-80 ℃, the drying time is 10-24 h, the pre-sintering time is 1-5 h, the binder removal time is 4-6 h, and the sintering time is 1-2 h.
Preferably, the linear speed of the film belt of the casting machine is 0.15-0.5 rad/min.
Preferably, the viscosity of the casting slurry is 600 to 800 mPas.
Preferably, the thickness of the thick film ceramic is 37-43 μm.
The preparation method of the zirconium-titanium-tin lead niobate thick film ceramic comprises the following specific steps:
s1, mixing PbO and ZrO according to stoichiometric ratio2、SnO2、TiO2、Nb2O5Adding ethanol, and ball-milling and mixing; drying the ball-milled powder at 60-80 ℃, and sieving to obtain ceramic powder;
s2, pre-sintering ceramic powder at 950-1000 ℃, then adding ethanol, carrying out secondary ball milling, drying the mixed powder at 60-80 ℃, and sieving to obtain ceramic powder;
s3, adding a dispersing agent, a binder and a mixed solution into the ceramic powder to obtain casting slurry;
s4, drying the casting slurry on a casting machine with the film belt linear velocity of 0.15-0.5rad/min, discharging glue from a casting-molded green body at 400-600 ℃, and sintering at 1250-1300 ℃ to obtain the zirconium-titanium-tin-lead niobate thick film ceramic.
The zirconium-titanium-tin-lead niobate thick film ceramic is applied to the field of electric card refrigeration.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention utilizes PbxNby(ZrnSnmTiv)zO3The (PNZST) system is obtained by designing a ternary phase diagram, wherein x is 0.90-0.99, y is 0.00-0.05, n is 0.1-1.5, m is 0.0-1.5, v is 0.0-0.15, and z is 0.90-1.00; isothermal entropy change and adiabatic temperature change of the ceramic are calculated through Maxwell relation, and knowledge accumulation and theoretical support are provided for practical application of the antiferroelectric/ferroelectric ceramic in the field of novel refrigeration technology and pulse power technology.
2. The PNZST powder is synthesized by adopting a solid-phase method, and the thickness-controllable lead niobium zirconate titanate stannate thick film ceramic is prepared by a tape casting process. The pre-sintered powder obtained by X-ray diffraction (XRD) is of a perovskite structure, and the sintered crystal particles of the sample are uniformly and compactly distributed and have the size of about 1-3 mu m when observed by a Scanning Electron Microscope (SEM).
3. The dielectric loss of the PNZST is lower than 5%, the ferroelectric hysteresis loop changes from a ferroelectric phase to an antiferroelectric phase and then to a paraelectric phase along with the temperature change, and the PNZST component is proved to be in a PNZST antiferroelectric tetragonal phase region. And estimating the adiabatic temperature change value and the isothermal entropy change value of the sample according to the delta T and the delta S. At 25MV/m and 450K, respectively, 2.8K and 2.48 J.K-1·kg-1. The thick film has the advantages of small size and good compatibility with the integrated circuit, and the refrigeration of microelectronic devices such as the integrated circuit and the like can be realized by utilizing the electric card effect of the thick film has great significance.
Drawings
FIG. 1 shows Pb in examples 1 and 20.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3(PNZST)And (3) pre-burning the powder for 2 hours at 980 ℃ and 950 ℃ to obtain an X-ray diffraction pattern of the powder.
FIG. 2 shows Pb in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3SEM image of the thick film ceramic sintered at 1300 ℃ for 3 h.
FIG. 3 shows Pb in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3The thick film ceramic has dielectric constant and dielectric loss of 1-1000kHz at normal temperature.
FIG. 4 shows Pb in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3The thick film ceramic has a hysteresis loop (a) at different temperatures and current versus field curves at (b)30 ℃, (c)120 ℃ and (d)180 ℃.
FIG. 5 shows Pb in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3The thick film ceramic has maximum polarization intensity (a), pyroelectric coefficient (b), adiabatic temperature change (c) and isothermal entropy change (d) at different temperatures.
Detailed Description
The following examples are presented to further illustrate the present invention and should not be construed as limiting the invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
In the embodiment of the invention, PbO and ZrO are adopted2、SnO2、TiO2、Nb2O5All purchased from Shanghai Aladdin Biotechnology, Inc.
Example 1
1. Adding PbO (excessive 2-5 wt%) and ZrO according to stoichiometric ratio2、SnO2、TiO2、Nb2O5Placing the mixture in a nylon ball milling tank (250mL), wherein the ball milling medium is zirconium dioxide balls (the ball diameter is 3mm and 5mm, and the mass ratio is about 1: 1); by using the commonAnd (3) carrying out ball milling by a planetary ball mill, adding ethanol, setting the rotating speed to be 250rmp, and carrying out ball milling for 24 h.
