EP1578730A2 - Piezokeramische zusammensetzung, piezokeramischer körper mit der zusammensetzung und verfahren zum herstellen der zusammensetzung und des körpers - Google Patents
Piezokeramische zusammensetzung, piezokeramischer körper mit der zusammensetzung und verfahren zum herstellen der zusammensetzung und des körpersInfo
- Publication number
- EP1578730A2 EP1578730A2 EP03729863A EP03729863A EP1578730A2 EP 1578730 A2 EP1578730 A2 EP 1578730A2 EP 03729863 A EP03729863 A EP 03729863A EP 03729863 A EP03729863 A EP 03729863A EP 1578730 A2 EP1578730 A2 EP 1578730A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- piezoceramic
- composition
- transition metal
- pzt
- rare earth
- 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.)
- Withdrawn
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 82
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000005245 sintering Methods 0.000 claims abstract description 50
- 150000003624 transition metals Chemical class 0.000 claims abstract description 47
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 46
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 39
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 9
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011651 chromium Substances 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 5
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 3
- 229910052773 Promethium Inorganic materials 0.000 claims abstract description 3
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims abstract description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 3
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 claims abstract description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims abstract 2
- 150000002910 rare earth metals Chemical class 0.000 claims description 36
- 239000011572 manganese Substances 0.000 claims description 26
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 25
- 229910052748 manganese Inorganic materials 0.000 claims description 25
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 238000001465 metallisation Methods 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052709 silver Inorganic materials 0.000 claims description 9
- 239000004332 silver Substances 0.000 claims description 9
- 238000010276 construction Methods 0.000 claims description 5
- 238000005452 bending Methods 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 21
- 239000000919 ceramic Substances 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 10
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 3
- 229910052451 lead zirconate titanate Inorganic materials 0.000 description 62
- 239000004848 polyfunctional curative Substances 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 10
- 239000004014 plasticizer Substances 0.000 description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 6
- 150000001768 cations Chemical class 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 229910052726 zirconium Inorganic materials 0.000 description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002019 doping agent Substances 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 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
- 230000007423 decrease Effects 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- SWELZOZIOHGSPA-UHFFFAOYSA-N palladium silver Chemical compound [Pd].[Ag] SWELZOZIOHGSPA-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000009036 growth inhibition Effects 0.000 description 1
- 239000003966 growth inhibitor Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- -1 samarium Rare earth metal Chemical class 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
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
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/006—Compounds containing, besides zirconium, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/093—Forming inorganic materials
- H10N30/097—Forming inorganic materials by sintering
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/853—Ceramic compositions
- H10N30/8548—Lead-based oxides
- H10N30/8554—Lead-zirconium titanate [PZT] based
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/05—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes
- H10N30/053—Manufacture of multilayered piezoelectric or electrostrictive devices, or parts thereof, e.g. by stacking piezoelectric bodies and electrodes by integrally sintering piezoelectric or electrostrictive bodies and electrodes
Definitions
- Piezoceramic composition piezoceramic body with the composition and method for producing the composition and the body
- the invention relates to a piezoceramic composition in the form of a lead zirconate titanate (Pb (Ti, Zr) 0 3 , PZT).
- a piezoceramic body with the composition as well as a process for producing the
- composition and a method of making the body specified.
- Lead zirconate titanate is a perovskite in which the A-positions of the perovskite are filled with divalent lead (Pb 2+ ) and the B-positions of the perovskite with tetravalent zirconium (Zr 4+ ) and tetravalent titanium (Ti 4+ ).
- the composition is generally doped to influence an electrical or piezoelectric property such as permittivity, coupling factor or piezoelectric charge constant (for example d 33 coefficient).
- Hart PZT In a so-called Hart PZT, lower-value cations are installed on the A or B position of the perovskite. These cations are called hardener doping. This type of doping results in a relatively low loss angle tg ⁇ and thus a high mechanical vibration quality Q m for a classic hard PZT.
- the mechanical vibration quality Q m is, for example, 1000.
- the high vibration quality means that an internal loss is low, which occurs when a component is electrically controlled with the Hart PZT.
- the d 33 coefficient of the Hart PZT in particular is relatively low. Hart PZT is therefore not suitable for such an application in which the largest possible piezoelectrically induced deflection is to be achieved. Hart PZT is therefore used in a piezoelectric actuator or rarely used in a piezoelectric bending transducer.
