WO2007097460A1 - セラミック部材の製造方法、並びにセラミック部材、ガスセンサ素子、燃料電池素子、フィルタ素子、積層型圧電素子、噴射装置、及び燃料噴射システム - Google Patents
セラミック部材の製造方法、並びにセラミック部材、ガスセンサ素子、燃料電池素子、フィルタ素子、積層型圧電素子、噴射装置、及び燃料噴射システム Download PDFInfo
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- WO2007097460A1 WO2007097460A1 PCT/JP2007/053650 JP2007053650W WO2007097460A1 WO 2007097460 A1 WO2007097460 A1 WO 2007097460A1 JP 2007053650 W JP2007053650 W JP 2007053650W WO 2007097460 A1 WO2007097460 A1 WO 2007097460A1
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- layer
- metal
- ceramic
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- ZBSCCQXBYNSKPV-UHFFFAOYSA-N oxolead;oxomagnesium;2,4,5-trioxa-1$l^{5},3$l^{5}-diniobabicyclo[1.1.1]pentane 1,3-dioxide Chemical compound [Mg]=O.[Pb]=O.[Pb]=O.[Pb]=O.O1[Nb]2(=O)O[Nb]1(=O)O2 ZBSCCQXBYNSKPV-UHFFFAOYSA-N 0.000 description 2
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- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
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- 239000003345 natural gas Substances 0.000 description 1
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
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- 239000005361 soda-lime glass Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
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- 239000010936 titanium Substances 0.000 description 1
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/12—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte
- H01M8/124—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte
- H01M8/1246—Fuel cells with solid electrolytes operating at high temperature, e.g. with stabilised ZrO2 electrolyte characterised by the process of manufacturing or by the material of the electrolyte the electrolyte consisting of oxides
-
- 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
- C04B35/16—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 silicates other than clay
- C04B35/18—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 silicates other than clay rich in aluminium oxide
- C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
-
- 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
- H10N30/508—Piezoelectric or electrostrictive devices having a stacked or multilayer structure adapted for alleviating internal stress, e.g. cracking control layers
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- H10N30/80—Constructional details
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- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/54—Particle size related information
- C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
- C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
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- F02M51/00—Fuel-injection apparatus characterised by being operated electrically
- F02M51/06—Injectors peculiar thereto with means directly operating the valve needle
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- H01M2300/0065—Solid electrolytes
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- H01M2300/0077—Ion conductive at high temperature based on zirconium oxide
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/31678—Of metal
Definitions
- the present invention relates to a method for producing a ceramic member and a ceramic member obtained thereby. More specifically, the present invention relates to, for example, an indoor atmosphere detection, an atmosphere detection in a cave or tunnel, a gas sensor element used for exhaust gas detection, a fuel cell element used for power generation or the like, a filter element, and a fuel injection device for an automobile engine.
- the present invention relates to a ceramic member such as a laminated piezoelectric element used in a micro drive device, a piezoelectric sensor device, a piezoelectric circuit and the like, and a manufacturing method thereof.
- Gas sensor elements and fuel cell elements have a function of bringing a gas into contact with the ceramic members constituting them to adsorb or permeate specific components in the gas onto the ceramic surface.
- the metal layer has a high porosity structure to improve gas permeability, or even a dense electrode has a pattern such as a comb shape. Attempts have been made to control the area covered by the electrodes (see, for example, Patent Documents 1 and 2).
- a ceramic layer and an electrode metal are simultaneously formed after printing an electrode pattern using a metal without sintering unless the sintering temperature is higher than the sintering temperature of the ceramic. There is a method of firing.
- Patent Document 3 Another method for producing a metal layer having a high porosity is described in, for example, Patent Document 3 and includes a method for firing a Pt pressure film electrode.
- Patent Document 1 JP-A-6-317555
- Patent Document 2 JP-A-6-258281
- Patent Document 3 Japanese Patent Laid-Open No. 11-51899 Disclosure of the invention
- a representative method for producing a ceramic member of the present invention includes a step of producing a laminated molded body in which a plurality of metal paste layers containing a metal component M are laminated via ceramic green sheets, A step of producing the laminated molded body, wherein X is a mass percentage of the metal component M with respect to the total amount of metal components contained in the metal paste layer. At least one layer is a second metal paste layer having a mass percentage X higher than that of a metal paste layer adjacent in the stacking direction, and the second metal paste layer contains ceramic powder.
- the ceramic member according to the present invention includes a metal layer containing the metal component M and a plurality of ceramic lumps spaced apart from each other via voids, and the lumps-containing layer having more voids than the metal layer. And a three-layer structure including the metal layer and a ceramic layer sandwiched between the lump containing layers.
- the lump-containing layer in the ceramic member may further include a plurality of metal lumps that include the metal component M and are spaced apart from each other via a gap.
- At least one of the plurality of metal paste layers is more than the total amount of metal components contained in the metal paste layer than the metal paste layers adjacent in the stacking direction.
- the mass percentage X of the metal component M with respect to is high! This is the second metal paste layer, and the second metal paste layer contains ceramic powder.
- the metal component M between adjacent metal paste layers through the ceramic green sheet M By firing the laminated molded body with a difference (concentration gradient) in the mass percentage X of the metal, the metal component Mi can be diffused through the ceramic layer toward a high mass percentage X, a low force, and a low.
- the volume is reduced and the voids are increased as more metal components M are diffused out of the second metal paste layer in the firing process.
- the ceramic powder contained in the second metal paste layer is aggregated and sintered to the extent that it is in the firing process, and becomes a plurality of ceramic lumps.
- the mass percentage X of the metal component M is differentiated between the first metal paste layer and the second metal paste layer that are adjacent via the ceramic green sheet, and By firing a laminated molded body containing ceramic powder in the second metal paste layer, it is possible to obtain a ceramic brazing material having a mass-containing layer interspersed with a plurality of ceramic masses and having many voids. it can.
- FIG. 1 is a cross-sectional view showing a ceramic member that can be applied to an embodiment of the present invention.
- FIG. 3 is a schematic diagram schematically showing the ceramic member shown in FIG. 2.
- FIG. 4] (a) to (c) are conceptual diagrams showing a method of manufacturing a ceramic member that is useful in one embodiment of the present invention.
- FIG. 5 is a cross-sectional view showing a ceramic member having external electrodes formed on side surfaces.
- FIG. 6 is a cross-sectional view showing a ceramic member that is useful in another embodiment of the present invention.
- FIG. 7] (a) to (c) are conceptual diagrams showing a manufacturing method for producing a ceramic member that is effective in the embodiment shown in FIG.
- FIG. 8 is a cross-sectional view showing a ceramic member that is useful in still another embodiment of the present invention.
- FIG. 9 is a graph schematically showing features of the embodiment of FIG.
- FIG. 10 is a cross-sectional view showing a ceramic member that is useful in still another embodiment of the present invention.
- FIG. 11] (a) to (c) are conceptual diagrams showing a manufacturing method for producing a ceramic member that is effective in the embodiment shown in FIG.
- FIG. 12 is a cross-sectional view showing a ceramic member that is useful in still another embodiment of the present invention.
- FIGS. 13 (a) to (c) are conceptual diagrams showing a manufacturing method for producing a ceramic member that is effective in the embodiment shown in FIG.
- FIG. 14 Cross-sectional views showing ceramic members that are useful in still another embodiment of the present invention.
- FIG. 15 is a cross-sectional view showing a gas sensor element that works according to an embodiment of the present invention.
- FIG. 16 is a cross-sectional view showing a gas sensor element that works according to another embodiment of the present invention.
- FIG. 17 is a cross-sectional view showing a fuel cell element that works according to an embodiment of the present invention.
- FIG. 18 is a cross-sectional view showing a fuel cell element according to another embodiment of the present invention.
- FIG. 19 is a cross-sectional view showing a filter element that works according to an embodiment of the present invention.
- FIG. 20 is a cross-sectional view showing a filter element that works according to another embodiment of the present invention.
- FIG. 21 is a cross-sectional view showing a filter element that works according to still another embodiment of the present invention.
- FIG. 22 is a cross-sectional view showing a filter element that works according to still another embodiment of the present invention.
- FIG. 23 is a cross-sectional view showing a laminated piezoelectric element that works according to an embodiment of the present invention.
- FIG. 24 is a cross-sectional view showing a multilayered piezoelectric element that works according to another embodiment of the present invention.
- FIG. 25 is a cross-sectional view showing a laminated piezoelectric element that is useful in still another embodiment of the present invention.
- FIG. 26 is a cross-sectional view showing a multilayered piezoelectric element that can be applied to still another embodiment of the present invention.
- FIG. 27 is a cross-sectional view showing a multilayer piezoelectric element according to still another embodiment of the present invention. ⁇ 28] (a) is a perspective view showing a multilayer piezoelectric element that is useful in still another embodiment of the present invention, and (b) is a diagram illustrating a piezoelectric layer and an internal electrode layer in the multilayer piezoelectric element. It is an expanded view for demonstrating a lamination
- FIG. 29 is a cross-sectional view showing a peripheral portion of the element shown in FIG. 28.
- FIG. 30 is a cross-sectional view showing an injection device that works according to an embodiment of the present invention.
- FIG. 31 is a schematic view showing a fuel injection system according to an embodiment of the present invention.
- FIG. 32 is a perspective view showing a multilayer piezoelectric element that is useful in still another embodiment of the present invention.
- FIG. 33 is a cross-sectional view taken along line AA in FIG.
- FIG. 34 is an enlarged cross-sectional view of the vicinity of a composite layer of an element that is useful in still another embodiment of the present invention.
- FIG. 35 Internal electrode structure and composite layer structure in still another embodiment of the present invention.
- FIG. 36 is a perspective view showing a multi-layer piezoelectric element according to still another embodiment of the present invention.
- FIG. 37 is a partial perspective view showing a stacked state of a piezoelectric layer and internal electrodes in the stacked piezoelectric element of FIG. 36.
- FIG. 38 (a) is a cross-sectional view showing a cross section taken along a plane perpendicular to the stacking direction of the laminate and including the lump containing layer, and (b) is a lump containing the lump in (a).
- FIG. 3 is a cross-sectional view showing a cross section when a piezoelectric layer adjacent to a layer in the stacking direction is included and cut by a plane perpendicular to the stacking direction.
- FIG. 39 is a cross-sectional view showing a cross section when the laminate is cut along a plane parallel to the stacking direction of the laminate.
- FIG. 40 (a) is a cross-sectional view showing another example of a cross section taken along a plane perpendicular to the stacking direction of the laminate and including the massive-containing layer, and (b) is a cross-sectional view of the laminate.
- FIG. 10 is a cross-sectional view showing still another example of a cross section when cut by a plane perpendicular to the stacking direction and including a block-containing layer.
- FIG. 41 (a) is a perspective view showing a laminated piezoelectric element that works according to an embodiment of the present invention, and (b) shows a laminated state of the piezoelectric layer and the metal layer in (a). It is a fragmentary perspective view.
- FIG. 42 is an enlarged cross-sectional view of a joint portion between the external electrode and the side surface of the multilayer body in FIG. 41.
- FIG. 43 is a cross-sectional view of the laminated body in FIG. 41 cut along a plane including a block-containing layer in a direction perpendicular to the laminating direction.
- FIG. 44 is a cross sectional view showing a state of a sample before firing in Example 5.
- FIG. 45 is a cross sectional view showing a state of a sample after firing in Example 5.
- FIG. 46 is a conceptual diagram showing cross sections of sample numbers 1, 3, and 4 in Example 7.
- FIG. 47 is a conceptual diagram showing a cross section of Sample No. 5 in Example 7.
- FIG. 48 is a conceptual diagram showing a cross section of Sample No. 6 in Example 7.
- FIG. 1 is a cross-sectional view showing a ceramic member that works on this embodiment.
- the ceramic member 17 is sandwiched between the metal layer 13 containing the metal component M, the lump-containing body-containing layer 11 having a larger void than the metal layer 13, and the metal layer 13 and the lump-containing body layer 11. It has a ceramic layer 15 and a powerful three-layer structure.
- the lump containing layer 11 includes a plurality of ceramic lumps 3a that are spaced apart from each other.
- FIGS. 2A to 2C are cross-sectional views respectively showing specific examples of the lump containing layer 11 in the present embodiment.
- the block-containing layer 11 in FIG. 2 (a) is a porous layer having a plurality of ceramic blocks 3a and metal regions 3c that are spaced apart from each other and having a plurality of voids 3b.
- the mass-containing layer 11 includes a plurality of ceramic masses 3a that are spaced apart from each other via the voids 3b and a plurality of metal masses that are spaced apart from each other via the voids 3b.
- the mass-containing layer 11 in FIG. 2 (c) is composed of a plurality of ceramic masses 3a that are spaced apart from each other via the gap 3b.
- the “void” refers to a gap formed between the ceramic massive bodies 3a.
- FIG. 3 is a cross-sectional view schematically showing a cross section of the ceramic member 17 having the three-layer structure.
- the ceramic member 17 is formed by laminating a metal layer 13 and a lump containing layer 11 having more voids than the metal layer 13 via the ceramic layer 15.
- a manufacturing method according to an embodiment of the present invention for manufacturing the ceramic member 17 provided with the lump containing layer 11 is as follows.
- 4 (a) to 4 (c) are conceptual diagrams showing a method for manufacturing a ceramic member according to this embodiment.
- a laminated molded body 17a in which metal paste layers 1 la and 13a are laminated via ceramic green sheets 15a is produced.
- a step of firing the laminated molded body 17a is produced.
- a metal paste layer 1la and a metal paste layer 13a are laminated on both main surfaces of the ceramic green sheet 15a to produce a laminated molded body 17a.
- the metal paste layer 11a and the metal paste layer 13a are disposed at positions facing each other in the stacking direction.
- the metal paste layer 11a and the metal paste layer 13a contain the metal component M as a main component.
- the second metal paste layer 11a is more than the first metal paste layer 13a adjacent in the stacking direction. It is prepared so that the mass percentage X is high.
- the second metal paste layer 1 la may be referred to as a high-rate metal paste layer 1 la. This second metal paste layer 1 la contains ceramic powder.
- the ceramic powder in the present invention is a non-metallic inorganic powder and generally has a polycrystalline, single crystalline, or amorphous crystalline structure, such as alumina, lead zirconate titanate, titanium, etc.
- the second metal paste layer 11a preferably contains 0.01 to 115 parts by mass of ceramic powder with respect to 100 parts by mass of the total amount of metal components.
- the ceramic powder is less than 0.01 parts by mass with respect to 100 parts by mass of the total amount of metal components, most of the ceramic powder is absorbed by the ceramic layer, making it difficult to form a ceramic mass.
- the ceramic powder exceeds 115 parts by mass with respect to 100 parts by mass of the total amount of metal components, the ceramic powder is mainly sintered and the diffusion phenomenon of the metal components hardly occurs.
- Laminated ceramic member of the present invention When applied to a piezoelectric element, it is preferable to contain 0.1 to 75 parts by mass of ceramic powder with respect to 100 parts by mass of the total amount of metal components because a high stress relaxation effect can be obtained.
- 1 to 50 parts by mass of ceramic powder with respect to 100 parts by mass of the total amount of metal components More preferably, it is contained below.
- a method for producing the ceramic green sheet 15a is as follows. First, a slurry is prepared by mixing a ceramic raw material powder, a binder having an organic polymer power such as acrylic or petital, and a plasticizer such as DBP (dibutyl phthalate) or DOP (dioctyl phthalate). . Next, this slurry is formed into a sheet shape by a tape forming method such as a well-known doctor blade method or calendar roll method to obtain a ceramic green sheet 15a.
- a slurry is prepared by mixing a ceramic raw material powder, a binder having an organic polymer power such as acrylic or petital, and a plasticizer such as DBP (dibutyl phthalate) or DOP (dioctyl phthalate). .
- this slurry is formed into a sheet shape by a tape forming method such as a well-known doctor blade method or calendar roll method to obtain a ceramic green sheet 15a.
- the method for producing the second metal paste layer 1la and the first metal paste layer 13a is as follows. First, a metal base is prepared by adding and mixing a binder, a plasticizer, and the like to metal powder, alloy powder, and the like. At this time, the metal paste for the high-rate metal paste layer 11a is prepared such that the mass percentage X of the metal component M is higher than the metal paste for the metal paste layer 13a. The ceramic powder as described above is added to the high-rate metal paste layer 11a. The amount of the ceramic powder added may be appropriately determined according to the amount and size of the ceramic mass to be scattered in the mass-containing layer in the fired ceramic member.
- the obtained metal paste is printed on one main surface and the other main surface of the ceramic green sheet 15a by a method such as screen printing to form the high-rate metal paste layer 1 la and the metal paste layer 13a. And dry.
- the laminated molded body 17a thus obtained may be cut into a desired shape if necessary!
- the thicknesses of the high-rate metal paste layer 1 la and the metal paste layer 13a are adjusted to a range of about 1 to 40 m, for example.
- the laminated molded body 17a can also be produced by forming a metal paste layer and laminating two ceramic Darin sheets so that the principal surfaces are aligned with each other.
- the laminated compact 17a obtained as described above is subjected to a binder removal treatment at a predetermined temperature, and then fired at about 800 to 1500 ° C.
- Figure 4 (b) shows a laminated compact 17b during firing.
- FIG. 4 (c) shows the ceramic member 17 after firing.
- the mass-containing layer in which the plurality of ceramic masses 3a are interspersed and there are many voids can be formed at a desired position of the ceramic member.
- the sintering of the metal layer can proceed sufficiently, and even if acrylic resin is not used as in the prior art, V, and so on, impurity residues such as resin are added to the metal layer. Can be very little.