2. Putting the ball-milled powder in an oven, drying for 10h at 60 ℃, and respectively sieving by a 40-mesh sieve and a 80-mesh sieve to obtain ceramic powder;
3. presintering ceramic powder in a muffle furnace at 980 ℃ for 2h, then ball-milling by adopting a common planetary ball mill, adding ethanol, setting the rotating speed to be 250rmp, carrying out secondary ball-milling for 24h, placing the ball-milled powder in an oven, drying for 10h at 60 ℃, and respectively sieving by using 40-mesh and 80-mesh sieves to obtain ceramic powder;
4. preparing casting slurry: the obtained ceramic powder (about 50g) was placed in a tumbling jar, and 0.9g of a dispersant (polyoxyethylene ether) and 40g of a solvent (anhydrous ethanol and acetone in a mass ratio of 1: 1) were added. Tumbling for 20h at the rotating speed of 220rpm to obtain premixed slurry; adding 1.5g of binder (polyvinyl alcohol) and performing roll milling at the rotating speed of 200rpm for 10 hours, adding 18g of solvent (absolute ethyl alcohol and acetone in a mass ratio of 1: 1) and 4g of binder (polyvinyl alcohol) and performing ball milling at the rotating speed of 200rpm for 12-16 hours to obtain uniformly mixed casting slurry (the viscosity is 600-800 mPa & s);
5. drying the casting slurry on a casting machine with the film belt linear velocity of 0.15-0.5 r/min, discharging the glue of the casting formed blank at 400 ℃, and sintering at 1300 ℃ to obtain the zirconium-titanium-tin-lead niobate thick film ceramic with the chemical formula of Pb0.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3(PNZST) having a thickness of 37 to 43 μm.
Example 2
The difference from the embodiment is that: in the step 3, the pre-sintering temperature is 950 ℃; the temperature of the binder removal in the step 5 is 600 ℃, the sintering temperature is 1250 ℃, and the zirconium-titanium-tin-lead niobate thick-film ceramic is prepared, wherein the chemical molecular formula is Pb0.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3(PNZST) having a thickness of 37 to 43 μm.
Material structure characterization and performance test: and (3) analyzing a crystal structure: japan science DMAX-UltimaIV X-ray diffractometer (XRD). Analyzing the surface appearance: hitachi S-3400 (II) type Scanning Electron Microscope (SEM). Dielectric properties: HP 4284A precision impedance analyzer, Hewlett packard, USA. Ferroelectric properties: the American Radiant company RT-66A ferroelectric comprehensive test system. Electric card effect: and calculating Maxwell relation.
FIG. 1 is an X-ray diffraction pattern of the powder prepared in examples 1 and 2 by solid-phase reaction at 980 ℃ and 950 ℃ for 2 hours. As can be seen from fig. 1, the diffraction peak of the powder is sharp and has no impurity peak, which is consistent with the diffraction peak of the standard card PNZST sheet, and the PNZST powder with perovskite structure has been synthesized at both temperatures.
FIG. 2 shows Pb obtained in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3Scanning electron microscope images of thick film ceramics. As can be seen from FIG. 2, the obtained thick film ceramic is relatively dense, and has close connection between crystal grains and less pores. The grain size of the thick film ceramic is mainly distributed between 1-3 μm. The thickness of the ceramic sample was measured to be about 41 μm in cross section. Measuring actual density of sample by Archimedes method, calculating theoretical density by lattice constant obtained by XRD, and analyzing by software to obtain powder with density of 7.89g/cm3。
FIG. 3 shows Pb in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3The thick film ceramic has a dielectric constant and dielectric loss of 1-1000kHz at normal temperature. As can be seen from FIG. 3, the test voltage is 1V, the test frequencies are 1-1000kHz respectively, and the dielectric loss is less than 5%. The relative dielectric constant was 530.2 at 1kHz, and its value gradually decreased with increasing frequency, 445.7 at 1000kHz, due to the fact that the electric dipole flip could not follow the frequency change at high frequencies, and thus the dielectric loss gradually increased with increasing frequency.