- a soft PZT In a so-called soft PZT, on the other hand, higher-quality cations are installed in the A or B position of the perovskite. These cations are called plasticizer doping.
- Such a soft PZT is known, for example, from WO 97/40537, in which trivalent neodymium (Nd 3+ ) occupies a small proportion of the A site of the perovskite PZT.
- the general formula for the piezoceramic composition of the soft PZT is Pbo, 98 Ndo, o 2 Zro, 54 Ti 0 , 4 6 ⁇ 3 .
- a classic soft PZT is characterized by a relatively high d 33 coefficient both in the small signal range (with field strengths of a few V / mm) and in the large signal range (with field strengths of a few kV / mm).
- Soft PZT is therefore suitable for use in actuators or bending transducers.
- the disadvantage of this is that the loss angle tg ⁇ is very high and therefore a mechanical vibration quality Q m is very low.
- the mechanical vibration quality Q m is, for example, 80.
- the object of the present invention is to provide a piezoceramic composition which has both a high mechanical vibration quality Q m and a large d 33 coefficient.
- a piezoceramic composition with the general summation formula Pb ⁇ - a RE b Zr x Ti y TR z 0 3 , in which RE at least one selected from the group europium, gadolinium, lanthanum, neodymium, praseodymium, promethium and / or samarium Rare earth metal with a rare earth metal content b, TR is at least one transition metal selected from the group consisting of chromium, iron and / or manganese with a transition metal valence W TR and a Transition metal component is z and the following relationship is valid: z> b / (4 - W TR ) •
- a method for producing the piezoceramic composition in which a maximum grain growth of the piezoceramic composition is determined at a specific sintering temperature.
- a piezoceramic body with the piezoceramic is used to solve the task
- the method has the following method steps: providing a green body with the piezoceramic composition and sintering the green body to form the piezoceramic body.
- the rare earth metal RE and the transition metal TR are dopants of the PZT.
- the PZT can be doped with several rare earth metals K___ with corresponding rare earth metal components b_.
- the rare earth metal component b can represent a sum of several rare earth metal components b_.
- the PZT can also be doped with a plurality of transition metals TR-, with corresponding transition metal fractions z-.
- the transition metal component z can thus be a sum of the transition metal components z D.
- the possible rare earth metals are selected so that they have an ionic radius that is similar to that of Pb 2+ . As a result, these rare earth metals primarily occupy the A positions of the Perovskite PZT.
- the rare earth metals are preferably present as trivalent cations RE 3+ , so that the A sites are partially occupied with dopants of higher quality than Pb + .
- the possible transition metals are selected such that they primarily occupy the B positions of the perovskite PZT due to their ionic radii.
- the rare earth metals preferably occur with a valence of +2 or +3, so that the B sites are partially occupied with dopants that are lower than those of Ti + and Zr + .
- the doping ratio of plasticizer to hardener doping expressed by the relationship of the transition metal component z, the deviation of the value W TR from +4 (the value of titanium and zirconium at the B positions) is of particular importance. and the rare earth portion b.
- PZT crystals are accessible which have a relatively large grain size.
- PZT crystals with a are almost independent of the sintering temperature Particle diameters of well over 1 ⁇ m accessible.
- the particle diameter of 1 ⁇ m is regarded as the critical minimum grain size for PZT, from which PZT shows good and therefore technically usable piezoelectric properties.
- the large grain sizes are possible in that a maximum grain growth of the PZT crystals can be set based on the connection of the doping according to the invention. At maximum grain growth there are almost no growth inhibitors such as vacancies in the A or B sites or local doping complexes.
- Doping ratio eliminates almost any grain growth inhibition.
- the dopants are incorporated homogeneously into a growing PZT crystal both in thermodynamic equilibrium and in charge equilibrium at a given sintering temperature.
- the largest possible PZT crystals are obtained under a given sintering condition (for example, sintering temperature or sintering atmosphere).
- the range of maximum grain growth is to be determined empirically. The following relationship approximately applies: (4-b) / (4 - W TR )>z> b / (4 - W TR ).
- the maximum grain growth of a piezoceramic composition with a neodymium fraction b Nd of 2 mol% and a manganese fraction z ⁇ of about 1.5 mol% PZT crystals with a particle diameter of up to 13 ⁇ m are obtained.
- doping with iron instead of manganese with an iron content z Fe of approximately 4 mol% leads to maximum grain growth, PZT crystals with a particle diameter of up to 10 ⁇ m being achievable.