- the diffusion of the metal component M in this way is presumed to be based on the following reasons! That is, by making a difference in the mass percentage X of the metal component M between the high-rate metal paste layer and the adjacent metal paste layer through the ceramic green sheet, the difference in mass percentage of the metal component M according to Fick's law As a driving force, it is presumed that more metal component M diffuses from the high-rate metal paste layer to the adjacent metal paste layer.
- the high-rate metal paste layer 11a at least one of "alloy powder” containing the metal component M and "metal powder” made of the metal component M is blended.
- the metal paste layer 13a adjacent to the high-rate metal paste layer 11a in the stacking direction includes “alloy powder” containing the metal component M and the metal component M.
- metal powders are combined.
- alloy powders may be collectively referred to as “metal powders”.
- Metal component M and metal component M are combinations in which an alloy is formed between them.
- these metal components are a combination that hardly forms an intermetallic compound. It is more preferable that the combination of these metal components is a solid solution.
- the metal component M is a Group 11 element of the periodic table, and the metal component M
- 1 2 is preferably a group 10 element of the periodic table. Since the alloys of these Group 11 elements and Group 10 elements are completely dissolved, alloys of any concentration can be formed, and stable diffusion of metal components can be achieved. It becomes possible. Moreover, firing is possible even in an oxidizing atmosphere where the melting point is higher than the sintering temperature of the ceramic. Of these, silver platinum alloys and silver palladium alloys that can be fired simultaneously with ceramics are preferred.
- the metal component M is silver and the metal component M is palladium.
- the reason for this is the force that the silver oxide produced when silver is heated is a substance that forms the liquid phase of ceramics at low temperatures. Therefore, the sintering of the ceramic layer 15 proceeds at a low temperature by containing silver.
- Noradium and silver are all solid solution systems, and since the liquidus and solidus are close to each other, they can be easily dissolved in each other. For this reason, when the silver component diffuses from the lump containing layer l ib having a high silver concentration into the metal layer 13b through the liquid phase, it is selectively attracted and alloyed with various composition ratios. Is possible. As a result, silver having a lower melting point than palladium diffuses ahead of palladium, and this diffusion proceeds in a short time (see Fig. 4 (b)).
- the mass percentage X ((metal component M (mass) Z metal component total amount (mass)) X 100) in the high-rate metal paste layer 11a is 85 ⁇ X ⁇ 10 in terms of stabilizing the electrical properties of the ceramic member. It is preferably in the range of 0. When the mass percentage X is less than 85, the specific resistance of the metal layer having a high porosity increases, and when the ceramic member is energized, the metal layer may be difficult to dissipate heat.
- the range is 85 ⁇ X ⁇ 99.999. In terms of improving the durability of the ceramic member, it is more preferable that the range is 90 ⁇ X ⁇ 99.9. When higher durability is required, it is particularly preferable to be within the range of 90.5 ⁇ X ⁇ 99.5. When higher durability is required, it should be within the range of 92 ⁇ X ⁇ 98. There should be.
- the mass percentage X in the metal paste layer 13a is preferably in the range of 85 ⁇ X ⁇ 100 from the viewpoint of stabilizing the electrical characteristics of the ceramic member. Further, in order to suppress ion migration of the Group 11 element in the metal layer to the ceramic layer, it is more preferable that the range is 85 ⁇ X ⁇ 99.999.
- a force S in the range of 90 ⁇ X ⁇ 99.9 is more preferable. If higher durability is required, 90.5 ⁇ X ⁇ 99.5 In the case of seeking higher durability that is particularly preferable, it is better to be in the range of 92 ⁇ X ⁇ 98.
- the mass percentage X in the high-rate metal paste layer 1 la may be set higher than that of the metal paste layer 13a adjacent in the stacking direction. These mass percentage differences (mass percentage XH of high-rate metal paste layer 1 la—mass percentage XL of metal paste layer 13a) are not particularly limited.
- metal component M is silver and the metal component M is strong palladium or platinum is taken as an example.
- the mass percentage difference is preferably in the following range.
- the mass percentage difference is preferably 0.1 or more in that the diffusion of the metal component M is easy to proceed. Further, the mass percentage difference is preferably 30 or less in that the metal component M is prevented from excessively diffusing into the metal paste layer 13a and bonding between adjacent ceramic layers. Therefore, the mass percentage difference is preferably 0.1 or more and 30 or less.
- the diffusion rate of the metal component M is slow, a large amount of the metal component M remains in the ceramic when the ceramic in the ceramic green sheet 15a adjacent to the high-rate metal paste layer 11a is completely sintered. There are things to do.
- the diffusion rate of the metal component M can be increased by increasing the mass percentage difference. In terms of increasing the diffusion rate of the metal component M, the mass percentage difference is preferably 1 or more.
- the mass percentage difference is 10 or less. Therefore, the mass percentage difference is preferably 1 or more and 10 or less, more preferably 2 or more and 10 or less.
- the mass percentage difference is particularly preferably 3 or more and 5 or less from the viewpoint that both the stress relaxation function and the insulation can be achieved.
- the mass percentage difference is 3 or more and 5 or less, silver diffusion occurs moderately, so that the mass-containing layer 11 obtained after firing is composed of a plurality of metal masses separated from each other through voids. become.
- These metal blocks are interspersed between ceramic layers in a state of being electrically insulated from each other. Therefore, the lump containing layer 11 is an excellent insulating layer that does not function as an electrode.
- the plurality of metal blocks are dispersed in an appropriate size and an appropriate amount between the ceramic layers, it is possible to prevent the adjacent ceramic layers on both sides from being bonded during firing.
- the mass-containing layer 11 formed by interspersing a plurality of metal masses as described above is extremely excellent in the function of relieving stress during driving when used as, for example, a laminated piezoelectric element. Since such a lump containing layer 11 has lower rigidity than other parts in the element, stress at the time of driving tends to concentrate on the lump containing layer 11. In particular, stress tends to concentrate near the boundary between a plurality of metal blocks and a piezoelectric body. It is assumed that the stress is relieved by the local deformation of the piezoelectric material at the boundary.
- Metal component M (mass) Z Total amount of metal components (mass)) X 100)
- the mass percentage Z is preferably in the range of 0.001 ⁇ Z ⁇ 15. There should be.
- the range is 0.1 ⁇ Z ⁇ 10. 0.5 ⁇ Z ⁇ 9.5 for better heat transfer and higher durability It is particularly preferable to be in the range of 2 ⁇ Z ⁇ 8 when higher durability is desired.
- the content (mass) of the metal components M and M in the metal layer is
- EPMA Electro Probe Micro Analysis
- Silver is easily bonded to palladium.
- the acid oxide (acid silver) produced when silver is heated is formed at a temperature considerably lower than the melting point of Ag.
- This oxide is a component that forms a liquid phase with ceramic components. Therefore, when silver powder is blended in the high-rate metal paste layer 11a and silver palladium alloy powder is blended in the metal paste layer 13a,
- platinum is mixed with silver in the high-rate metal paste layer 11a, and platinum is mixed with palladium in the metal paste layer 13a.
- silver is selectively alloyed with palladium.
- the diffusion rate is slower than that of palladium. Due to the presence of platinum, a part of silver forms an alloy with platinum. Therefore, it is possible to suppress excessive diffusion of silver even when firing in which a large temperature distribution is generated in the stacked molded body 17a during firing or firing at a high temperature increase rate is performed. Thereby, it can suppress that all the silver and palladium in a metal paste diffuse, and a metal layer lose
- the metal component M is silver (Ag) and the metal component M is strong palladium (Pd).
- the high-rate metal paste layer 11a at least one of “alloy powder” containing Ag such as Ag—Pd alloy and Ag—Pt alloy and “metal powder” such as Ag alloy is blended.
- the metal paste layer 13a is blended with at least one of “alloy powder” containing Ag and Pd such as Ag—Pd alloy and “mixed powder” containing Ag powder and Pd powder.
- Pd powder tends to be oxidized at a lower temperature than Pd in an Ag-Pd alloy. For this reason, in comparison with the case of using an Ag—Pd alloy as the raw material of the metal paste, when the Pd powder is used, the volume of the metal layer may be increased due to oxidation during firing. Therefore, when the metal component is M-strength palladium (Pd), it is used as a raw material for the metal paste.
- an Ag—Pd alloy it is preferable to use an Ag—Pd alloy.
- the powder is a mixture of Ag powder and Ag-Pd alloy powder, the melting point of Ag is low, so Ag starts to diffuse first, increasing the Ag concentration of Ag-Pd alloy. This is preferable because it induces diffusion and achieves the fastest and stable diffusion.
- the ceramic green sheet 15a before firing is in a state where a filler is filled between ceramic raw material powder particles, but in the middle of sintering shown in FIG. One volatilizes and a fine gap is formed between ceramic particles. As the firing temperature rises further, the ceramic particles start to sinter, and the metal powder contained in the printed metal paste layer also starts to sinter.
- the mass percentage X of 1 lb of the mass-containing layer is prepared so as to be higher than the mass percentage of the metal layer 13b.
- the mass percentage of the same metal between metal layers Due to the difference, it is presumed that silver in the lump containing layer l ib diffuses and moves to the metal layer 13b through the ceramic layer 15b during sintering according to the difference in mass percentage (concentration gradient) of silver.
- the lump-containing layer 11 has a high fluidity in the liquid phase during sintering in addition to the fact that the silver is diffused and transferred to the metal layer 13 to reduce the volume. Or silver palladium alloy agglomerates.
- the lump containing layer 11 is a porous layer in which a plurality of closed cells are dispersed and the inside of the ceramic layer 15 is not uniformly coated with a metal component.
- Fig. 2 (a) or composed of a plurality of ceramic masses separated from each other via voids and a plurality of metal masses separated from each other via voids
- Fig. 2 (c) consists of a plurality of ceramic masses separated from each other through a gap
- the metal layer 13 becomes a relatively dense metal layer because silver diffuses and moves from the lump containing layer 11. It is preferable to add a sintering aid to the ceramic green sheet 15a and the metal paste so that a liquid phase is easily formed during sintering.
- the lump containing layer 11 includes a metal component (metal region 3c or metal lump 3c) as shown in FIGS. 2 (a) and 2 (b).
- a metal component metal region 3c or metal lump 3c
- the mass percentage Y is preferably set high.
- the ceramic member When the ceramic member is installed and used in an environment where it is exposed to high temperatures, migration may proceed if there is a light and dark composition between the metal layer 13 and the lump containing layer 11.
- the mass percentage Y of the lump containing layer 11 is higher than that of the metal layer 13, it is possible to suppress the movement of the metal component M from the metal layer 13 toward the lump containing layer 11. Therefore, the high porosity of the lump containing layer 11 is maintained. As a result, it is expressed by a high porosity.
- the sensor function and the stress relaxation function are maintained, and a highly durable ceramic member can be obtained.
- FIG. 5 is a cross-sectional view showing a ceramic member having external electrodes 19 formed on the side surfaces.
- This external electrode may be formed as follows, for example.
- a metal paste is prepared by adding a noinder, a plasticizer, or the like to the metal powder.
- the metal paste is printed on a predetermined portion, dried, and then fired. At this time, the metal paste may be printed on the ceramic member as it is, but it is preferable to perform printing after the printing surface is flattened by polishing or the like.
- the other parts are denoted by the same reference numerals as those in FIG.
- “many voids” means that the total area occupied by the voids in the cross section of the metal layer is large.
- the following may be performed. Using a scanning electron microscope (SEM), metal microscope, optical microscope, etc., observe the cross section of the lump containing layer 11 and the cross section of the metal layer 13 (cross section parallel to the stacking direction or cross section perpendicular to the stacking direction). What is necessary is just to obtain a cross-sectional image and evaluate this cross-sectional image.
- the porosity of the metal layer (or the mass-containing layer) of the ceramic member can be measured, for example, as follows. That is, first, the ceramic member is laminated using a known polishing apparatus until the cross section (cross section parallel to the lamination direction or cross section perpendicular to the lamination direction) of the metal layer or the lump containing layer whose porosity is to be measured is exposed. Polish in the direction. Specifically, for example, a table polishing machine KEMET-V-300 manufactured by Kemet Japan Co., Ltd. can be used as a polishing apparatus.
- the cross section exposed by the polishing process is observed with, for example, a scanning electron microscope (SEM), a metal microscope, an optical microscope, and the like to obtain a cross section image, and the porosity is measured by performing image processing on the cross section image. It can.
- SEM scanning electron microscope
- the magnification for observation with SEM or the like should be set to about 1000 to 1000 times.
- the metal layer (or lump) It is preferable to polish to the position of about 1Z2 of the thickness of the body-containing layer) and observe the exposed cross section.
- the entire cross section of the metal layer may not be exposed by the polishing process.
- the polishing process is performed until a part of the metal layer or the lump containing layer is exposed, the exposed part is observed to obtain a cross-sectional image, and then the polishing is further progressed and observed.
- the operation of observing other parts other than may be repeated several times. It would be good if the entire cross-section of the metal layer (or lump containing layer) can be observed by adding together the observation images obtained in this way.
- a specific example of image processing is as follows. For example, for a cross-sectional image taken with an optical microscope, the void portion is painted black, and the portion other than the void is painted white, and the ratio of the black portion, that is, (area of the black portion) Z (black portion).
- the void ratio can be calculated by calculating (area + white area) and expressing it as a ratio.
- the photographed cross-sectional image data can be loaded into a computer, and the porosity can be measured by image processing software.
- the cross-sectional image is a color, it is better to convert it into a gray scale and separate it into a black part and a white part.
- the threshold value of the boundary it is necessary to set the threshold value of the boundary to make two gradations in the black part and the white part, set the threshold value of the boundary by image processing software or visual observation, and then binarize it. Oh ,.
- FIG. 6 is a cross-sectional view showing a ceramic member 27 that is useful in another embodiment of the present invention. As shown in FIG. 6, the ceramic member 27 is formed by laminating a lump containing layer 21 and a metal layer 23 with a ceramic layer 25 interposed therebetween.
- the lump containing layer 11 includes the metal component in the form shown in FIGS. 2 (a) and 2 (b)
- the mass percentage of the metal component M with respect to the total amount of the metal component contained in the metal layer is Y
- the body-containing layer 21 preferably has a higher mass percentage Y and a higher porosity than the metal layers 23, 23 on both sides adjacent to each other in the stacking direction.
- the ceramic member 27 includes a metal layer 23 containing the metal component M (first metal layer 23), a block-containing layer 21 (second metal layer 21) having more voids than the metal layer 23, and these metals. It includes two three-layer structures consisting of a ceramic layer 25 sandwiched between layers. The ceramic member 27 has a five-layer structure composed of two three-layer structures that share the lump containing layer 21 (second metal layer 21). It is.
- the production method of the present invention for producing the ceramic member 27 provided with such a mass-containing layer 21 is as follows.
- 7 (a) to 7 (c) are conceptual diagrams showing a manufacturing method for manufacturing a ceramic member that is effective in the present embodiment.
- This manufacturing method includes a step of producing a laminated molded body 27a in which the metal paste layers 21a and 23a are laminated via the ceramic green sheets 25a, and a step of firing the laminated molded body 27a. .
- the method for producing the ceramic green sheet and the metal paste is the same as described above.
- a plurality of ceramic green sheets 25a are prepared, and a metal paste layer 21a or 23a is printed on one main surface of each green sheet 25a by a method such as screen printing, and metal paste layers are formed on both sides of the metal paste layer 21a in the stacking direction.
- a laminated molded body 27a is obtained (FIG. 7 (a)).
- the metal paste layer 21a and the metal paste layer 23a contain the metal component M as a main component.
- the metal paste layer 21a is prepared so that the mass percentage X is higher than the metal paste layers 23a and 23a on both sides adjacent to each other in the stacking direction.
- the metal paste layer 21a is referred to as a high-rate metal paste layer 21a.
- the present embodiment is different from the basic structure described above in that the metal paste layers 23a are arranged on both sides in the stacking direction of the high-rate metal paste layer 21a.
- the metal paste layers 23a are arranged on both sides in this way, the metal component M of the high-rate metal paste layer 21a is diffused into the metal paste layers 23a on both sides by firing the laminated compact 27a.
- the laminated compact 27a shown in Fig. 7 (a) undergoes the sintering process shown in Fig. 7 (b) to become the ceramic member 27 shown in Fig. 7 (c), as described above.
- the metal layers 23 and 23 are relatively dense metal layers because the metal component diffuses and moves from the lump containing layer 21.
- FIG. 8 is a cross-sectional view showing a ceramic member that can be applied to still another embodiment of the present invention.
- the ceramic member 37 is formed by laminating a lump containing layer 21 and a metal layer 23 with a ceramic layer 25 interposed therebetween.
- a plurality of the mass-containing layers 21 are arranged in the stacking direction.
- These block-containing layers 21 are respectively disposed with a plurality of metal layers 23 sandwiched therebetween.
- These lump containing layers 21 are laminated Are arranged regularly (according to a predetermined rule). Specifically, the lump containing layer 21 is arranged via a predetermined number of metal layers 23.
- the production method of the present invention for producing the ceramic member 37 provided with the plurality of mass-containing layers 21 as described above is as follows. That is, the ceramic green sheet 25a, the metal paste layer 23a, and the high-rate metal paste layer 21a are respectively produced in the same manner as described above, and the metal paste layer 23a or the high-rate metal paste layer is formed on the main surface of the ceramic green sheet 25a. Print 21a.
- each high-rate metal paste layer 21a is arranged with a plurality of metal paste layers 23a sandwiched therebetween, and each high-rate metal paste layer 21a is regularly arranged in the stacking direction.
- Each green sheet 25a is laminated to produce a laminated molded body. Subsequently, the laminated member is fired to obtain a ceramic member 37.