FIG. 4 shows Pb in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3The electric hysteresis loop (a) of the thick film ceramic at different temperatures and the current-dependent electric field curves at (b)30 ℃, (c)120 ℃ and (d)180 ℃. Wherein (a) in FIG. 4 is the electric hysteresis of the thick film ceramic at different temperatures measured under an electric field of 200kV/cmThe loop, the test frequency is 10Hz, and the polarization intensity gradually decreases with the increase of the temperature. From fig. 4 (b) - (d), at 30 ℃, the typical hysteresis loop of the ferroelectric is obtained by testing, at 120 ℃, the current shows double peaks along with the change of the electric field, which proves that the anti-ferroelectric phase transition occurs, and in combination with the phase diagram of PNZST, the composition sample is in the PNZST anti-ferroelectric tetragonal phase region, at 180 ℃, the typical hysteresis loop of the linear dielectric is shown.
FIG. 5 shows Pb in example 10.99Nb0.02(Zr0.50Sn0.45Ti0.05)0.98O3The thick film ceramic has maximum polarization intensity (a), pyroelectric coefficient (b), adiabatic temperature change (c) and isothermal entropy change (d) at different temperatures. As can be seen from FIG. 5, the maximum polarization intensity reached 31. mu.C cm at 30 ℃ under an electric field of 25MV/m-2. The pyroelectric coefficient is a negative value, which indicates that the positive charge-card effect is obtained. At an electric field of 450K and 25MV/m, the values of Δ T and Δ S reach maximum values of 2.8K and 2.48 J.K, respectively-1·kg-1. The results show that the thick film ceramic has better electrical card effect.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. The zirconium-titanium-tin-lead niobate thick film ceramic is characterized in that the molecular formula of the thick film ceramic is PbxNby(ZrnSnmTiv)zO3Wherein x is 0.9-0.99, y is 0-0.02, n is 0.1-1.5, m is 0-1.5, v is 0-0.15, and z is 0.9-1; the thick film ceramic is prepared by mixing PbO and ZrO according to stoichiometric ratio2、SnO2、TiO2、Nb2O5Adding ethanol, ball-milling and mixing, drying and sieving to obtain ceramic powder; pre-sintering ceramic powder at 950-1000 ℃, then adding ethanol, carrying out secondary ball milling, drying mixed powderScreening, namely adding a dispersing agent, a binder and a mixed solution into the obtained ceramic powder to obtain casting slurry; and drying the casting slurry on a casting machine, discharging the glue of a casting-molded green body at 400-600 ℃, and sintering at 1250-1300 ℃ to obtain the casting-molded green body.
2. The lead zirconate titanate tin niobate thick film ceramic of claim 1, wherein the dispersant is a polyoxyethylene ether; the binder is more than one of polyvinyl butyral, polyvinyl alcohol or acrylic resin.
3. The lead zirconate titanate tin niobate thick film ceramic of claim 1, wherein the mixed solution is ethanol and acetone.
4. The lead zirconate titanate tin niobate thick film ceramic of claim 3, wherein the mass ratio of ethanol to acetone is 1: (1-5).
5. The lead niobate thick-film ceramic of zirconium titanium tin, according to claim 1, wherein the mass ratio of the ceramic powder, the dispersant, the binder and the mixed solution is (40-50): (0.9-1.2): (4-6): (40-50).
6. The lead zirconate titanate niobate thick film ceramic of claim 1, wherein the drying temperature is 60-80 ℃, the drying time is 10-24 h, the pre-sintering time is 1-5 h, the binder removal time is 4-6 h, and the sintering time is 1-2 h.
7. The lead niobate thick film ceramic of zirconium titanium tin, according to claim 1, wherein the tape linear velocity of the tape of the casting machine is 0.15 to 0.5 rad/min; the viscosity of the casting slurry is 600-800 mPa & s.
8. The lead zirconate titanate niobate thick film ceramic of claim 1, wherein the thickness of the thick film ceramic is 37 to 43 μm.
9. The method for preparing the lead zirconate titanate niobate thick film ceramic of any one of claims 1 to 8, comprising the following specific steps:
s1, mixing PbO and ZrO according to stoichiometric ratio2、SnO2、TiO2、Nb2O5Adding ethanol for ball milling and mixing, drying the ball milled powder at 60-80 ℃, and sieving to obtain ceramic powder;
s2, pre-sintering ceramic powder at 950-1000 ℃, then adding ethanol, carrying out secondary ball milling, drying the mixed powder at 60-80 ℃, and sieving to obtain ceramic powder;
s3, adding a dispersing agent, a binder and a mixed solution into the ceramic powder to obtain casting slurry;
s4, drying the casting slurry on a casting machine with the film belt linear velocity of 0.15-0.5rad/min, discharging glue from a casting formed green body at 400-600 ℃, and sintering at 1250-1300 ℃ to obtain the zirconium-titanium-tin-lead niobate thick film ceramic.
10. Use of the lead zirconate titanate niobate thick film ceramic of any one of claims 1 to 8 in the refrigeration field of electronic cards.
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