- the result in the area of maximum grain growth are relatively large PZT crystals.
- the value of the mechanical vibration quality Q m is in the range from 50 to 1800 inclusive. It has been shown that the electrical and piezoelectric properties of the composition can be tuned from those of a classic soft PZT to the properties of a classic hard PZT are.
- the type of transition metal plays an important role. Doping with manganese leads, for example, to increased grain growth and, at the same time, a reduction in the
- Loss angle tg ⁇ These effects also occur with small amounts of manganese.
- a large d 33 coefficient (for example 550 pm / V with a control of 2 kV / mm) can thus be achieved with a low internal loss.
- the method for producing the piezoceramic composition comprises the following process steps: determining the rare earth metal component b, determining the transition metal component z, sintering the piezoceramic composition at the sintering temperature, determining a grain size of the sintered piezoceramic composition and repeating the determination of the transition metal component z, sintering and determining the grain size, the transition metal fraction z being varied.
- Mixed doping of manganese and iron is used in particular to set a desired ratio of the piezoceramic properties of a classic hard PZT and that of a classic soft PZT.
- a mixture of manganese and chrome can be used.
- the transition metal iron with an iron content z Fe and the transition metal manganese with a manganese content z___ are preferably used, so that the relationship to z Fe + 2-Z M ⁇ > b results and with the variation of the manganese content Z M ⁇ essentially the loss angle tg ⁇ of the composition and with the variation of the iron content z Fe essentially the maximum grain growth of the composition can be set.
- Rare earth metal doping with rare earth metal content b selected a manganese content z ⁇ that is lower than that
- x + y + z 1.
- Zirconium, titanium and the transition metal are primarily installed on the B place of the perovskite.
- the morphotropic phase boundary of the tetragonal and rhombohedral crystal structure necessary for the piezoelectric properties of the PZT can be empirically set from measured piezoelectric properties.
- the piezoceramic composition can be the only piezoceramic material.
- the material can be a sintered or calcined piezoceramic.
- the material can exist in different crystalline phases.
- a morphotropy of the PZT is of crucial importance for the application of the PZT in a piezoceramic component.
- PZT is at a certain ratio of
- Portion x of the zircon and portion y of the titanium in a tetragonal and rhombohedral crystal structure (morphotropy).
- the piezoceramic material is, for example, part of a sintered piezoceramic body.
- the piezoceramic material is a monolithic PZT ceramic.
- a density of the piezoceramic material in the piezoceramic body is preferably more than 96%.
- the piezoceramic material is a powder that is used to produce a piezoceramic body with the composition.
- the powder consists only of powder particles with the piezoceramic composition.
- the powder is in the form of a powder mixture of various oxides, which give the composition with the general (nominal) formula.
- the powder mixture consists of (1-a) lead oxide (PbO), b
- a component of the powder mixture can also be a mixed oxide such as zirconium titanate ((Zr x Ti ⁇ - x ) 0 2 ), which is accessible, for example, by hydrothermal precipitation.
- the lead portion (1-a) is set in such a way that there is a lead oxide excess in the percentage range before sintering begins. This excess of lead oxide advantageously leads to compaction of the powder at a relatively low temperature.
- the powder is produced from the powder particles with the piezoceramic composition, for example starting from the powder mixture described in a so-called mixed oxide process.
- Chemical production processes such as hydrothermal or sol-gel processes, which in themselves lead to homogeneous powder particles, are particularly advantageous for producing the powder.
- a homogeneous doping incorporation of the rare earth and transition metals from grain to grain is also possible when using the inexpensive mixed oxide method.
- the inexpensive mixed oxide method In a special embodiment, the
- Rare earth metal portion selected from a range of 0.2 mol% to 3 mol%.
- the low proportion of rare earth metals has a positive effect on the grain size.
- the total sum of the rare earth metal parts and the transition metal parts is less than 6 mol%. It is advantageous if, in addition to a low proportion of rare earth metals, the transition metal proportion is also low. This also contributes to the fact that even at a low sintering temperature, PZT crystals are obtained which have at least the critical minimum size of 1 ⁇ m.
- the Curie temperature T c of the piezoceramic composition is not reduced too much by a low doping component.
- the ceramic composition has a Curie temperature T c which is above 280 ° C. The relatively high Curie temperature leads to the application of the piezoceramic composition at a higher temperature.