- a ceramic member 37 having the characteristics shown in FIG. 9 is produced by adjusting the amount of the metal component Ml diffused from the high-rate metal paste layer 21a to the metal paste layer 23a by adjusting the firing conditions. Can do.
- the mass percentage Y has a peak in the lump containing layer 21, and from this lump containing layer 21 to at least two metal layers 23 on both sides in the stacking direction. It gradually decreases over time (in the case of the form shown in FIGS. 2 (a) and 2 (b) in which the lump containing layer 11 contains a metal component).
- the reason why the mass percentage Y shows the characteristics shown in Fig. 9 is as follows.
- the mass percentage X of 2 lb of the mass-containing layer is prepared so as to be higher than the mass percentage of the metal layer 23b as described above.
- the difference in the mass percentage of the same metal between the metal layers causes the metal component of the mass-containing layer 21b to pass through the ceramic layer 25b during sintering according to the mass percentage difference of the metal component. It diffuses and moves to the metal layer 23b. Since the metal layer 23b is in a state in which the mass percentage Y of the metal component M is higher than that of the metal layer 23b adjacent to the metal layer 23b, a concentration gradient is also generated between the metal layers 23b and 23b.
- the mass percentage Y has a peak in the lump containing layer 21, and the lump containing layer 21 has both peaks in the stacking direction. It is possible to obtain the ceramic member 37 having a structure that gradually decreases over at least two metal layers 23 on the side. When the firing time is lengthened, the difference in the mass percentage Y of each metal layer becomes smaller, and eventually approaches the same value.
- the ceramic member 37 having such a structure has an advantage that the thermal shock resistance is strong because the metal component concentration gradually decreases without abrupt change. This is due to the fact that metal is superior to ceramics in thermal conductivity and that the thermal conductivity changes depending on the metal composition. That is, since the metal component concentration gradually decreases without abrupt change, it is possible to suppress a change in heat conduction characteristics in the ceramic member.
- FIG. 10 is a cross-sectional view showing a ceramic member that can be applied to still another embodiment of the present invention.
- this ceramic member 28 is formed by laminating a metal layer 22 and a lump containing layer 24 via a ceramic layer 26, respectively.
- the adjacent metal layer 24 with the metal layer 22 sandwiched from both sides has a mass greater than that of the metal layer 22. It is preferable that the percentage Y is low and the porosity is high.
- the ceramic member 28 includes a metal layer 22 containing the metal component M (first metal layer 22), a block-containing layer 24 (second metal layer 24) having more voids than the metal layer 22, and these metals. It includes two three-layer structures consisting of a ceramic layer 26 sandwiched between layers. In addition, the ceramic member 28 has a five-layer structure having two three-layer structural forces that share the metal layer 22 (first metal layer 22).
- FIGS. L l (a) to (c) are conceptual diagrams showing a manufacturing method for producing a ceramic member that is effective in the embodiment shown in FIG.
- This manufacturing method includes a step of producing a laminated molded body 28a in which metal paste layers 22a, 24a are laminated via ceramic green sheets 26a, and a step of firing the laminated molded body 28a.
- the method for producing the ceramic green sheet and the metal paste is the same as described above.
- a plurality of ceramic green sheets 26a are prepared, and a metal paste layer 22a or 24a is printed on one main surface of each green sheet 26a by a method such as screen printing.
- a method such as screen printing.
- the metal paste layer 22a and the metal paste layer 24a contain the metal component M as a main component.
- the metal paste layer 22a is prepared such that the mass percentage X is lower than the metal paste layers 24a and 24a on both sides adjacent to each other in the stacking direction.
- the metal paste layer 22a is referred to as a low-rate metal paste layer 22a.
- the present embodiment differs from the basic structure described above in that the metal paste layer 24a is disposed on both sides of the low-rate metal paste layer 22a.
- the metal paste layer 24a is arrange
- the mass percentage X of the metal layer 22b sandwiched between the mass-containing layers 24b is prepared so as to be lower than the mass percentage of the metal layers 24b and 24b.
- the difference in the mass percentage of the same metal between the metal layers allows the metal components of the block-containing layer 24b on both sides to pass through the ceramic layer 26b during the sintering in accordance with the mass percentage difference of the metal components. Therefore, both side forces of metal layer 22b diffuse and move (Fig. Ll (b)).
- a ceramic member 28 as shown in FIG. 11 (c) is obtained (FIG. 11 (c)).
- the metal layer 22 becomes a relatively dense metal layer because the metal component diffuses and moves from the lump containing layer 24.
- the mass percentage X in the low-rate metal paste layer 22a may be set lower than that in the metal paste layer 24a adjacent to both sides in the stacking direction. These mass percentage differences (mass percentage XH of metal paste layer 24a—mass percentage XL of low percentage metal paste layer 22a) are not particularly limited.
- metal component M is silver and the metal component M is palladium or platinum is taken as an example.
- the mass percentage difference is preferably in the following range.
- the mass percentage difference is preferably 0.1 or more in that the diffusion of the metal component M is easy to proceed. Further, it is preferable that the mass percentage difference is 30 or less in that the metal component M is excessively diffused into the low-rate metal paste layer 22a and the adjacent ceramic layers are prevented from being bonded to each other. Therefore, the mass percentage difference should be 0.1 or more and 30 or less.
- the mass percentage difference is 1 or more. Preferably above. In addition, it is preferable that the mass percentage difference is 2 or more at the point where the above-described interdiffusion phenomenon occurs more actively.
- silver diffuses from the metal paste layer 24a located on both sides in the stacking direction with respect to the low rate metal paste layer 22a to the low rate metal paste layer 22a.
- the mass percentage difference is more preferably 25 or less from the viewpoint of increasing the sintered density of the ceramic by suppressing the diffusion rate of the metal component M.
- the mass percentage difference should be 10 or more. Therefore, the mass percentage difference is more preferably 10 or more and 25 or less.
- FIG. 12 is a cross-sectional view showing a ceramic member 127 that is useful in still another embodiment of the present invention. As shown in FIG. 12, the ceramic member 127 is obtained by laminating a lump containing layer 121 and a metal layer 123 via a ceramic layer 125, respectively.
- the lump containing layer 121 includes a part of the metal layer 121 and a part of the region 124 having more voids than the other region 122. Some of the regions 124 preferably have a higher mass percentage Y and higher porosity than the other regions 122 and the metal layer 123. Hereinafter, a part of the region 124 is referred to as a porous region 124.
- the production method of the present invention for producing the ceramic member 127 having the porous region 124 in the metal layer 121 is as follows.
- 13 (a) to 13 (c) are conceptual diagrams showing a manufacturing method for producing the ceramic member according to the present embodiment.
- This manufacturing method includes a step of producing a laminated molded body 127a in which the metal paste layers 121a and 123a are laminated via the ceramic green sheet 125a, and a step of firing the laminated molded body 127a. Yes.
- the method for producing the ceramic green sheet and the metal paste is the same as described above.
- a plurality of ceramic green sheets 125a are produced, and a metal paste layer 121a or 123a is printed on one main surface of each green sheet 125a by a method such as screen printing, and the metal paste is formed on both sides of the metal paste layer 121a in the stacking direction.
- Each green so that layer 123a is placed By laminating the sheets, a laminated molded body 127a is obtained (FIG. 13 (a)).
- the metal base layer 121a works together with the metal paste layer 122a for the other region 122 and the metal paste layer 124a for the partial region 124.
- the metal paste layer 121a (122a, 124a) and the metal paste layer 123a contain the metal component M as a main component.
- the metal paste layer 124a is prepared such that the mass percentage X is higher than that of the metal paste layer 122a and the mass percentage X is higher than that of the metal paste layers 123a and 123a on both sides adjacent to each other in the stacking direction.
- the metal paste layer 124a is referred to as a high-rate metal paste layer 121a.
- the metal component M of the high-rate metal paste layer 124a is formed in the same plane by firing the laminated molded body 127a. It diffuses into the metal paste layers 123a on both sides preferentially over diffusion.
- the laminated molded body 127a shown in Fig. 13 (a) is subjected to the sintering process shown in Fig. 13 (b) and the ceramic member 127 shown in Fig. 13 (c), as described above. Become. In this way, regions (porous region 124 and other regions 122) having different porosity can be formed in the same layer.
- FIG. 14 is a cross-sectional view showing a ceramic member that can be applied to still another embodiment of the present invention.
- the mass-containing layer 29 has a plurality of ceramic masses interspersed between the ceramic layers 25, 25 adjacent to the mass-containing layer 29 in the stacking direction.
- the body (or metal block (partial metal layer)) 29a, 29a,..., And these blocks 29a are arranged apart from each other!
- the plurality of massive bodies 29a are in a state of being electrically insulated from each other via the gap 29b.
- the lump containing layer 29 has a form in which a plurality of lumps 29a are scattered on the ceramic layer 25 when the lump containing layer 29 is viewed in plan.
- the body-containing layer 29 functions as an excellent stress relaxation layer and also has excellent insulating properties.
- the ceramic member as described above has, for example, ZnO, SnO on the ceramic layer.
- the lump containing layer can be formed using a ceramic material such as cordierite, alumina, or Zr 2 O used for the ceramic layer.
- the body-containing layer can be used as a filter for removing harmful substances contained in exhaust gas.
- a ceramic material of solid electrolyte material represented by ZrO is used for the ceramic layer.
- the metal layer and the lump containing layer can be energized and driven, or conversely, can be used as a piezoelectric element capable of obtaining an electromotive force.
- a piezoelectric material such as lead (PZT) or ZnO
- the porosity of the mass-containing layer in the ceramic member of the present invention is not particularly limited as long as it is appropriately set depending on the application.
- the porosity can be changed by appropriately adjusting the mass percentage X, firing time, firing temperature and the like.
- the ceramic member 17 shown in FIG. 3 can be used as a gas sensor element.
- this ceramic member 17 is applied to a gas sensor element, as a material constituting the ceramic layer 15, for example, a ceramic material exhibiting oxide semiconductor characteristics represented by ZnO, SnO, TiO
- FIG. 15 is a cross-sectional view showing a gas sensor element according to another embodiment of the present invention having excellent characteristics.
- This gas sensor element 41 has a ceramic layer 43 with a solid typified by ZrO.
- the metal layer 45 is in contact with the gas, and the mass-containing layer 47 with a high porosity is in contact with the atmosphere.
- the lump containing layer 47 is sealed from the surroundings by the external electrode 49 and the ceramic layer 51 so that the gas in contact with the metal layer 45 does not contact the metal layer 47.
- gases having different oxygen concentrations can be in contact with the main surfaces on both sides of the ceramic layer 43, which is a solid electrolyte.
- the gas sensor element is provided with a gas introduction hole.
- the detected signal can be transmitted at high speed through the dense electrode (metal layer 53). That is, the external electrode 49 functions as a guide for guiding the atmosphere as a reference gas, and further has a function of transmitting signals at high speed.
- the ceramic layers 51 and 55 are made of an alumina ceramic material having heat resistance and high heat conduction performance, rapid heating is possible when the gas sensor element is heated and used. can do.
- the ceramic layers 43, 51, 55 are made of a solid electrolyte typified by ZrO.
- FIG. 16 is a cross-sectional view showing another embodiment of the gas sensor element.
- a heater body type oxygen sensor in which the heating element 57 is built in the ceramic layer 55 can also be provided.
- a method for manufacturing the gas sensor element shown in FIG. 15 will be described. First, a powder of ZrO ceramic (stable zirconia) added with Ca and Y is mixed with the binder and the plasticizer.
- the slurry is formed into a ceramic liner sheet in the same manner as described above.
- a metal paste for forming the metal layer 53 is produced.
- This metal paste is obtained mainly by adding and mixing a binder, a plasticizer and the like to a metal powder made of silver palladium powder.
- This metal paste is printed on one side of the green sheet by screen printing or the like.
- a metal paste for forming the high-porosity lump-containing body containing layer 47 is produced.
- This metal paste is obtained by adding and mixing a binder, a plasticizer and the like to a metal powder containing silver as a main component.
- This metal paste is printed on a green sheet by screen printing or the like.
- a green sheet on which these metal paste layers are formed is laminated, and another green sheet is further laminated on the high-rate metal base and dried to obtain a laminated molded body.
- the thickness of the metal paste layer is preferably about 1 to 40 / ⁇ ⁇ .
- the laminated molded body is debindered at a predetermined temperature, and then fired at 800 to 1000 ° C.
- silver diffuses from the metal layer 47 having a high silver concentration to the metal layer 53 to form a metal layer 47 having a high porosity, and a relatively dense metal layer 53 is formed.
- a metal paste is produced by adding and mixing a noinder, a plasticizer, and the like to a metal powder mainly having platinum power.
- the ceramic layer can be sintered more densely than the ceramic. Platinum having a high liquidus point does not become a dense sintered body, and a metal layer 45 having a high porosity is formed.
- a more porous electrode can be produced by using a metal paste obtained by adding the same amount of acrylic beads having an average particle diameter of 5 ⁇ m to platinum powder having an average particle diameter of 1 m.
- the external electrode 49 is formed.
- the external electrode 49 is made by adding a binder, a plasticizer, glass powder and the like to a metal powder mainly made of silver powder to prepare a metal paste, and applying this metal paste to the side of the sintered body by screen printing or the like.
- Yo It can be formed by printing and firing at 600-800 ° C.
- a binder, a plastic, a metal powder mainly having a platinum power is included in a ceramic green sheet for forming the ceramic layer 55. If there is a step of printing a metal paste made by adding and mixing agents, glass powder, etc., in the form of a heating element pattern,
- the porosity of the agglomerate-containing layer is preferably 30 to 90% in that gas supply is performed stably and the durability of the metal layer itself is also achieved. . Further, it is more preferably 50 to 90% from the viewpoint that the stress generated from the difference in coefficient of thermal expansion between the electrode and the ceramic can be relaxed by the cushioning effect of the air layer. Furthermore, the turbulent flow is a part where the supplied gas is stirred as a turbulent flow and the gas detection function is improved by forming a laminar flow at the boundary between metal and ceramics in the gap. More preferably, it is 70 to 90% where a space having both a laminar flow portion and a laminar flow portion is created.
- the porosity of the metal layer other than the block-containing layer is preferably 0.1 to 40% because the denser the electric conductivity is, the higher the signal can be transmitted.
- metal since metal has higher thermal conductivity than ceramics, if the metal layer is dense, the metal layer can transmit heat to the ceramics even when the sensor is activated, and a sensor with a high rise speed can be obtained.
- the porosity is more preferably 0.1 to 20%.
- FIG. 17 is a cross-sectional view showing a fuel cell element according to one embodiment of the present invention.
- a fuel cell can be obtained by collecting electromotive force generated by bringing a gas having a different oxygen concentration into contact with a solid electrolyte.
- electromotive force generated by bringing a gas having a different oxygen concentration into contact with a solid electrolyte.
- it is important to store and combine many fuel cell elements in a small volume and efficiently integrate electromotive force.
- an electrode layer 63 having a high porosity is used for a layer in which oxygen flows (so-called air electrode), and also for a layer having a very low oxygen concentration (so-called fuel electrode).
- An electrode layer 65 having a high porosity is used.
- the ceramic layer 67 in between is represented by ZrO. Sandwich solid electrolyte. The basic part of the fuel cell can now be formed.
- the external electrode 69 and the ceramic layers 67, 71 can seal the electrode layer 63 serving as an air electrode, the surrounding force can be sealed, so that a large amount of oxygen can flow through the electrode 63 having a high porosity. Further, since the dense electrode layer 73 is connected to the electrode layer 63 having a high porosity through the external electrode 69, the electromotive force can be transmitted efficiently.
- the external electrode 69 and the ceramic layers 67 and 75 can seal the electrode layer 65 that serves as the fuel electrode, the surrounding force can be sealed, so that a gas with a very low oxygen concentration (for example, natural gas) can flow through the electrode layer 65 with a high porosity. ) In large quantities. Furthermore, since the dense electrode 77 is connected to the high porosity electrode 65 via the external electrode 69, the electromotive force can be transmitted efficiently.
- a gas with a very low oxygen concentration for example, natural gas
- the power generation efficiency of the fuel cell is improved by heating it. At that time, when used in a high-temperature atmosphere, there was a problem that the electrode components diffused and moved in the past, but the metal layers 73, 77 and the metal layers 63, 65 with high porosity are Since component M is the main component, differences in ionization tendency and differences in electronegativity can be kept small.
- metal ions can be prevented from moving or diffusing when functioning as a battery, so that the element has stable durability. Furthermore, as shown in FIG. 18, by stacking fuel cell elements and connecting external electrodes of the same polarity, a small and high-density fuel cell element can be produced.
- a slurry is prepared by mixing the agent.
- ceramic green sheets for the ceramic layers 67, 71, 75, 79, 81 are produced in the same manner as described above.
- a metal paste for the metal layers 73 and 77 is produced.
- This metal paste is mainly obtained by adding and mixing a noinder, a plasticizer, etc. to a metal powder having a silver ⁇ radium power.
- This metal paste is printed on one side of the green sheet by screen printing or the like.
- a metal paste for the metal layers 63 and 65 having a high porosity is produced.
- This metal paste is obtained by adding and mixing a binder, a plasticizer and the like to metal powder containing silver as a main component.
- This metal paste is printed on one side of the green sheet by screen printing or the like.
- green sheets printed with each metal paste are stacked so as to have the structure shown in FIG.
- the thickness of the metal paste layer can be about 1 to 40 ⁇ m for screen printing.
- the laminated molded body is debindered at a predetermined temperature, and then fired at 800 to 1000 ° C. Then, silver diffuses from the metal layer having a high silver concentration to the alloy layer, and metal layers 63 and 65 having a high porosity are formed, and relatively dense metal layers 73 and 77 are formed.
- the external electrode 69 is formed after the sintered body is cast to a desired dimension.