- a component with the piezoceramic composition can be used in the engine compartment of a motor vehicle.
- the piezoceramic composition advantageously has a maximum of three different dopings.
- RE is a single rare earth metal and TR is selected from a maximum of two transition metals, or TR a single transition metal and RE is selected from a maximum of two rare earth metals. Due to the small number of different dopings, the dopings are installed very homogeneously from grain to grain and within each of the grains. This contributes to very good grain growth.
- the piezoceramic body with the piezoceramic composition it has at least one metallization selected from the group consisting of silver, copper and / or palladium.
- the piezoceramic body is produced in particular by joint sintering of the piezoceramic composition and the metallization (cofiring).
- the metallization can be an alloy of silver and palladium.
- a palladium content is selected from the range from 0% to 30% inclusive. 0% means that there is almost no palladium.
- the palladium content is preferably at most 5%. Because the piezoceramic composition enables access to a PZT ceramic with large PZT crystals and a high ceramic density, even at a relatively low sintering temperature
- Metallizations with a low melting temperature such as silver or copper are sintered together with the ceramic material.
- inexpensive copper as a metallization is possible.
- the possibility of using silver or a silver-palladium alloy with a low palladium content as the metallization also significantly reduces the costs for the production of such components.
- the piezoceramic composition Another advantage with regard to the piezoceramic composition is that the likelihood of an interaction of the metallization and the piezoceramic material during sintering is reduced to a minimum.
- the number of empty spaces in the A and B spaces is minimal.
- This reaction consists, for example, of a diffusion of silver or copper from the metallization into the vacancies. By suppressing this reaction, the Check the interaction of the PZT with the metallization very easily.
- the piezoceramic body has a monolithic multilayer construction, in which piezoceramic layers with the piezoceramic composition and electrode layers with the metallization are arranged alternately one above the other.
- the piezoceramic body is a monolithic piezo actuator in a multi-layer construction.
- the piezoceramic body is a component selected from the group of actuator, bending transducer, motor and / or transformer.
- the actuator can be used, for example, for active vibration damping or for multiple injection in a motor vehicle. With multiple injection, the actuator is actuated several times per revolution of the motor of the motor vehicle. If a classic soft PZT were used, the component could overheat due to the high internal loss and the associated self-heating. With the piezoceramic composition, this problem can be avoided.
- a green body with a metallization is provided, which is selected from the group consisting of silver, copper and / or palladium.
- the green body consists, for example, of green foils stacked on top of one another and provided with corresponding metallizations. This green body is converted into a piezoceramic body in a monolithic multilayer construction in a common sintering process.
- the sintering is carried out in particular in an oxidizing or reducing sintering atmosphere.
- an oxidizing sintering atmosphere there is almost no oxygen in a reducing sintering atmosphere.
- Oxygen partial pressure is less than 1-10 "2 mbar and preferably less than 1-10 " 3 mbar.
- a sintering temperature is preferably selected from the range from 900 ° C. to 1100 ° C. inclusive. Despite the low sintering temperature, a ceramic body with a high density is accessible. The ceramic density is, for example, 96%.
- the resulting piezoceramic body consists of relatively large PZT crystals.
- the PZT crystals obtained during sintering have a particle diameter of well over 1 ⁇ m even at a sintering temperature of 950 ° C. to 1100 ° C. that is low for PZT.
- a green body with a large number of grain growth nuclei can be used to ensure PZT crystals with a certain minimum size.
- Grain growth nuclei have in particular the piezoceramic composition.
- the grain growth nuclei can, for example, be produced from monolithic PZT of the same composition sintered at a higher temperature by comminution (for example grinding) with particle diameters of 1 ⁇ m and added to the powder in a number before the production of the green body, for example by film pulling, in a number that corresponds to the number the PZT crystals after sintering the green body to the piezoceramic body.
- the piezoceramic composition is selected so that a piezoceramic with very large grain sizes also low sintering temperature is accessible.
- the final density of the piezoceramic is very high (over 96%).
- the piezoceramic with the piezoceramic composition is characterized by a high homogeneity from grain to grain and within each grain. This is achieved in particular with a pure chromium, iron or manganese doping. The result is excellent small and large signal values for hard and / or soft PZTs.
- a metallization with a low melting temperature can be used to produce a monolithic ceramic body by sintering the metallization and the ceramic composition together.
- the piezoelectric characteristic values can thus be set in a defined manner and the production of the piezoceramic can be carried out stably and reproducibly.