- the external electrode 69 is made by adding a binder, a plasticizer, glass powder, etc. to a metal powder mainly made of silver powder to produce a metal paste, and applying this metal paste to the side of the sintered body by screen printing or the like. Therefore, it can be formed by printing and baking at 600 to 800 ° C.
- the silver concentration is high, the silver concentration is low from the metal paste layer, and the metal diffuses into the metal paste layer to form a metal layer 47 with a high porosity, thereby forming a relatively dense metal layer 53.
- other conventionally known methods other than the above steps may be used. In the case of the form shown in FIG. 18, further necessary steps may be added from the above steps.
- the porosity of the agglomerate-containing layer is preferably 30 to 90% in that gas supply is performed stably and the durability of the metal layer itself is also achieved. Further, it is more preferably 50 to 90% from the viewpoint that the stress caused by the difference in thermal expansion coefficient between the electrode and the ceramic can be relieved by the cushioning effect of the air layer.
- the solid electrolyte can detect the oxygen concentration accurately. From the viewpoint of improvement, it is more preferably 70 to 90% in which a space having both a turbulent flow portion and a laminar flow portion is created.
- the porosity of the metal layer other than the block-containing layer is preferably 0.1 to 40% because the higher the density, the higher the electric conductivity and the faster the signal can be transmitted.
- the metal since the metal has higher thermal conductivity than the ceramic, if the metal layer is dense, the metal layer can transmit heat to the ceramic even when the fuel cell is started, so that a fuel cell element having a high rise speed can be obtained.
- the porosity is more preferably 0.1 to 20%.
- FIG. 19 is a cross-sectional view showing a filter element that works according to an embodiment of the present invention.
- Figure 19 As shown, in this filter element 61, an electrode layer 63 having a high porosity is used as a gas flowing layer, and an electrode layer 73 for heating or heat transfer is used. A ceramic layer typified by cordierite and alumina is sandwiched in the ceramic layer 71 therebetween. The basic part of the filter can now be formed. Further, since the electrode layer 63 having a high porosity can be sealed from the surroundings with the ceramic layers 67 and 79, the porosity is high, and a large amount of gas can flow through the electrode 63.
- the metal itself of the electrode layer 63 having a high porosity functions as a catalyst, and can be locally burned or selectively adsorbed, so that a specific substance can be selectively removed.
- the use of the filter while heated improves the harmful substance removal efficiency.
- the force that conventionally caused the problem of electrode components to diffuse and move The metal layer 73 and the metal layer 63 with a high porosity are mainly composed of the metal component M. Therefore, the difference in ionization tendency and the difference in electronegativity can be kept small. For this reason, metal ions can be prevented from moving or diffusing as much as possible, so that a highly durable element that can be used stably can be obtained.
- FIG. 20 by stacking filter elements and connecting external electrodes of the same polarity, it is possible to produce a small and high-density filter element.
- a powder is prepared by mixing the powder, the binder, and the plasticizer.
- ceramic green sheets for the ceramic layers 67, 71, and 79 are prepared from the slurry by using the tape molding method described above.
- a metal paste for the metal layer 73 is produced in the same manner as described above.
- the green sheets on which the respective metal pastes are printed are stacked so as to have the structure shown in Fig. 19 and dried to obtain a laminated molded body before firing.
- the laminated molded body can be cut into a desired form.
- the thickness of the metal paste layer can be about 1 to 40 ⁇ m for screen printing.
- the laminate molded body was debindered at a predetermined temperature, and then at 800 to 1000 ° C. Bake. Then, silver diffuses from the metal layer having a high silver concentration to the alloy layer, thereby forming a metal layer 63 having a high porosity, and a relatively dense metal layer 73 is formed.
- the necessary steps among the above steps may be further added.
- the metal layer 63 having a high porosity may be pattern-printed.
- the ceramic powder contained in the lump containing layer 63 is formed as a liquid phase during firing, and at the same time, precipitates from the liquid phase. At that point, it creates a strong bond with the surrounding metal particles.
- the porosity of the agglomerate-containing layer is preferably 30 to 90% in that gas supply is performed stably and the durability of the metal layer itself is also achieved. . It is more preferably 50 to 90% in that the stress generated by the air layer cushioning effect can relieve the stress caused by the difference in coefficient of thermal expansion between the electrode and the ceramic.
- the supplied gas is agitated as a turbulent flow and a laminar flow is formed at the boundary between the metal and ceramics in the void, the metal particles supported on the filter improve the function as a catalyst. From this point, it is more preferable that it is 70 to 90% where a space having both a turbulent flow portion and a laminar flow portion is created.
- the denser the metal layer the higher the heat conduction characteristics, and the filter temperature can reach the desired temperature at a high speed. Therefore, a metal layer other than the lump containing layer (relatively dense metal layer)
- the porosity of is preferably 0.1 to 40%.
- the metal layer since the metal has higher thermal conductivity than ceramics, if the metal layer is dense, the metal layer can transmit heat to the ceramics even when the filter is activated, so that a filter element with a high rise speed can be obtained. In this respect, the porosity is more preferably 0.1 to 20%.
- FIG. 23 is a cross-sectional view showing a multilayer piezoelectric element that works according to an embodiment of the present invention.
- the multilayer piezoelectric element 91 includes a multilayer body in which a plurality of metal layers 93 functioning as internal electrodes and a mass-containing layer 95 are stacked via a ceramic layer 97, and a pair of external electrodes 101 are provided on the side surfaces of the multilayer body. , 101 are formed. Ceramic layers (inactive layers) 99 that do not contribute to piezoelectric driving may be disposed on both ends in the stacking direction of the stack.
- the lump containing layer 95 has more voids than the first metal layer 93 adjacent in the stacking direction. This lump The shape-containing layer 95 may be in a misaligned form as shown in FIGS. 2 (a) to (: c)! /.
- the material of the ceramic layer 97 a piezoelectric material such as PZT (lead zirconate titanate) is used.
- the metal layers 93 and the lump containing layers 95 are arranged so as to be alternately exposed on the opposite side surfaces of the laminate. Thereby, a voltage can be applied to the ceramic layer 97 disposed between the metal layers 93 through the external electrode 101. When a voltage is applied, the element expands and contracts and functions as a piezoelectric actuator.
- the mass-containing layer 95 is formed so that the metal layer 93 having a high porosity is relatively dense, so that the metal layer is dense and has a high signal transmission speed. 93 ⁇ This is easy to concentrate voltage. Only a relatively small voltage is applied to the block-containing layer 95 having a high porosity and a high resistance.
- the electrode area where the lump containing layer 95 is in contact with the adjacent ceramic layer 97 is reduced.
- the area of the deformed ceramic layer 97 is smaller than the ceramic layer 97 adjacent to the dense metal layer 93. Therefore, the piezoelectric displacement amount of the ceramic layer 97 sandwiched between the metal layers 93 is increased, and the piezoelectric displacement amount of the ceramic layer 97 in which at least one of the adjacent metal layers is the lump containing layer 95 having a high porosity is reduced. .
- the mass-containing layer 95 having a high porosity as described above is adjacent to the ceramic layer 99 which is an inactive layer existing at the boundary between the region to be displaced and the region that is not displaced.
- the lump containing layer 95 functions as a stress relaxation layer. Since at least one of the internal electrodes sandwiching the ceramic layer 97 is the mass-containing layer 95 having a high porosity and a high resistance, the piezoelectric displacement amount of the ceramic layer 97 adjacent thereto is reduced, and stress relaxation is performed. An effect is obtained. As a result, a highly durable laminated piezoelectric element can be obtained.
- Fig. 24 is a cross-sectional view showing a multilayer piezoelectric element 91 'that can be applied to another embodiment of the present invention.
- This multilayer piezoelectric element 91 ′ is different from the multilayer piezoelectric element 91 in that a lump containing layer 95 having a high porosity is connected to an external electrode 101 having the same polarity as the metal layer 93 adjacent in the stacking direction. is there.
- no voltage is applied to the ceramic layer 97 sandwiched between the lump containing layer 95 and the metal layer 93 adjacent thereto, so that no piezoelectric displacement occurs. Yes.
- the ceramic layer 97 that has piezoelectric force exists at this boundary the piezoelectric body is deformed according to the stress and the stress is relieved. .
- the lump containing layer 95 having a high porosity functions as an electrode, and two ceramic layers 97 are sandwiched between different electrodes.
- the applied voltage is halved and the drive deformation is reduced, the stress relaxation effect is increased.
- a multilayer piezoelectric element with stable performance can be obtained.
- a method for manufacturing the multilayer piezoelectric element 91 shown in FIG. 23 will be described.
- a slurry is produced by mixing lead zirconate titanate (PZT) powder, the binder, and the plasticizer.
- PZT lead zirconate titanate
- a ceramic green sheet for the ceramic layers 97 and 99 is prepared from the slurry by using a tape forming method such as a known doctor blade method or calendar roll method.
- a metal paste for the metal layer 93 is produced.
- This metal paste is obtained by adding and mixing a needle, a plasticizer, etc. to a metal powder mainly having silver palladium power.
- This metal paste is printed on one side of the green sheet by screen printing or the like.
- a metal paste for the mass-containing layer 95 having a high porosity is produced.
- This metal paste is obtained by adding a binder, a plasticizer and the like to a metal powder containing silver as a main component. This metal page The strike is printed on one side of the green sheet by screen printing or the like.
- the green sheets on which the respective metal pastes are printed are stacked so as to have the structure shown in FIG. 19 and dried to obtain a laminated molded body before firing.
- the thickness of the metal paste layer can be about 1 to 40 ⁇ m for screen printing.
- the laminated molded body is debindered at a predetermined temperature, and then fired at 800 to 1000 ° C.
- silver diffuses from the metal layer having a high silver concentration to the alloy layer to form a massive-containing layer 95 having a high porosity, and a relatively dense metal layer 93 is formed.
- the external electrode 101 is formed after the sintered body is cast to a desired dimension.
- the external electrode 101 is made by adding a binder, a plasticizer, glass powder, etc. to a metal powder mainly made of silver and mixing it to produce a metal paste, and printing this metal paste on the side of the sintered body by screen printing or the like. It can be formed by firing at 600 to 800 ° C.
- the silver concentration is high, the silver concentration is low from the metal paste layer, and silver is diffused into the metal paste layer to form a mass-containing layer 95 having a high porosity, and a relatively dense metal layer 93 is formed.
- other conventionally known methods other than the above steps may be used.
- Fig. 25 is a cross-sectional view showing a multilayer piezoelectric element 111 that is useful in still another embodiment of the present invention.
- the multilayer piezoelectric element 111 of the present embodiment includes a multilayer body in which a plurality of metal layers 93 and a plurality of mass-containing layers 95 are stacked via a ceramic layer 97.
- a pair of external electrodes 101, 101 are formed on the side surfaces.
- the mass-containing layer 95 having more voids than the metal layers 93 on both sides adjacent to each other in the stacking direction is arranged via the plurality of metal layers 93.
- the plurality of lump containing layers 95 are regularly arranged in the stacking direction of the stacked body. In this way, the massive body-containing layer 95 having a high porosity is disposed via the plurality of metal layers 93, thereby suppressing the strength of the laminate from being lowered.
- the plurality of lump containing layers 95 are arranged regularly (in accordance with a predetermined rule) in the stacking direction, the stress relaxation effect can be exhibited evenly in the stacking direction.
- the mass-containing layer is "regularly arranged" as well as the stress generated in the laminate as well as when the intervals at which the plurality of mass-containing layers are arranged are all the same. So that the lump containing layers can be effectively dispersed in the stacking direction. It is a concept that includes similar cases. Specifically, the arrangement interval of the lump-containing layers is preferably within a range of ⁇ 20%, more preferably within a range of ⁇ 15%, and even more preferably with respect to the average value of the arrangement intervals of each lump-containing layer. Should all be the same number.
- the lump containing layer 95 is scattered between two piezoelectric layers 97 and 97 adjacent to the lump containing layer 95 in the stacking direction as shown in Fig. 2 (b) or Fig. 2 (c).
- a sponge-like form having a large number of independent voids in the metal layer as shown in Fig. 2 (a)
- the stress relaxation layer is remarkably improved.
- the lump containing layer 95 in the laminated piezoelectric element 111 is thinner than the lump containing layer 95 on both sides adjacent to each other in the stacking direction. ,.
- the lump containing layer 95 having a small thickness is more easily deformed than the metal layer 93 having a large thickness.
- the stress generated by the displacement of the piezoelectric layer 97 can be absorbed. Therefore, by arranging the massive body-containing layer 95 with a small thickness as shown in FIG. 21, the stress generated by the displacement of the multilayer piezoelectric element 111 can be effectively absorbed.
- the mass percentage X in the metal paste layer for the mass-containing layer is higher than the mass percentage X in the metal paste layer for the other metal layers, according to the mass percentage difference of the metal component It can be utilized that the metal component of the lump containing layer diffuses and moves to the adjacent metal layer through the ceramic layer being sintered. That is, for example, even if the thickness of the metal paste layer is approximately the same before firing, the thickness of the lump containing layer after the metal component is diffused is thinner than the thickness of the other metal layers.
- the thickness of the lump containing layer metal paste layer may be changed to other methods. The method of making it thinner than the thickness of the metal paste layer for this metal layer is mentioned.
- the lump containing layer 95 in the multilayer piezoelectric element 111 has a higher electrical resistance than the lump containing layer 95 on both sides adjacent to each other in the stacking direction. Is preferred.
- the piezoelectric layer 97 adjacent to the block-containing layer 95 having a high electrical resistance has a smaller displacement than the piezoelectric layer 97 adjacent to the metal layer 93 having a low electrical resistance. like this Since a plurality of piezoelectric layers 97 with small displacement are present in the multilayer piezoelectric element 111, the distribution of stress caused by the displacement can be dispersed, so that occurrence of defects such as cracks can be suppressed.
- the mass-containing layer 95 in the multilayer piezoelectric element 111 preferably has a mass percentage Y higher than the metal layers 93 on both sides adjacent to each other in the stacking direction.
- the mass percentage Y preferably has a peak in the lump containing layer 95 and gradually decreases from this lump containing layer 95 to at least two metal layers 93 on both sides in the stacking direction.
- the multilayer piezoelectric element 111 having such a structure has an advantage of excellent thermal shock resistance because the metal component concentration gradually changes in a plurality of metal layers. This is due to the fact that metals are superior to ceramics in heat conduction characteristics and that the heat conduction characteristics change depending on the metal composition. That is, since the metal component concentration is gradually decreased in the plurality of metal layers, a rapid change in the heat conduction characteristics in the ceramic member can be suppressed.
- FIG. 26 is a cross-sectional view showing a multilayer piezoelectric element 112 that can be applied to still another embodiment of the present invention.
- the lump containing layers 95 and the metal layers 93 other than the lump containing layers 95 are alternately arranged.
- each piezoelectric layer 97 is sandwiched between the lump containing layer 95 and the metal layer 93. Since the lump containing layer 95 having an excellent stress relaxation effect is in contact with all the piezoelectric layers 97 that are driven and displaced, the stress relaxation effect can be further enhanced. Since the porous metal layer and the dense metal layer are alternately present, the metal layer 93 applies a voltage to the piezoelectric layer 97 to enable piezoelectric displacement.
- the metal layer Since the lump containing layer 95 on the opposite side through the piezoelectric layer 97 is porous, the metal layer has a weak force for clamping the piezoelectric layer 97, and therefore, the generation of stress is small. Therefore, since the piezoelectric layer 97 is not clamped, a large displacement is generated. In addition, the stress generated between the metal layer 93 and the piezoelectric layer 97 can be relaxed.
- the porosity of the lump containing layer 95 is preferably 7% or more and 70% or less.
- the porosity is 70% or less, the conductivity of the lump containing layer 95 is suppressed from being lowered, a sufficient electric field can be applied to the adjacent piezoelectric layer, and the amount of displacement can be increased. Can do.
- the porosity is 7% or more, it is possible to suppress an excessive increase in the bonding force with the piezoelectric layer adjacent to the lump containing layer 95. As a result, cracks are likely to be generated at the interface between the lump containing layer 95 and the piezoelectric layer 97 during driving, and therefore the generation of cracks in the piezoelectric layer itself can be suppressed.
- the porosity of the lump containing layer 95 is preferably 24 to 98%, more preferably 24 to 90%. Thereby, insulation can be improved.
- the force with which the metal layer restrains the piezoelectric body can be reduced to reduce the stress during driving.
- the drive displacement of the piezoelectric body can be increased. Further, it is more preferably 70 to 90% from the viewpoint that the air layer in the gap produces a heat insulating effect and the thermal shock resistance of the multilayer piezoelectric element is excellent.
- the porosity is preferably 70% or more in terms of imparting higher insulating properties.
- the porosity of the metal layer other than the mass-containing layer is preferably 0.1 to 40% in terms of enhancing the electric conduction characteristics and efficiently applying the driving voltage of the piezoelectric body. Further, it is more preferably 0.1 to 20% in that the electric conduction can be further enhanced and the piezoelectric body can be greatly displaced.
- the mass-containing layers 95 are respectively disposed at both ends in the stacking direction of the plurality of metal layers.
- the metal layer adjacent to the ceramic layer 99 is preferably the lump containing layer 95.
- the lump containing layer 95 when the lump containing layer 95 functions as an internal electrode, it is desirable that the lump containing layer 95 is a positive electrode.
- the electric field is locally concentrated due to the edge effect, and local driving deformation occurs.
- the phase transition of the crystal structure of the piezoelectric body due to stress may occur simultaneously and heat may be generated locally.
- the oxygen partial pressure around the multilayer piezoelectric element is lower than the oxygen partial pressure at which the oxygen ions of the piezoelectric body dissociate at the generated temperature! With nephew! If the soot condition is satisfied, oxygen vacancies that serve as ion conductors are locally generated in the piezoelectric body, which may cause the characteristics of the multilayer piezoelectric element to change.
- the ionized oxygen vacancies have a negative charge
- migration of the ionized oxygen vacancies is more likely to occur in the metal layer on the positive electrode side than on the negative electrode side.
- oxygen is easily supplied around the piezoelectric body, so that the generation of oxygen vacancies is suppressed, and a decrease in durability can be suppressed.
- Fig. 27 is a cross-sectional view showing a multilayer piezoelectric element 113 according to still another embodiment of the present invention.
- the multilayer piezoelectric element 113 is obtained by laminating a metal layer 93 containing a metal component M and a lump containing layer 9 via a piezoelectric layer 97.
- the plurality of metal layers include a plurality of dense metal layers 93 ′ having fewer voids than the massive body-containing layers 95 ′ on both sides adjacent to each other in the stacking direction.
- the metal layer 9 is a lump containing layer.
- Mass-containing layer 95 'force excellent in stress relaxation effect When there is only one layer, the stress applied to the device tends to concentrate on the periphery. Since the piezoelectric layer 97 in contact with the metal layer 93 adjacent to the lump containing layer 95 ⁇ is driven and displaced, the piezoelectric portion sandwiched between the metal layer 93 adjacent to the lump containing layer 95 'and the element surface Stress tends to concentrate on the surface.
- the mass-containing layer can absorb the stress generated in the laminated body more effectively when the element is driven.
- the piezoelectric layer adjacent to the lump-containing layer may be applied with voltage applied to the internal electrode. Do not drive.
- the lump containing layer is sandwiched between the same poles as described above, a driven portion and a non-driven portion are formed, and stress is easily concentrated near the boundary.
- stress concentration as described above hardly occurs.
- Fig. 28 (a) is a perspective view showing a multilayer piezoelectric element that works on the present embodiment, and Fig. 28 (b) shows a piezoelectric layer and internal electrode layers (metal layers) in this multilayer piezoelectric element.
- FIG. 28 (b) shows a piezoelectric layer and internal electrode layers (metal layers) in this multilayer piezoelectric element.
- this multilayer piezoelectric element has a multilayer body 104 in which a plurality of piezoelectric layers 107 are stacked via an internal electrode layer 102. .
- a pair of external electrodes 105 in which a plurality of internal electrode layers 102 are connected every other layer is formed.
- the plurality of internal electrode layers 102 are not formed on the entire main surface of the piezoelectric layer 107, and the area of the internal electrode layer 102 is smaller than the area of the main surface of the piezoelectric layer 107. It has a partial electrode structure.
- These internal electrode layers 102 are laminated so as to be alternately exposed on the side surfaces of the laminated body 104 facing each other.
- the internal electrode layer 102 has a partial electrode structure as described above, when a voltage is applied to the external electrodes 105, 105, two sheets positioned above and below the piezoelectric layer 107 Only the portion sandwiched between the internal electrode layers 102, that is, the region where one internal electrode layer 102 overlaps the other internal electrode layer 102 in the stacking direction (displacement portion 170) is displaced. On the other hand, in the piezoelectric layer 107, as shown in FIG. 28 (b), the internal electrode layer 102 is formed, and in the portion (peripheral portion 131), the piezoelectric layer 107 is not displaced (the non-displacement portion). 171).
- the lead wire 106 is connected and fixed to the external electrode 105 by solder, and the lead wire 106 is connected to the external voltage supply unit. You can continue. By applying a predetermined voltage to the external electrodes 105 and 105 through the lead wire 106 as the external voltage supply force, each piezoelectric layer 107 can be displaced by the inverse piezoelectric effect.
- this multilayer piezoelectric element is located between two piezoelectric layers 107 adjacent to each other in the stacking direction, and has a side end 102a of the internal electrode layer 102.
- a peripheral edge 131 located between the side surface 104a of the laminate 104 is provided.
- at least one peripheral portion 131 has a region where a plurality of ceramic blocks 103 and Z or metal blocks (partial metal layers) 103 are scattered. Is formed.
- these lumps 103 are scattered over almost the entire periphery 131. Instead of the lump 103, other substances that are easier to deform than piezoelectric ceramics may be interspersed.
- the “deformation” referred to here may be any form of deformation such as elastic deformation, plastic deformation, and brittle deformation.
- the lump bodies 103 are scattered in the peripheral portion 131 in a state of being insulated from the internal electrode layer 102.
- spotted in an insulated state from the internal electrode layer 102 means that the plurality of lumps 103 are not electrically connected to the internal electrode layer 102 and the lumps 103 This refers to the state in which the two are separated from each other and electrically conductive (Fig. 29).
- the position of the lump 103 in the stacked body 104 is not particularly limited.
- the aggregates 103 may be scattered all over the peripheral portions 131 (peripheral portions 131 adjacent to all the internal electrode layers 102), or may be interspersed with arbitrarily selected peripheral portions 131.
- the material constituting the mass 103 the same material as the piezoelectric body or the same material as the internal electrode layer 102 can be used, and PZT or silver-palladium alloy is preferable. Silver palladium alloy is soft and easily deformed even among metals, so even a small amount is highly effective in reducing the restraining force of the non-displacement part. In addition, since the silver-palladium alloy has high oxidation resistance that resists metal fatigue, the durability of the multilayer piezoelectric element can be suppressed from decreasing. Lump There are no particular restrictions on the shape, size, number, etc. of the peripheral portion 131, as long as they are in the state of being scattered as described above.
- the ratio of the total area of the plurality of lumps 103 to the area of the rim 131 when the periphery 131 dotted with the lumps 103 is viewed from the stacking direction of the laminate 104. Is preferably 0.1 to 50%, more preferably 5 to 30%.
- the maximum diameter r of the massive body 103 when the massive body 103 is viewed from the stacking direction of the multilayer body 104 is not particularly limited.
- the maximum diameter r of the preferred lump 103 is 1Z2 or less, preferably 1Z10 or less, which is the shortest distance L between the internal electrode layer 102 and the external electrode 105 at the peripheral portion 131.
- the maximum diameter r of the region 3 is 500 / z m or less, preferably 100 m or less. Thereby, moderate bending strength and insulation can be maintained.
- the ceramic that exists between the adjacent lump bodies 103 and connects the piezoelectric layers 107 is not particularly limited.
- the ceramic is the same material as that of the piezoelectric layers 107.
- lead zirconate titanate is used as the material of the piezoelectric layer 107
- lead zirconate titanate is used as the insulating ceramic for connecting the piezoelectric layers 107 to each other at the peripheral portion 131. Is preferred. As a result, in addition to preventing the occurrence of problems due to the difference in thermal expansion, it is possible to obtain a high bonding strength for bonding the piezoelectric layers 107 to each other.
- the peripheral portions 131 interspersed with the lump bodies 103 are more preferably arranged at equal intervals in the stacking direction of the stacked body 104.
- the plurality of lump bodies 103 are scattered on the plurality of peripheral portions 131 of the Is good. As described above, since the lump bodies 103 are scattered on the plurality of peripheral portions 131 selected at equal intervals, the displacement performance and the bending strength can be set in a more balanced manner.
- the piezoelectric layer 107 is not particularly limited.
- a Bi layer compound a layered bobsite compound
- a tungsten bronze type Compounds Nb-based perovskite compounds (Nb-acid alkaline compounds (NAC) such as sodium Nb acid, Nb-acid alkaline earth compounds (NAEC) such as barium Nb), lead magnesium niobate (PMN), nickel niobate
- NAC Nb-acid alkaline compounds
- NAEC Nb-acid alkaline earth compounds
- PMN lead magnesium niobate
- nickel niobate nickel niobate
- a perovskite-type compound containing at least Pb is particularly preferable.
- lead magnesium niobate (PMN), nickel niobate (PNN), lead zirconate titanate (PZT) containing Pb, lead titanate, etc. are preferred.
- lead zirconate titanate and lead titanate are suitable for adding large displacement.
- Piezoelectric ceramics have a high piezoelectric strain constant d indicating their piezoelectric properties.
- the material of the internal electrode layer 102 for example, gold, silver, noradium, platinum, copper, aluminum or an alloy thereof can be used. Specific examples of the alloy include silver palladium alloy.
- the thickness of the internal electrode layer 102 needs to be conductive and not to prevent displacement, and is generally about 0.5 to 7 / zm, preferably about 1 to 5 / zm.
- the thickness of the piezoelectric layer 1, that is, the distance between the internal electrode layers 2 is preferably about 50 to 200 ⁇ m.
- the thickness of the piezoelectric layer 107 is in the above range, the size and height of the actuator can be reduced, and dielectric breakdown can be suppressed.
- the material of the external electrode 105 for example, gold, silver, iron ⁇ radium, platinum, copper, aluminum, nickel, or an alloy thereof can be used.
- a glass powder and a binder are added to silver powder to produce a silver glass conductive paste.
- This conductive paste is marked on the opposite side surfaces 104a and 104a of the laminate 104 by a method such as screen printing. Print and dry. Thereafter, the external electrode 105 can be formed by baking at 500 to 800 ° C. At this time, instead of printing, a sheet of 5 m or less obtained by drying the above silver glass paste may be baked.
- the laminated body 4 on which the external electrode 105 is formed is dipped in a silicone rubber solution, and the silicone rubber solution is vacuum degassed. Coat with silicone rubber. Thereafter, the silicone rubber coated on the side surface of the laminated body 104 is cured to complete a laminated piezoelectric element that is effective in the present embodiment.
- a lead wire is connected to the external electrode 105, and a DC voltage of 3 kVZmm is applied to the pair of external electrodes 105 via the lead wire to polarize the laminated body 104, thereby the present invention.
- a piezoelectric actuator using the multilayer piezoelectric element is completed.
- the lead wire is connected to an external voltage supply unit, and a voltage is applied to the metal layer 102 via the lead wire and the external electrode 105, whereby each piezoelectric layer 107 is largely displaced by the inverse piezoelectric effect.
- it functions as an automobile fuel injection valve that injects and supplies fuel to the engine.
- FIG. 30 is a schematic cross-sectional view showing an injection device according to an embodiment of the present invention.
- the multilayer piezoelectric element of the present invention represented by the above embodiment is accommodated in a storage container 331 having an injection hole 333 at one end.
- a one-dollar valve 335 capable of opening and closing the injection hole 333 is disposed.
- a fuel passage 337 is arranged in the injection hole 333 so as to be communicable according to the movement of the one-dollar valve 335.
- This fuel passage 337 is connected to an external fuel supply source, and fuel is always supplied at a constant high pressure. Therefore, when the needle valve 335 opens the injection hole 333, the fuel supplied to the fuel passage 337 is configured to be injected into a fuel chamber of an internal combustion engine (not shown) at a constant high pressure.
- the upper end portion of the needle valve 335 has a large inner diameter, and a cylinder 339 formed in the storage container 331 and a slidable piston 341 are disposed.
- the piezoelectric actuator 343 including the multilayer piezoelectric element described above is stored. ing.
- the ejection device of the present invention includes a container having ejection holes and the multilayer piezoelectric element, and causes the liquid filled in the container to eject ejection hole force by driving the multilayer piezoelectric element. It may be configured. In other words, the element does not necessarily have to be inside the container, and may be configured so that pressure is applied to the inside of the container by driving the multilayer piezoelectric element.
- the liquid includes various liquid fluids (such as conductive paste) in addition to fuel and ink.
- FIG. 31 is a schematic diagram showing a fuel injection system according to an embodiment of the present invention.
- the fuel injection system 351 according to the present embodiment includes a common rail 352 that stores high-pressure fuel, a plurality of the above-described injection devices 353 that inject fuel stored in the common rail 352, and the common rail 352.
- a pressure pump 354 that supplies high-pressure fuel, and an injection control unit 355 that supplies a drive signal to the injection device 353 are provided.
- the injection control unit 355 controls the amount and timing of fuel injection while sensing the state of the combustion chamber of the engine with a sensor or the like.
- the pressure pump 354 serves to feed the fuel from the fuel tank 356 to the common rail 352 at about 1000 to 2000 atmospheres, preferably about 1500 to 1700 atmospheres.
- the fuel sent from the pressure pump 354 is stored, and is appropriately fed into the injection device 353.
- the injection device 353 injects a small amount of fuel into the combustion chamber in the form of a mist through the injection hole 333 as described above.
- FIG. 32 is a perspective view showing a multilayer piezoelectric element according to another embodiment 1.
- FIG. Figure 33 shows FIG. 33 is a cross-sectional view taken along line AA in FIG.
- FIG. 34 is an enlarged cross-sectional view including the composite layer of the present invention.
- the multilayer piezoelectric element has a multilayer body 410 in which a plurality of piezoelectric layers 1 are laminated via internal electrodes 402.
- a pair of external electrodes 404a and 404b are electrically bonded to the opposite side surfaces of the laminated body at every other end of the internal electrodes 402! /.
- a lead wire 406 is connected and fixed to the outer electrodes 404a and 404b by a solder or the like.
- the internal electrode 402 is powered by the first internal electrode 402a that is electrically connected to the positive external electrode 404a and the second internal electrode 402b that is electrically conductive to the negative external electrode 404b.
- the multilayer piezoelectric element of the present embodiment is arranged between two piezoelectric layers 4 Ola, 401a and these piezoelectric layers 401a, 401a.
- Inorganic composition A composite layer 411 composed of a block-containing layer (inorganic layer) 403 interspersed with a plurality of 403a is disposed between adjacent internal electrodes 402a and 402b of different polarities, ! /
- the composite layer 411 includes a massive body-containing layer 403 in which massive bodies 403a are interspersed between two piezoelectric layers 40la and 401a sandwiched between different-polarity internal electrodes 402a and 402b. Therefore, when a voltage is applied to the internal electrodes 402a and 402b, the piezoelectric layer 401a adjacent to the lump containing layer 403 does not have a lower electric field force than the other piezoelectric layers 401b. Accordingly, the piezoelectric layer 401a adjacent to the lump containing layer 403 has a smaller strain than the other piezoelectric layers 402b.
- the stress generated by the distortion of the composite layer 411 force laminate 410 composed of the lump containing layer 403 and the piezoelectric layers 401a and 401a can be effectively absorbed. Therefore, it is possible to prevent excessive stress from being applied to the piezoelectric layer even when driven continuously for a long time under a high electric field and high pressure. Can be obtained.
- the composite layer it is possible to suppress the generation of a beating sound caused by the occurrence of a resonance phenomenon in which the displacement behavior of each piezoelectric layer coincides, and the drive frequency. It is possible to prevent the generation of a harmonic signal that is an integer multiple of the number, thereby preventing noise components.
- the durability of the element is improved by providing the composite layer, it is possible to suppress a change in the amount of displacement and to obtain a stable amount of displacement in a long-term continuous operation.
- the length in the direction perpendicular to the stacking direction of the stacked body 410 is preferably 0.1 to 100 m.
- the length of the mass constituting the mass-containing layer 403 is 0.1 to 100 m, the electric field applied to the piezoelectric layer 401a disposed on both sides of the mass-containing layer 403 is reduced, The strain of the piezoelectric body layer 401a can be reduced, and the stress generated by the expansion and contraction of the multilayer body 410 can be dispersed and absorbed by the bulk body 403a. More preferably, the length of the block 403a is 1 to 10 m.
- the shape of the block 403a may be a substantially spherical shape or another shape.
- the lump containing layer 4003 may be formed in a part of the region between the piezoelectric layers or in the entire region.
- the lump-containing layer 403 preferably has more voids 403b (low dielectric) than the internal electrode 402.
- the void ratio may be measured.
- the piezoelectric layer 401a adjacent to the lump containing layer 403 has another piezoelectric material. Compared to the layer lb, it is low !, it only takes an electric field, and more stress reduction is possible!
- the porosity of the mass-containing layer 403 is preferably from the viewpoint of interspersing the mass 403a and effectively reducing the electric field applied to the piezoelectric layer 401a adjacent to the mass-containing layer 4003. 10 to 95 0/0, by a force of more is preferably ⁇ or 40 to 90 0/0! ⁇ is.
- the composite layer 411 composed of the inclusion layer 403 is preferably disposed on one end side or both end side in the stacking direction of the stacked body 410. That is, the inactive layer 409 that does not undergo piezoelectric displacement even when a voltage is applied is disposed at both ends in the stacking direction of the stack 410, but when the stack 410 is driven by applying a voltage. In the piezoelectric layer 1, the piezoelectric displacement and the piezoelectric displacement! A large stress is generated at the interface of the inert layer 409.
- the stress generated between the inactive layer 409 and the piezoelectric layer 1 can be greatly reduced, and the inactive layer 409 during driving can be reduced. It is possible to suppress the occurrence of cracks in the piezoelectric layer 1 due to stress acting in the vicinity.
- the end of the laminate 410 in the stacking direction is disposed at the end of the stack 410 in the stacking direction.
- the piezoelectric layer 1 is preferably within the 25th, more preferably within the 10th, counting from the inactive layer 409.
- the composite layer 411 is formed at the end in the stacking direction of the plurality of the layer-containing layers 403.
- the laminated body 410 includes a stress relaxation region including a plurality of piezoelectric layers having a layer thickness larger than that of the central piezoelectric layer 1 on one end side or both end sides in the stacking direction, It is desirable to have a composite layer in the stress relaxation region.
- the stress relaxation region provided on the end side in the stacking direction is thicker than the piezoelectric layer 1 in the center of the stacking direction, and has a plurality of piezoelectric layers 1, so that when a voltage is applied, The generated strain is smaller than the central piezoelectric layer 1.