- Multi-layer component accessible with any properties between optimal soft PZT and optimal hard PZT.
- Figure la shows the dependence of the grain size on the transition metal content of a first
- Figure lb shows the dependence of the loss angle tg ⁇ and the mechanical vibration quality Q m on the transition metal portion of the first embodiment.
- Figure 2a shows the dependence of the grain size on the transition metal content of a second embodiment.
- Figure 2b shows the dependence of the loss angle tg ⁇ and the mechanical vibration quality Q m on the transition metal portion of the second embodiment.
- Figure 3 shows a piezoceramic body with the piezoceramic composition.
- FIG. 4 shows a method for producing the piezoceramic body.
- the piezoceramic composition has the following general formula: Pb ⁇ - a Ndo, o 2 Zr x Ti y Mn z 0 3 .
- Figure la is the dependence of the grain size of the composition on
- the grain size increases even with a low doping with manganese.
- PZT crystals with a maximum grain size are obtained for a manganese fraction which, at a sintering temperature of 1100 ° C., is approximately 1.3 mol%, ie above b Nd / 2 (1 mol%).
- FIG. 1b shows the dependence of the loss angle tg ⁇ and the mechanical vibration quality Q m on the manganese fraction z ⁇ of the composition sintered at 1250 ° C. Even with low doping with manganese, the loss angle tg ⁇ drops drastically. This increases the mechanical vibration quality Q m . The resulting piezoceramic is characterized by low internal losses.
- the minimum grain size required for a PZT ceramic is also achieved with a sintering temperature of less than 950 ° C, which is necessary for metallization from copper or silver.
- the piezoceramic composition has the following general formula: Pb ⁇ - a Ndo, o 2 Zr x Ti y Fe z 0 3 .
- FIG. 2a shows the dependence of the grain size of the composition on the iron content z Fe in mol% and on the sintering temperature.
- PZT crystals with a maximum grain size are obtained for an iron content that is about 3 mol%, ie above b Nd (2 mol%), at a sintering temperature of 1130 ° C.
- the non-symmetrical doping of the rare earth metal neodymium and the transition metal iron leads to maximum grain size.
- Figure 2b shows the associated dependence of the loss angle tg ⁇ and the mechanical vibration quality Q m on the iron content. Only when there is a major deviation from the stoichiometric ratio of the proportion of neodymium and iron (z Fe > 3 mol%) does the loss angle tg ⁇ decrease significantly.
- the composition according to embodiment 1 is used to produce a piezoceramic body 1 (FIG. 3).
- the piezoceramic body is a piezo actuator in a monolithic multilayer construction, in which ceramic layers 2 with the piezoceramic composition and internal electrodes 3 are arranged alternately one above the other.
- the inner electrodes 3 are made of a metallization made of a silver-palladium alloy, in which palladium is contained in a proportion of 5% by weight.
- the piezo actuator To manufacture the piezo actuator, green foils with the piezoceramic composition are provided (method step 41, FIG. 4). For this purpose, a powder with the composition is mixed with an organic binder. The ceramic green sheets are cast from the slip obtained in this way. The green foils are printed with a paste with the metallization, stacked on top of one another, debindered and sintered to form the piezo actuator under an oxidic atmosphere (method step 42, FIG. 4).
- the piezo actuator is characterized by a very good large signal d 33 coefficient with very low internal losses. When the piezo actuator is used, the electrical activation of the piezo actuator does not lead to undesired self-heating.
- the piezo actuator is therefore also suitable for the use of multiple injections in the engine of a motor vehicle.