- the metal component constituting the mass 403a is at least one selected from Ni, Pt, Pd, Rh, Ir, Ru, and Os, which are Group L0 metals of the periodic table, and the periodic table. It is preferably an alloy that has at least one selected from the group 11 metals such as Cu, Ag, and Au. This is a force that is a metal composition with excellent mass productivity in recent alloy powder synthesis technology. Further, the metal component constituting the massive body 403a may be a group 11 metal simple substance in the periodic table. In particular, Ag alone or an alloy containing Ag as a main component is desirable.
- the lump 403a constituting the lump containing layer 403 is made of a piezoelectric material
- the lump containing layer 403 can be used even when a high compressive force is applied to the lump containing layer 403 even when used under high pressure.
- the piezoelectric material constituting 403a can be deformed by a compressive force. For this reason, stress It is possible to suppress the occurrence of cracks in the piezoelectric layer 1 where no concentration occurs.
- the lump 403a constituting the lump containing layer 403 is preferably made of a metal material and a compacted material. This is because the metal material has a low Young's modulus and does not restrain displacement, and the piezoelectric material can be deformed under a high compressive force.
- the metal material constituting the lump containing layer 403 and the main component of the internal electrode 402 are the same.
- the piezoelectric layer 1, the internal electrode 402, and the metal material can be fired simultaneously, and an inexpensive multilayer piezoelectric element can be manufactured.
- the main component of the metal material the same as the main component of the internal electrode 402, it is possible to suppress the occurrence of delamination due to the shrinkage mismatch between the internal electrode 402 and the metal material during firing.
- the piezoelectric material constituting the lump containing layer 403 and the main component of the piezoelectric layer 1 are the same.
- the piezoelectric layer 1 and the internal electrode 402 and the lump containing layer 403 can be co-fired, An inexpensive laminated piezoelectric element can be manufactured. In addition to this, it is possible to suppress the occurrence of delamination due to shrinkage mismatch between the piezoelectric layer 1 and the mass-containing layer 403 during firing.
- the inorganic paste for forming the lump containing layer 403 is produced as follows.
- an inorganic paste is prepared by adding a binder, a plasticizer, etc. to a metal powder such as silver or an alloy such as silver-palladium containing silver as a main component.
- a metal powder such as silver or an alloy such as silver-palladium containing silver as a main component.
- an inorganic paste is prepared by adding and mixing a binder, a plasticizer, and the like to a calcined powder such as PZT.
- the block 403a is composed of a metal material and a piezoelectric material
- a binder or a possible binder is added to the metal powder such as silver or an alloy such as silver-palladium mainly containing silver and the calcined powder such as PZT.
- An inorganic paste is prepared by adding and mixing a plasticizer or the like.
- the lump containing layer 403 having an arbitrary porosity By containing an organic substance such as acrylic beads in the inorganic paste, the lump containing layer 403 having an arbitrary porosity can be formed. Thereby, the lump containing layer 403 having a desired porosity can be formed.
- the green paper on which the inorganic paste forming the lump containing layer 403 is printed As shown in FIG. 35, the green paper on which the inorganic paste forming the lump containing layer 403 is printed.
- the green sheets on which the conductive paste forming the internal electrode 402 is printed on both sides of the sheet are laminated so as to be opposite to each other.
- a composite layer 411 including the layer 403 can be formed.
- a plurality of green sheets having a layer thickness greater than that of the green sheet forming the piezoelectric layer 1 in the center is laminated on one end side or both end sides in the stacking direction.
- a stress relaxation region including a plurality of piezoelectric layers can be formed that is thicker than the central piezoelectric layer.
- a laminate 410 including the composite layer 411 in the stress relaxation region can be manufactured.
- FIG. 36 is a perspective view showing a laminated piezoelectric element according to another embodiment 2
- FIG. 37 is a partial perspective view showing a laminated state of the piezoelectric layer and internal electrodes in FIG.
- the multilayer piezoelectric element of the present embodiment has a multilayer body 513 in which a plurality of piezoelectric layers 51 la and a plurality of internal electrodes 512 are stacked alternately.
- a pair of external electrodes 515 are disposed on the opposite side surfaces of the laminate 513.
- the multilayer piezoelectric element of the present embodiment includes a plurality of lump containing layers (small cross-sectional area piezoelectric layers) 5 ib.
- This lump containing layer 51 lb is composed of six lumps (partial piezoelectric layers) 511c which are interspersed between two piezoelectric layers 511a and 511a adjacent in the stacking direction.
- FIG. 38 (a) is a cross-sectional view showing a cross section when cut by a plane perpendicular to the stacking direction of the stacked body 513 and including the lump containing layer 51 lb.
- FIG. 38 (b) FIG. 38A is a cross-sectional view showing a cross section taken along a plane that includes a piezoelectric layer 51 la adjacent to the lump containing layer 51 lb in 38 (a) in the stacking direction and is perpendicular to the stacking direction.
- the ratios Xa and Xb should be at least in the relationship of (Xb / Xa) ⁇ 1, but preferably (X b / Xa) ⁇ 0.8, more preferably 0.1 ⁇ (Xb / Xa ) ⁇ 0.7, more preferably 0.2 ⁇ (Xb / Xa) ⁇ 0.5.
- the ratio Xa is preferably 0.8 to 1.0, more preferably 0.75 to 0.95-1. Harm ij combined Xbi, preferably ⁇ to 0,05-0.8, more preferably in the range of 0.1 to 0.5.
- the ratio Xb in the mass-containing layer 51 lb and the ratio Xa in the piezoelectric layer 51 la can be measured in the same manner as in the method for measuring the porosity described above.
- FIG. 39 is a cross-sectional view showing a cross section of the multilayer body 513 cut along a plane parallel to the stacking direction of the multilayer body 513.
- the area of the piezoelectric body is larger than the area of the mass-containing layer 51 lb.
- the area of the piezoelectric layer 511a in the piezoelectric layer 51 la adjacent to the lump containing layer 511b in the cross section when the laminated body 513 is cut along a plane parallel to the stacking direction of the piezoelectric layer is Yb.
- the ratio of the area of the piezoelectric material to Ya is assumed to be Ya.
- the ratio Yb in the lump containing layer 51 lb is smaller than the ratio Ya in the piezoelectric layer 51 la adjacent on both sides in the stacking direction.
- the ratios Ya and Yb need only be in a relationship of at least (Yb / Ya) ⁇ 1, but preferably (Y b / Ya) ⁇ 0.8, more preferably 0.1 ⁇ (Yb / Ya) It is preferable that the relationship is ⁇ 0.7, more preferably 0.2 ⁇ (Y b / Ya) ⁇ 0.5. Also, the ratio Ya is preferably 0.8 to 1.0, more preferably ⁇ to a force in the range of 0.995-1. Harm ij combined Ybi, preferably ⁇ 0,05-0.8, more preferably in the range of 0.1-0.5.
- the lump containing layer 5 l ib As a result, a sufficient stress relaxation effect can be obtained, and a reduction in the strength of the element due to the lump containing layer 5 ib can be suppressed.
- the ratio Yb in the mass-containing layer 51 lb and the ratio Ya in the piezoelectric layer 51 la can be measured in the same manner as in the method for measuring the porosity described above.
- the lump containing layer 511b since the lump containing layer 511b is disposed, the displacement of the piezoelectric layer 511a around the lump containing layer 5 ib is reduced, and the lump is contained. Since the displacement around the piezoelectric layer 51 la away from the body-containing layer 51 lb is large, the large displacement portion and the small displacement portion can be dispersed in the element. By disposing such a lump containing layer 511b in the element, stress applied to the element can be dispersed.
- the plurality of lumps 511c constituting the lumps-containing layer 5 ib are substantially uniformly disposed between the piezoelectric layers 511a and 11a.
- the lumps-containing layer 51 lb is formed over the entire cross-section of the element, so that stress due to element deformation does not concentrate in part. It acts as a stress relaxation layer for the piezoelectric layer.
- the mass-containing layer 51 lb is preferably disposed at approximately the center between the two internal electrodes disposed at both ends of the stacked body 513 in the stacking direction.
- Laminate 513 in the stacking direction The approximate center between the internal electrodes located at both ends (ie, approximately the center of the active layer) is a site where large stress concentrates. By doing so, the durability of the element can be improved.
- the second most important arrangement site after the approximate center between the internal electrodes is the approximate center between the internal electrodes located at both ends in the stacking direction, and the internal electrodes positioned at one end and the other end in the stacking direction. Roughly Central (ie, the edge force of the active layer is also about 1Z4 away from the length of the active layer). In the following, based on the same concept! /, It is preferable to arrange 51 lb of the mass-containing layer.
- the element When the multilayer piezoelectric element is used in a fuel injection device or the like, the element is stored in a storage container having an injection hole at one end. In this case, since one end side of the element is in contact with the inner wall of the storage container, it becomes a fixed end, while the other end side (the injection hole side of the storage container) of the element becomes a free end and can be freely expanded and contracted. It has become. In such a case, since a larger stress tends to be generated on the free end side than on the fixed end side, a larger mass containing layer 51 lb may be arranged on the free end side.
- a part of the plurality of lumps 511c constituting the lumps-containing layer 5 ib is adjacent to both ends in the thickness direction of the lumps 511c.
- the remaining portions of the plurality of lumps 511c constituting the lumps-containing layer 511b are in contact with the piezoelectric layer 51 la only at one end in the thickness direction of the lumps 511c. Is desirable.
- the plurality of blocks 511c constituting the block-containing layer 5 l ib are in contact with the piezoelectric layers 11 on both sides thereof at both ends or one end in the thickness direction. Since there is a lump 51 lc that is in contact with / contacts the piezoelectric layer 511a only at one end, the degree of freedom of the piezoelectric layer 51 la adjacent to the lump containing layer 51 lb becomes larger, and the amount of displacement In addition, the stress relaxation effect can be enhanced.
- the width W of the massive body 511c in the cross section when the laminated body 513 is cut in a plane parallel to the laminating direction is such that the width W gradually becomes smaller or larger as it approaches the piezoelectric layer 511a adjacent in the laminating direction. It is good to be.
- the width W of the massive body 511c is the maximum near the center in the thickness direction, and gradually decreases as it approaches the piezoelectric layers 51la on both sides in the stacking direction.
- the stress generated at the interface between the piezoelectric body and the internal electrode 512 when the multilayer piezoelectric element is driven and deformed is used. It is necessary to relax without concentrating one point.
- the width W of the plurality of lumps 511c constituting the lumps-containing layer 5 ib is gradually decreased in the region near the adjacent piezoelectric layer 511a as it approaches the piezoelectric layer 51 la. Or, it is gradually increased to suppress the concentration of stress at one point. Further, as shown in FIG.
- a gap l id exist between the plurality of adjacent lump bodies 51 lc.
- the void l id exists between the plurality of lumps 511c, when the stress is applied, the lumps 511c are deformed due to the presence of the gap, and the stress can be dispersed and relaxed.
- the piezoelectric body 11a in contact with the lump containing layer 511b undergoes piezoelectric displacement, the presence of the void portion causes the piezoelectric body 11a to be partially clamped, and thus the piezoelectric body 11a than when clamping the entire surface. Therefore, the amount of displacement can be increased because the piezoelectric layer 511a is easily displaced.
- the multilayer piezoelectric element of the present embodiment is also characterized in that a plurality of voids id are dotted in a direction perpendicular to the lamination direction of the piezoelectric layers.
- the plurality of voids l id are preferably substantially uniform in length in the stacking direction.
- the length of the gap l id (the length in the stacking direction) is not particularly limited, but is preferably 0.1 to: LO / zm, more preferably about 0.5 to 2.0 m. Is good.
- the length force of the void l id is O. 1 to 10 / ⁇ ⁇ , it is possible to suppress a decrease in the buffering effect due to the block 511c during driving of the element and a decrease in the strength of the element. .
- a preferable range of the length of the massive body 511c is the same as the preferable range of the above-described void id.
- a glass layer or a resin other than a gap may be present between a plurality of adjacent masses 511c.
- Examples of the glass component include lead alkali and acid glass.
- lead alkali silicate glass By using lead alkali silicate glass, there is an effect that damage in the manufacturing process of the multilayer piezoelectric element having high interface strength with the piezoelectric layer can be reduced.
- the glass component for example, silica glass may be used. Silica glass, like lead alkali silicate glass, has the effect of reducing damage in the manufacturing process of a laminated piezoelectric element having high interface strength with the piezoelectric layer.
- the resin component include epoxy resin. Using epoxy resin This has the effect of effectively relieving stress concentration.
- polyimide resin may be used as the resin component. Using polyimide resin has the effect of being able to drive even in high-temperature environments.
- the following may be performed.
- 51 lb of the mass-containing layer was added to a calcined powder of piezoelectric ceramic and a powder of glass component, and a binder and a plasticizer were added and mixed to prepare a piezoelectric material 'glass mixed paste. This is printed on the upper surface of the green sheet by screen printing.
- a conductive paste is prepared by adding and mixing a binder, a plasticizer, and the like to the metal powder constituting the internal electrode 512 such as silver-palladium, and this is printed on the upper surface of each green sheet by screen printing or the like. Then, a plurality of green sheets on which paste for 51 lb of the mass-containing layer is printed and green sheets on which conductive paste constituting the internal electrode 512 is printed are stacked in a predetermined order, and debinding is performed at a predetermined temperature. After that, the laminate 513 is manufactured by firing at 900 to 1200 ° C.
- a plurality of green sheets printed with paste for 51 lb of the mass-containing layer and green sheets printed with the conductive paste constituting the internal electrode 512 are laminated in a predetermined order, and debinding is performed at a predetermined temperature.
- the laminate 513 is produced by firing at 900 to 1200 ° C.
- paste such as epoxy resin or polyimide resin is injected into the voids of the mass-containing layer 5 ib.
- the side force of the laminate 513 is penetrated into the voids by surface tension using a brush containing a grease paste, or the laminate 513 is immersed in a bath filled with a grease paste and then placed in a vacuum container. It is possible to cure the resin by heating and heating after the resin is infiltrated into 51 lb of the lump containing layer by a method such as putting the resin into the voids under a reduced pressure environment.
- piezoelectric ceramics The calcined powder, the binder, and the plasticizer are mixed to prepare a slurry, and a ceramic green sheet is prepared by a known method using the slurry.
- 51 lb of the mass-containing layer was prepared by adding a binder, a plasticizer, and the like to the calcined powder of piezoelectric ceramic to prepare a piezoelectric paste, which was then printed on the upper surface of each green sheet by screen printing or the like. Print to a thickness of 1 to 40 m.
- the piezoelectric ceramic powder used in this piezoelectric paste be the same powder as the piezoelectric layer 51 la in order to prevent cracking due to shrinkage differences in the firing process.
- a conductive paste is prepared by adding a binder, a plasticizer, and the like to the metal powder constituting the internal electrode 512 such as silver-palladium, and this is screen printed on the upper surface of each green sheet. Print to a thickness of 1-40 m. In the same manner as described above, the thickness of the internal electrode 512, the gap in the internal electrode, and the like can be changed. After stacking a plurality of green sheets printed with conductive paste and green sheets printed with a paste for the lump containing layer 5 ib in a predetermined order and debinding at a predetermined temperature, A laminate 513 is produced by firing at 900 to 1200 ° C.
- a groove is formed in the piezoelectric portion between the internal electrode 512 and the external electrode 515 on the side surface of the multilayer piezoelectric element, and a resin or rubber having a lower Young's modulus than the piezoelectric member 511 is formed in the groove. Etc. are formed.
- the groove is formed on the side surface of the laminate 513 by an internal dicing apparatus or the like. Other portions may be formed in the same manner as described above.
- the lump containing layer in the present embodiment may be in the form shown in Fig. 40 (a) or Fig. 40 (b). That is, as shown in FIG. 40 (a), the mass-containing layer 21b may be composed of a plurality of masses 21c arranged at random, or as shown in FIG. 40 (b). In addition, the lump containing layer 4031b may have a form in which a plurality of voids (or resin layers) 531c are present randomly in the piezoelectric layer.
- the internal electrode 512b has six massive forces.
- the size, the number, the arrangement state, etc. of the massive body are not particularly limited. Therefore, the internal electrode 512b may be one in which a large number of aggregates having different sizes are randomly arranged.
- the inclusion layer 511b may be adjacent to the piezoelectric layers 51la on both sides in the stacking direction via the internal electrode 512a! /.
- FIG. 41 (a) is a perspective view showing a laminated piezoelectric element that is effective in the present embodiment
- FIG. 41 (b) shows a laminated state of the piezoelectric layer and the metal layer in FIG. 41 (a).
- FIG. 42 is an enlarged cross-sectional view of a joint portion between the external electrode 615 and the side surface of the multilayer body 615 in the embodiment of the present invention in FIG.
- the multilayer piezoelectric element of the present embodiment has a plurality of piezoelectric layers 11 and a plurality of metal layers 12 (12a, 12b) alternately stacked. And a pair of external electrodes 615 are disposed on opposite side surfaces of the laminate 615.
- the multilayer piezoelectric element of the present embodiment as shown in 041 (a) and (b), at least one of the plurality of metal layers 612 is separated from each other with a gap between the piezoelectric layers 11.
- This is a lump containing layer 612b composed of a plurality of ceramic lumps (piezoelectric regions) 12c and a plurality of lumps of metal (metal regions) 12d spaced apart from each other through gaps.
- the presence of at least one such mass-containing layer 612b can increase the durability of the multilayer piezoelectric element as well as increase the displacement of the entire multilayer piezoelectric element. .
- the displacement of the piezoelectric layer around the lump containing layer 612b is small, and the displacement of the piezoelectric layer 11 around the metal layer 612a is large. Locations with large and small displacements can be dispersed in the element. By disposing such a metal layer in the element, stress due to element deformation can be dispersed.
- the mass-containing layer 612b is composed of a plurality of ceramic masses separated from each other via a void and a plurality of metal masses separated from each other via a void.
- the stress relaxation effect is great when stress is applied to the child. The reason for this is that, when stress is applied to ceramic masses that are spaced apart from each other and have a high degree of freedom, the placement of ions in the piezoelectric crystal moves and the crystal deforms according to the stress direction. Is generated, and the stress can be relieved.
- the metal mass When a large stress that cannot be absorbed by the ceramic mass is applied, the metal mass mainly exhibits a relaxation effect, and the ceramic mass can respond to the high-speed stress respectively. .
- the plurality of ceramic blocks 612c and the plurality of metal blocks 612d constituting the block-containing layer 612b are scattered substantially uniformly between the piezoelectric layers.
- the plurality of ceramic lumps 612c and the metal lumps 612d are scattered almost uniformly between the piezoelectric layers, it is possible to suppress the concentration of stress due to element deformation to a part.
- the relaxation effect becomes larger. If the ceramic mass surrounds the metal mass, or conversely, the metal mass encloses the ceramic mass, the ceramic mass 612c and the metal mass 612d are placed in the stacking direction of the laminate. It becomes a form that is connected in series. The effect of connecting the relaxation effect in series to the stress applied in the stacking direction is created, and the high-speed stress can be followed. Since the relaxation effect can be expressed by the arrangement of ions that can be displaced at high speed, the relaxation effect is increased especially for continuous repeated stress.
- a plurality of the mass-containing layers 612b are present in the laminate 615.
- Each lump containing layer 612b is arranged via a plurality of piezoelectric layers 611 and a plurality of metal layers 612a, and is regularly arranged in the thickness direction of the laminate 615.
- the piezoelectric body 611 since the magnitude of displacement of the piezoelectric body 611 can be controlled by changing the ratio of the plurality of ceramic bodies 612c and the plurality of metal bodies 612d constituting the body-containing layer 612b, the piezoelectric body It is possible to obtain a structure with excellent mass productivity without having to change the thickness of 11.
- the lump containing layer 612b In order to drive the laminated piezoelectric element with a stable displacement, the lump containing layer 612b should not be easily deformed with respect to the load driven by the stacked piezoelectric element. Since the lump containing layer 612b includes a plurality of ceramic lumps 612c and a plurality of metal lumps 612d, the deformation state with respect to the load can be adjusted by the distribution.
- the relationship between the volume VI occupied by the ceramic mass 612c and the volume V2 occupied by the metal mass 612d is preferably VI> V2. Further, when considering the void volume V3 in the lump containing layer 612b, it is preferable that V3> V2, and it is more preferable that V3> VI> V2. Thereby, the displacement of the element is further increased, and a highly durable multilayer piezoelectric element can be obtained.
- the metal layer 612e adjacent to the lump containing layer 612b on both sides in the stacking direction is adjacent to the metal layer 612e on both sides in the stacking direction (the lump containing layer 612b and And the metal layer 612f) should have fewer voids.
- the contact area between the end portion of the dense metal layer 612e with few voids and the external electrode 615 is increased, and the conductive material is easily diffused.
- the bonding strength between the external electrode 615 and the side surface of the laminate 615 can be increased.
- the porosity of the metal layer 612e is preferably 95% or less of the porosity of other metal layers such as the metal layer 612f, more preferably 90% or less.
- the metal layer 612e 1S adjacent to the lump containing layer 612b on both sides in the stacking direction has a thickness greater than the metal layers (lump containing layer 612b and metal layer 612f) adjacent to the metal layer 612e on both sides in the stacking direction. Larger is desirable. This increases the contact area between the end of the thick metal layer 61 2e and the external electrode 615 and causes diffusion of the conductive material. It becomes easy. By this diffusion bonding (diffusion bonding), the bonding strength between the external electrode 615 and the side surface of the laminate 15 can be increased.
- the thickness of the metal layer 612e is preferably 105% or more of the thickness of other metal layers such as the metal layer 612f, more preferably 110% or more.
- a part 15c of the external electrode 615 enters between the two piezoelectric bodies 11 adjacent to each other in the stacking direction of the lump containing layer 612b.
- a part 15c of the external electrode 615 enters a part of the region between the adjacent piezoelectric bodies 11 and 11, so that the lateral force of the laminated body 615 also has a structure in which a pile is driven into the laminated body 615.
- the bonding strength between the external electrode 615 and the laminate 615 increases, and when the external electrode 615 peels off from the side of the laminate 615 even when it is driven continuously for a long time under high electrolysis and high pressure. Can be prevented. For this reason, the connection reliability between a part of the metal layers 612a and the external electrodes 615 is improved.
- the depth D at which the external electrode 615 enters a part of the region between the piezoelectric bodies 611 and 611 adjacent from the side surface of the laminate 615 is preferably 1 ⁇ m or more, more preferably 5 ⁇ m or more. Is good. When the depth D is within this range, a sufficient anchor effect can be obtained.
- the external electrode 615 in the present embodiment shown in FIG. 42 includes a plurality of layers 615a and 615b stacked in the direction perpendicular to the side surface of the stacked body 615. Of these, it is desirable that the external electrode layer 15a located on the side surface side of the laminate 615 has a higher glass material content than the external electrode layer 615b located on the outer surface side. Due to the large amount of glass component in the external electrode layer 15a adjacent to the side surface of the multilayer body 615, a part 615c of the external electrode 615 enters between the piezoelectric bodies 11 adjacent to each other in the stacking direction of the lump containing layer 612b. Thus, the bonding strength between the external electrode 615 and the stacked body 615 can be further increased.
- the bonding strength of the lead wire connected to the external electrode 615 by soldering can be increased. . This is because solder has low wettability with respect to glass components.
- FIG. 43 is a cross-sectional view of the laminated body 615 cut along a plane including the lump containing layer 612b in a direction perpendicular to the laminating direction.
- a portion 615c of the external electrode 615 that penetrates between the piezoelectric layers 611 and 611 is a ceramic block that forms the block-containing layer 612b. Touch the body 612c and the metal block 612d (join! /).
- the part 615c of the external electrode 615 is in contact with both the ceramic block 612c and the metal block 612d, and the following effects are obtained.
- the conductive component of the external electrode 615 has good wettability with the metal component of the metal block 612d, when a part of the external electrode 615 is in contact with the metal block 612d, they are firmly bonded. Is done. Further, since the glass component of the external electrode 615 has good wettability with the piezoelectric body of the ceramic block 612c, when a part of the external electrode 615 is in contact with the ceramic block 612c, they are firmly bonded. Furthermore, as described above, a part of the external electrode 615 enters between the two piezoelectric bodies 611 and 611 adjacent to both sides in the stacking direction of the mass-containing layer 612b! / Therefore, even when the element is driven with a large amount of displacement, the laminated body 615 has an effect of preventing the laminate 615 from being peeled off via the lump containing layer 612b. is there.
- the stress at the interface between the multilayer body 615 and the external electrode 615 generated by the expansion and contraction of the multilayer body 615 when the element is driven causes two stresses adjacent to both sides of the lump containing layer 612b in the stacking direction. It propagates to the piezoelectric layer 11 via a part 615c of the external electrode 615 that has entered between the piezoelectric layers 611 and 611. In accordance with the propagated stress, the crystal structure of the piezoelectric body in contact with the part 15c of the external electrode 615 changes, and the stress is absorbed.
- part 615c of external electrode 615 has a metal as a main component, the metal itself is deformed and an effect of relaxing stress is obtained, and part 615c of external electrode 615 is in contact with this. Since the force for pressing the piezoelectric body is large, the crystal structure of the piezoelectric body is likely to change.
- the surface of the multilayer piezoelectric element may be coated with an exterior resin (not shown), and a portion of the exterior resin may enter a part of the region between the two adjacent piezoelectric layers 611 and 611. preferable.
- a part of the exterior resin that is not only part of the external electrode 615 is also inserted between the two piezoelectric bodies 611 and 611 adjacent to both sides of the lump containing layer 612b in the stacking direction. Since the adjacent piezoelectric bodies 611 are connected to each other at V, the effect of preventing the laminate 615 from peeling off via the block-containing layer 612b even when the element is driven with a large amount of displacement. There is.
- the stress at the interface between the laminate 615 and the exterior resin caused by the expansion and contraction of the laminate 615 when the element is driven causes two piezoelectric bodies adjacent to both sides of the lump containing layer 612b in the lamination direction. Propagated to the piezoelectric layer 611 through a part of the exterior resin that has entered between the layers 611 and 611. In response to the propagated stress, the crystal structure of the piezoelectric body in contact with a part of the exterior resin changes, and the stress is absorbed.
- the piezoelectric body is oxidized and reduced according to the oxygen concentration and humidity of the surrounding atmosphere, and the piezoelectric characteristics are long-term use of the multilayer piezoelectric element. Although it may change, the influence of the environment of use can be suppressed by part of the exterior resin. As a result, the stress relaxation function of the piezoelectric body becomes highly durable, the bonding reliability between the covering member and the multilayer body is further improved, and a long-life multilayer piezoelectric element can be obtained.
- the multilayer piezoelectric element of this embodiment can be manufactured in the same manner as described above.
- a laminate is produced in the same procedure as described above.
- a binder is added to the glass powder to produce a silver glass conductive paste, which is formed into a sheet shape, and the green density of the dried (spattered solvent) is controlled to 6-9 gZcm 3 ,
- This sheet is transferred to the external electrode formation surface of the columnar laminate 615.
- This is baked at a temperature higher than the soft melting point of the glass, a temperature not higher than the melting point of silver (965 ° C), and a temperature equal to or lower than 4Z5, which is the firing temperature (° C) of the laminate 615.
- the noinder component in the sheet produced using the silver glass conductive paste is scattered and lost, and the external electrode 615 made of a porous conductor having a three-dimensional network structure can be formed.
- the paste constituting the external electrode 615 may be laminated on a multilayer sheet and baked with force, or may be laminated on each layer and baked, but may be laminated on a multilayer sheet. Baking at once for better mass production.
- the glass component for each layer it is sufficient to use a glass component with a different amount for each sheet.
- a very thin glass-rich layer is formed on the surface closest to the piezoelectric body 11!
- a method of laminating multilayer sheets after printing a glass-rich paste on the laminate 615 by a method such as screen printing is used.
- a sheet of 5 m or less may be used instead of printing.
- the baking temperature of the silver glass conductive paste effectively forms the neck, diffuses and joins the silver in the silver glass conductive paste and the metal layer 612, and creates voids in the external electrode 615. It is preferable to set the temperature within the range of 500 to 800 ° C. from the viewpoint that the external electrode 615 and the side surface of the columnar laminate 615 are partially joined.
- the soft spot of the glass component in the silver glass conductive paste is desirably 500 to 800 ° C.
- the baking temperature is 800 ° C or less, a porous conductor having an effective three-dimensional network structure can be formed. Baking is preferably performed at a temperature within 1.2 times the soft softness point of the glass. On the other hand, when the baking temperature is 500 ° C. or higher, sufficient diffusion bonding is performed between the end portion of the metal layer 612 and the external electrode 615 to form a neck portion.
- the laminated body 615 on which the external electrode 615 is formed is immersed in the silicone rubber solution, and the silicone rubber solution is vacuum degassed to fill the groove of the laminated body 615 with silicone rubber, and thereafter The silicone rubber solution force also raises the laminate 615 and coats the side of the laminate 615 with silicone rubber.
- the laminated piezoelectric element of the present invention is completed by curing the silicone rubber filled in the groove and coated on the side surface of the laminated body 615.
- a laminated body 615 is produced in the same manner as described above. Thereafter, a conductive paste prepared by adding a binder, a plasticizer, and a solvent to a conductive agent powder mainly composed of silver and glass powder to be the external electrode layer 615a is used as an external electrode 615. Printed on the side of the laminate 615 to be formed by screen printing or the like. Then, drying and baking are performed at a predetermined temperature.
- the glass amount of the external electrode 615a is increased, and the glass amount of the external electrode layer 615b is decreased.
- the external electrode 615 can be formed.
- the external electrode layer 615b is printed and dried on the external electrode layer 615b and baked at the same time to form the external electrode 615 composed of the external electrode layers 615a and 615b. Good.
- the force shown in the case of the external electrode 615 having two layers may be greater than that.
- the glass component enhances the bonding strength with the piezoelectric layer 11 and effectively penetrates between the piezoelectric layers 11 and 11, so that at least lead oxide or silicon oxide can be used. It is desirable that the glass has a soft melting point of 800 ° C or less including one kind.
- the glass components include silica glass, soda lime glass, lead alkali silicate glass, aluminoborosilicate glass, borosilicate glass, aluminosilicate glass, borate glass, phosphoric acid. Salt glass, lead glass, etc. can be used.
- alkaline earth metal oxides such as MgO, CaO, SrO, BaO
- Amounts containing 0 to: L0 mass%, alkali metal oxides 0 to: L0 mass% can be used.
- the borosilicate glass may be a glass containing 5 to 30% by mass of ZnO. ZnO has the effect of lowering the working temperature of borosilicate glass.
- Glasses containing ⁇ 30 mass%, ZnO 0 ⁇ 30 mass%, alkaline earth metal oxides 0 ⁇ 30 mass%, alkali metal oxides 0 ⁇ 10 mass% can be used.
- Glasses containing LO mass% can be used.
- the conductive agent constituting the external electrode 615 is preferably composed mainly of silver from the viewpoints of oxidation resistance, low Young's modulus, and low cost. In addition, you may add a trace amount platinum or palladium from the point of improving electrification-proof migration resistance.
- Example 1
- a gas sensor element was produced as follows. First, Zircoyu powder and glass mainly composed of stable Zircoure (ZrO containing 5 mol% Y) with an average particle size of 0.4 / z m
- a slurry in which powder, needle, and plasticizer were mixed was prepared, and a ceramic green sheet with a thickness of 150 ⁇ m was prepared by the doctor blade method.
- a conductive paste with a binder in raw powder such as silver alloy powder with the composition shown in Table 1 is printed to a thickness of 30 ⁇ m by screen printing. did.
- the heating element pattern was printed in a meandering shape so that the heat generation was concentrated on the portion where the heating element was formed, as in the conventional ceramic heater.
- a stabilized zirconium oxide (ZrO containing 5 mol% Y ⁇ ) powder with an average particle size of 0.4 m is used as the metal powder.
- the green sheets were laminated so as to have the shape shown in FIG. In places where the thickness of the ceramic layer was required, only the required number of green sheets was laminated without printing the conductive paste.
- the laminated molded body was debindered at a predetermined temperature, and then sintered at 800 to 1200 ° C to obtain a sintered body.
- a metal layer having a difference in silver concentration is formed through a ceramic layer, silver diffuses from a metal layer having a high concentration to a metal layer having a low concentration, and thus a lump containing layer having a high porosity. 45 was formed, and a relatively dense metal layer 47 was formed.
- a metal pattern 57 printed with platinum paste was formed and laminated. Thereby, a heater body type oxygen sensor was obtained.
- the gas sensor element temperature is maintained at 700 ° C, and then a mixed gas of hydrogen, methane, nitrogen, and oxygen is used to detect a mixed gas of air-fuel ratio 12 It was confirmed that the sensor was functioning by generating an electromotive force. afterwards, A mixed gas of air-fuel ratios 12 and 23 was sprayed IX 10 9 times alternately at intervals of 0.5 seconds, and it was confirmed that the electromotive force changed due to the difference in air-fuel ratio. After that, a mixed gas with an air-fuel ratio of 12 was sprayed onto the sensor, and it was confirmed whether the sensor was functioning based on whether or not the sensor generated an electromotive force. Table 1 shows the results.
- sample No. 1 in which the metal layer 45 is dense cannot generate gas through the metal layer 45 because the gas cannot be supplied to the ceramic layer 43, which is a solid electrolyte that functions the sensor.
- Sample No. 2 ⁇ L 1 functioned as an oxygen sensor.
- Samples Nos. 3, 5, 6, 10, and 11 in which the metal mass percentage X of the metal layers 45 and 47 is 90% or more and the mass percentage difference is 3 to 5% have the most excellent durability. It was.
- a filter element was produced as follows. First, cordierite powder whose main component is cordierite (containing 5 mol% Y Y-cordierite) powder with an average particle size of 0.4 / z m
- a slurry in which glass powder, a binder, and a plasticizer were mixed was prepared, and a ceramic green sheet having a thickness of 150 ⁇ m was prepared by a doctor blade method.
- a conductive paste with a binder in raw powder such as silver alloy powder with the composition shown in Table 1 is printed to a thickness of 30 ⁇ m by screen printing.
- the conductive paste for forming the mass-containing layer 63 includes cordierite (5 mol 0 / oY ⁇ containing cordierite) powder with an average particle size of 0.4 m.
- the multilayer molded body was debindered at a predetermined temperature, and then fired at 800 to 1200 ° C to obtain a filter element. Thereafter, exhaust gas synthesized experimentally was supplied, and the filter characteristics were measured while maintaining the temperature at 400 ° C. Thereafter, continuous operation at 400 ° C was performed for 1000 hours, and the filter characteristics were measured again. The results are shown in Table 2.
- a fuel cell element was produced as follows. First, zircoyu powder and glass powder mainly composed of stable cocoa powder (ZrO containing 5 mol% Y) with an average particle size of 0.4 / z m
- a slurry was prepared by mixing the powder, the needle, and the plasticizer, and a ceramic green sheet having a thickness of 150 m was prepared by the doctor blade method.
- the sintered body was processed into a desired dimension, and an external electrode was formed.
- a conductive paste for an external electrode was prepared by adding and mixing a binder, a plasticizer, a glass powder and the like to a metal powder whose main component is silver powder. This conductive paste was screen-printed on the portion on the side of the sintered body where the external electrode 69 was to be formed. Then, this was baked at 600-800 degreeC, the external electrode was formed, and the fuel cell element was obtained.