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- Inorganic Chemistry (AREA)
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Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE10223987 | 2002-05-29 | ||
DE10223987 | 2002-05-29 | ||
PCT/DE2003/001430 WO2003101946A2 (de) | 2002-05-29 | 2003-05-05 | Piezokeramische zusammensetzung, piezokeramischer körper mit der zusammensetzung und verfahren zum herstellen der zusammensetzung und des körpers |
Publications (2)
Publication Number | Publication Date |
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EP1578730A2 true EP1578730A2 (de) | 2005-09-28 |
EP1578730A3 EP1578730A3 (de) | 2005-12-14 |
Family
ID=29594192
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EP03729863A Withdrawn EP1578730A3 (de) | 2002-05-29 | 2003-05-05 | Piezokeramische zusammensetzung, piezokeramischer körper mit der zusammensetzung und verfahren zum herstellen der zusammensetzung und des körpers |
Country Status (6)
Country | Link |
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US (1) | US20050258718A1 (de) |
EP (1) | EP1578730A3 (de) |
JP (1) | JP2006501119A (de) |
AU (1) | AU2003240410A1 (de) |
DE (1) | DE10393064D2 (de) |
WO (1) | WO2003101946A2 (de) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE10245130A1 (de) * | 2002-09-27 | 2004-04-08 | Epcos Ag | Piezoelektrischer Transformator mit Cu-Innenelektroden |
DE102004031307A1 (de) * | 2004-06-29 | 2006-01-19 | Robert Bosch Gmbh | Verfahren zur Herstellung von PZT-basierten Hochleistungs-Piezokeramiken |
JP5053524B2 (ja) * | 2005-06-23 | 2012-10-17 | 日本碍子株式会社 | 電子放出素子 |
JP5103859B2 (ja) * | 2006-10-13 | 2012-12-19 | 株式会社デンソー | 積層圧電セラミックス素子及びその製造方法 |
DE102007010239A1 (de) * | 2007-03-02 | 2008-09-04 | Epcos Ag | Piezoelektrisches Material, Vielschicht-Aktuator und Verfahren zur Herstellung eines piezoelektrischen Bauelements |
WO2010108988A1 (de) | 2009-03-25 | 2010-09-30 | Tronox Pigments Gmbh | Bleizirkonattitanate und verfahren zu deren herstellung |
JP5640716B2 (ja) | 2010-12-15 | 2014-12-17 | ソニー株式会社 | 情報処理装置及び情報処理システム |
EP2846159A1 (de) * | 2013-09-06 | 2015-03-11 | Services Pétroliers Schlumberger | Fluidsensor mit piezoelektrischem Aktuator und Verfahren zur dessen Herstellung |
DE102016204888A1 (de) * | 2016-03-23 | 2017-03-16 | Continental Automotive Gmbh | Piezoelektrische Aktuatoreinheit und Herstellungsverfahren zum Herstellen einer Aktuatoreinheit |
DE102016107405A1 (de) * | 2016-04-21 | 2017-10-26 | Epcos Ag | Piezokeramik, Verfahren zu dessen Herstellung und elektrokeramisches Bauelement umfassend die Piezokeramik |
JP6913547B2 (ja) * | 2017-07-13 | 2021-08-04 | Njコンポーネント株式会社 | 圧電磁器組成物および圧電磁器組成物の製造方法 |
DE102018123611A1 (de) * | 2018-09-25 | 2020-03-26 | Tdk Electronics Ag | Keramisches Bauelement und Verfahren zur Herstellung des keramischen Bauelements |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
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US5453262A (en) * | 1988-12-09 | 1995-09-26 | Battelle Memorial Institute | Continuous process for production of ceramic powders with controlled morphology |
DE19615695C1 (de) * | 1996-04-19 | 1997-07-03 | Siemens Ag | Verfahren zur Herstellung eines Piezoaktors monolithischer Vielschichtbauweise |
JPH101364A (ja) * | 1996-06-18 | 1998-01-06 | Tokin Corp | 圧電磁器材料 |
-
2003
- 2003-05-05 JP JP2004509640A patent/JP2006501119A/ja active Pending
- 2003-05-05 US US10/516,078 patent/US20050258718A1/en not_active Abandoned
- 2003-05-05 AU AU2003240410A patent/AU2003240410A1/en not_active Abandoned
- 2003-05-05 WO PCT/DE2003/001430 patent/WO2003101946A2/de active Application Filing
- 2003-05-05 DE DE10393064T patent/DE10393064D2/de not_active Expired - Fee Related
- 2003-05-05 EP EP03729863A patent/EP1578730A3/de not_active Withdrawn
Non-Patent Citations (1)
Title |
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See references of WO03101946A2 * |
Also Published As
Publication number | Publication date |
---|---|
WO2003101946A3 (de) | 2005-10-27 |
US20050258718A1 (en) | 2005-11-24 |
AU2003240410A1 (en) | 2003-12-19 |
DE10393064D2 (de) | 2005-05-19 |
WO2003101946A2 (de) | 2003-12-11 |
EP1578730A3 (de) | 2005-12-14 |
AU2003240410A8 (en) | 2003-12-19 |
JP2006501119A (ja) | 2006-01-12 |
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