- a multilayer piezoelectric element was produced as follows. First, a slurry containing a raw material powder consisting mainly of lead zirconate titanate (PZT) powder with an average particle size of 0.4 m, a binder, and a plasticizer was prepared, and the thickness was 150 ⁇ m by the doctor blade method. A ceramic green sheet was prepared. Next, a conductive paste obtained by adding a binder to a raw material powder such as silver alloy powder having the compositional power shown in Table 4 on one side of the ceramic green sheet was printed to a thickness of 30 m by screen printing. In the metal paste layer for forming the mass-containing layer 95, 1% by mass of lead zirconate titanate (PZT) powder having an average particle size of 0.4 m was added to the metal powder. Table 4 is divided into Table 4 (1) and Table 4 (2).
- the green sheets were laminated so as to have the shape shown in FIG. 25 to obtain a laminated molded body.
- the metal layers were laminated so that the number of metal layers was 100, and the required number of green sheets was laminated without printing the conductive paste at places where the ceramic layer thickness was required.
- the multilayer molded body was debindered at a predetermined temperature, and then sintered at 800 to 1200 ° C to obtain a sintered body.
- a metal layer having a difference in silver concentration is formed through a ceramic layer, silver diffuses from a metal layer having a high concentration to a metal layer having a low concentration, and thus a lump containing layer having a high porosity. 95 was formed, and a relatively dense metal layer 93 was formed.
- a conductive paste for an external electrode was prepared by adding and mixing a binder, a plasticizer, a glass powder and the like to metal powder mainly composed of silver. This conductive paste was printed by screen printing or the like on the side where the external electrode 101 on the side surface of the sintered body was to be formed, and fired at 600 to 800 ° C. to form an external electrode. Thereby, a multilayer piezoelectric element was obtained.
- Sample Nos. 2 to 31, which are examples of the present invention, are required as piezoelectric actuators that do not significantly decrease the element displacement after being driven 1 X 10 9 times continuously. Has an effective displacement.
- the metal paste layer having a silver mass percentage X of 85% or more and a mass percentage difference of 2 to 10% was excellent in durability.
- FIG. 44 is a cross-sectional view showing the laminated molded body before firing.
- low-rate metal paste layers 95 are arranged on both ends in the stacking direction of the multilayer piezoelectric element.
- Table 5 shows the metal composition of the low-rate metal paste layer and the metal base layer on both sides of the low-rate metal paste layer.
- Samples No. 1 to 14 obtained were evaluated in the same manner as in Example 4. The results are shown in Table 5. The characteristics of sample No. 1 were degraded by the cycle test. The other samples gave good results. In particular, the mass percentage X of the metal paste layer was high and better, and the results tended to be obtained.
- a multilayer piezoelectric element as shown in FIG. 32 was produced as follows. First, calcined powder of piezoelectric ceramic mainly composed of PZT with an average particle size of 0.4 m, binder, and plasticizer A ceramic green sheet to be a piezoelectric layer 1 having a thickness of 150 m was prepared by a doctor blade method.
- a silver over palladium alloy (silver 90 mass 0/0, Bruno “radium 10 mass 0/0) for forming the internal electrodes 402 on one surface of the ceramic green sheet adding a binder to the conductive
- the best was formed to a thickness of 4 m by screen printing.
- acrylic beads having an average particle size of 0.5 ⁇ m are added to silver powder to 200% by volume with respect to 100% by volume of silver powder to form a lump containing layer 403 on one side of some ceramic liner sheets.
- an inorganic paste formed by adding a binder was formed to a thickness of 4 ⁇ m by screen printing.
- each ceramic green sheet is formed so that the lump containing layer 403 is formed at a ratio of one layer to 20 layers of the ceramic liner sheet on which the conductive paste for forming the internal electrode 402 is printed.
- Were laminated There were 300 green sheets on which the conductive paste for forming the internal electrodes 402 was printed, and 14 inorganic bases for forming the lump containing layer 403.
- ceramic green sheets on which conductive bases were printed were stacked so that the internal electrodes 402 had different polarities.
- the obtained laminated molded body was degreased at a predetermined temperature and fired at 980 to 1100 ° C. to obtain a laminated fired body.
- the obtained laminated fired body was ground with a surface grinder to obtain a laminate 410.
- a silver glass conductive paste for forming the external electrode 4 is formed on the side surface of the laminate 410 by screen printing with a thickness of 30 m and baked at 700 ° C for 30 minutes. External electrode 4 was formed.
- the porosity of the lump containing layer 403 was 80%, and the porosity of the internal electrode 402 was 20%.
- silver was scattered and distributed, and voids were formed between these silver.
- a lead wire is connected to the external electrode 4, a 3 kVZmm DC electric field is applied to the positive and negative external electrodes 4 through the lead wire for 15 minutes, and polarization is performed, as shown in FIG.
- a piezoelectric actuator using a piezoelectric element was fabricated.
- a DC voltage of 160 V was applied to the obtained multilayer piezoelectric actuator, a displacement of 40 m was obtained in the stacking direction.
- this multilayer piezoelectric actuator can be used with an AC voltage of 0 to + 160V at room temperature. The test was performed by applying a frequency of 50 Hz and continuously driving up to 1 ⁇ 10 9 times. Table 6 shows the results obtained.
- sample number 6 is provided with a stress relaxation region consisting of eight layers of piezoelectric lc with a thickness of 300 m from both ends.
- a laminated piezoelectric actuator was fabricated in the same manner as in Example 1 except that the composite layer was formed next to the fifth internal electrode 402 from both ends.
- the thickness of each of the piezoelectric layers 401a and la constituting the composite layer 41 1 was 150 m.
- a multilayer piezoelectric element as shown in FIG. 36 was produced as follows. First, piezoelectric ceramics mainly composed of lead zirconate titanate (? 1 ⁇ 1: 0—PbTiO) with an average particle size of 0.4 111
- a slurry in which a tasting calcined powder, a binder, and a plasticizer were mixed was prepared, and a ceramic green sheet to be a piezoelectric body 11 having a thickness of 150 ⁇ m was prepared by a doctor blade method.
- a silver - palladium alloy (silver 95 mass 0/0 - Palladium ⁇ arm 5 weight 0/0) resist thickness of the conductive paste obtained by adding a binder by screen printing on 20 / zm
- printing was carried out to a thickness of 10 m, 300 sheets formed were laminated and baked. Firing was performed at 1000 ° C after holding at 800 ° C.
- the part for forming the block-containing layer composed of a plurality of blocks was as follows.
- a piezoelectric paste is prepared by calcining a piezo-ceramic powder of the same material as the piezoelectric layer, and the thickness of the resist is 10 ⁇ m, and the thickness is 5 ⁇ m.
- a mixing base was prepared by adding a binder to a powder obtained by mixing silver powder of the same weight as the calcined powder of piezoelectric ceramics of the same material as the piezoelectric layer, and using a plate making with a resist thickness of 10 ⁇ m. Printing was performed to a thickness of 5 ⁇ m. The lump containing layer is placed on the 50th, 100th, 200th, and 250th layers of the laminate for sample Nos.
- the layers were arranged in the 50th, 100th, 150th, 200th, and 250th layers of the laminate.
- the mass-containing layer was not provided.
- the epoxy resin component was allowed to exist between adjacent blocks in the small cross-sectional layer by the following procedure. That is, after baking at 1000 ° C., epoxy resin paste was poured into the voids of the lump containing layer. The injection method was to penetrate the void by side force and surface tension of the laminate using a paste containing a resin paste, and then heated the temperature to cure the resin.
- the lump containing layer was formed by arranging 6 lump bodies as shown in FIG.
- a flaky silver powder having an average particle size of 2 ⁇ m and the balance of amorphous glass having a soft soft spot of 640 ° C mainly composed of a key particle having an average particle size of 2 ⁇ m Add 8 parts by mass of the noder to the mixture with the powder to 100 parts by mass of the total mass of the silver powder and the glass powder, and mix well to produce a silver glass conductive paste.
- the glass conductive paste was formed on the release film by screen printing, dried, and then peeled off from the release film to obtain a silver glass conductive paste sheet.
- the sheet of silver glass paste was transferred to the side surface of the laminate 513 and laminated, and baked at 700 ° C for 30 minutes to form the external electrode 515.
- a lead wire is connected to the external electrode 515, a 3 kVZmm DC electric field is applied to the positive and negative external electrodes 515 via the lead wire for 15 minutes, and polarization treatment is performed, as shown in FIG. A piezoelectric actuator using the multilayer piezoelectric element was manufactured.
- Sample No. 2 in which the stress relaxation layer (the mass-containing layer) and the stress concentration layer (the dense layer) are arranged next to each other via another piezoelectric body has a large element displacement. Can only do It can be seen that a stacked actuator with a stable element displacement can be produced.
- sample Nos. 3, 4, and 5 in which stress relaxation layers are regularly arranged for every 50 layers via the piezoelectric body, the element displacement amount can be changed almost as much as the element displacement amount can be maximized.
- sample No. 5 was printed with a paste containing a binder mixed with a powder of silver powder of the same weight as the calcined powder of piezoelectric ceramics of the same material as the piezoelectric layer, and a melting point of silver of 960 ° C. By firing at a higher temperature, all of the silver in the mixed paste diffused into the metal layer that passed through the piezoelectric body. As a result, a stress relaxation layer (block-containing layer) having the largest porosity in the sample could be formed, and a stacked actuator with extremely stable element displacement could be obtained.
- a multilayer piezoelectric element as shown in Fig. 41 was produced as follows. First, piezoelectric ceramics mainly composed of lead zirconate titanate (? 1 ⁇ 1: 0—PbTiO) with an average particle size of 0.4 111
- a slurry was prepared by mixing the calcined powder of the powder, the binder, and the plasticizer, and a ceramic green sheet to be the piezoelectric body 11 having a thickness of 150 ⁇ m was prepared by the doctor blade method.
- a silver - palladium alloy (silver 95 mass 0/0 - Palladium ⁇ arm 5 weight 0/0) was added to the binder in the conductive paste sheet formed by screen printing 300 sheets were laminated and fired to obtain a laminate 615. Firing is held at 800 ° C after 1000. Went in C.
- the green sheet forming the lump containing layer 612b is composed mainly of lead zirconate titanate (PbZrO-PbTiO).
- the ceramic lump paste consisting of the calcined piezoelectric ceramic powder, binder, and plasticizer was printed to a thickness of 5 m using a 10 m resist plate. Then, after drying at 80 ° C for 20 minutes, the conductive paste used to form the metal layer 612a is applied to the part where the metal agglomerate is to be formed, so that the resist thickness is 5 ⁇ m and the thickness is 5 ⁇ m.
- the lump containing layer 612b was arranged to be the 50th layer, the 100th layer, the 150th layer, the 200th layer, and the 250th layer.
- the lump containing layer 612b is composed of 10 ceramics as shown in Fig. 41 (b).
- the rack lump 12d and 10 metal lumps 12c were arranged.
- 8 parts by mass of a binder was added to 100 parts by mass of the total mass of the silver powder and the glass powder, and mixed well to prepare a silver glass conductive paste.
- This silver glass conductive paste was formed on a release film by screen printing, dried, and then peeled off from the release film cover to obtain a sheet of silver glass conductive paste. Then, this sheet was transferred to the side surface of the laminate 615 and laminated, and baked at 700 ° C. for 30 minutes to form an external electrode 615.
- a lead wire is connected to the external electrode 615, and a 3 kVZmm DC electric field is applied to the positive and negative external electrodes 615 via the lead wire for 15 minutes to perform polarization treatment, as shown in FIG.
- a piezoelectric actuator using the multilayer piezoelectric element was obtained.
- the “arrangement state of the ceramic mass” in Table 10 indicates a layer in which both ends in the thickness direction of the ceramic mass are in contact with adjacent piezoelectric layers on both sides.
- “Arrangement state of metal block” in Table 1 indicates a layer in which both ends of the metal block in the thickness direction are in contact with adjacent piezoelectric layers on both sides.
- sample No. 1 as a comparative example, the stress applied to the laminated interface was concentrated on one point, the load increased, and peeling occurred, and a beep and noise were generated.
- Sample Nos. 1 to 9 which are examples of the present invention, have effective displacement amounts required as piezoelectric actuators that do not significantly reduce the element displacement even after continuous driving 1 ⁇ 10 9 times. Had.
- sample numbers 2 to 5 and 8 in which the relationship between the volume VI occupied by the ceramic mass, the volume V2 occupied by the metal mass, and the volume V3 occupied by the void satisfies: ⁇ 3> ⁇ 1> ⁇ 2 8 9 can increase the amount of displacement of the element, both in the thickness direction of the ceramic block or metal block.
- Sample Nos. 2 to 7 in contact with the piezoelectric layers on both sides adjacent to each other the displacement amount of the element hardly changed, and it was possible to obtain a stacked actuator having a stable element displacement amount.
- a piezoelectric actuator having a multilayer piezoelectric element force as shown in Fig. 41 was produced as follows. First, lead zirconate titanate with an average particle size of 0.4 111 (? 1 ⁇ 1: 0—PbTiO)
- a ceramic ceramic sheet with a thickness of 150 ⁇ m was prepared by the doctor blade method using a ceramic ceramic calcined powder composed mainly of 33, mixed with a binder and a plasticizer.
- a silver - palladium alloy (silver 95 mass 0/0 - Palladium ⁇ arm 5 weight 0/0) was added to the binder in the conductive paste sheet formed by screen printing 300 sheets were laminated and fired to obtain a laminate. Firing is held at 800 ° C, then 1000. Went in C.
- the green sheet on which the metal layer 612a was formed was printed using a conductive paste with a resist thickness of 20 m so as to have a thickness of 10 m.
- the green sheet forming the lump containing layer 612b is composed mainly of lead zirconate titanate (PbZrO-PbTiO).
- the ceramic lump paste consisting of the calcined piezoelectric ceramic powder, binder, and plasticizer was printed to a thickness of 5 m using a 10 m resist plate. Then, after drying at 80 ° C for 20 minutes, the conductive paste used to form the metal layer 612a is applied to the part where the metal agglomerate is to be formed, so that the resist thickness is 5 ⁇ m and the thickness is 5 ⁇ m. Printed on. Further, on the green sheet forming the metal layer 612e, a conductive paste in which a binder was added to a silver-palladium alloy was printed with a resist thickness of 30 ⁇ m to a thickness of 15 m.
- the lump containing layer 612b is arranged so that it is 50th layer, 100th layer, 150th layer, 200th layer, 250th layer, and on both sides of the lump containing layer 612b in the stacking direction.
- the metal layer to be formed was arranged to be a dense metal layer 612e.
- the lump containing layer 612b was formed by arranging 10 ceramic lumps and 10 metal lumps as shown in FIG. 41 (b).
- silver powder and glass 8 parts by mass of a binder was added to 100 parts by mass of the total mass of the powder, and mixed well to prepare a silver glass conductive paste.
- This paste was printed on the side of the laminate 615 by screen printing and dried.
- a conductive paste prepared by adding a binder to flaky silver powder having an average particle size was printed so as to overlap therewith, dried, and then baked at 700 ° C. for 30 minutes.
- the external electrode 615 including the external electrode layers 615a and 615b was formed.
- a lead wire is connected to the external electrode 615, and a 3 kVZmm DC electric field is applied to the positive and negative external electrodes 615 via the lead wire for 15 minutes to perform polarization treatment, as shown in FIG.
- a piezoelectric actuator using the multilayer piezoelectric element was manufactured.
- the metal layer 612e adjacent to both sides of the lump containing layer 612b in the stacking direction is 1.3 times thicker than the other metal layer 612a, and the porosity is 4Z5 times. It was.
- a part of the external electrode 615 entered an average depth of 20 ⁇ m between two piezoelectric bodies 11 adjacent on both sides of the lump containing layer 612b in the stacking direction.
- the external electrode layer 15a located on the side surface of the laminate 615 has a greater glass material content than the external electrode layer 615b located on the outer side.
- the external electrode 615 has a laminated body 615 and the layer on the side surface side has a multi-layer structure of many glass components, and the metal located on both sides of the lump containing layer 612b in the stacking direction.
- the layer 612e is made thicker than the other metal layer 612a and the porosity is reduced, and part of the external electrode is partly between the piezoelectric bodies 11 located on both sides of the lump containing layer 612b in the stacking direction. It is something that has been entangled.
- the actuator of sample number 10 has a problem that even if it is continuously operated at high speed under a high electric field and high pressure, some of the external electrodes 615 are peeled off from the side surfaces of the laminate 615 and the displacement characteristics deteriorate. Did not occur.
Abstract
Description
Claims
Priority Applications (4)
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CN2007800068248A CN101390228B (zh) | 2006-02-27 | 2007-02-27 | 陶瓷构件的制造方法、陶瓷构件、气体传感器元件、燃料电池元件、过滤元件、层叠型压电元件、喷射装置以及燃料喷射*** |
JP2008501785A JP4987847B2 (ja) | 2006-02-27 | 2007-02-27 | セラミック部材の製造方法 |
US12/280,768 US8007903B2 (en) | 2006-02-27 | 2007-02-27 | Method for manufacturing ceramic member, and ceramic member, gas sensor device, fuel cell device, filter device, multi-layer piezoelectric device, injection apparatus and fuel injection system |
EP07714993.8A EP1998383B1 (en) | 2006-02-27 | 2007-02-27 | Method for manufacturing ceramic member, and ceramic member for gas sensor device, fuel cell device, filter device, multi-layer piezoelectric device, injection apparatus, and fuel injection system |
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EP (1) | EP1998383B1 (ja) |
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CN (1) | CN101390228B (ja) |
WO (1) | WO2007097460A1 (ja) |
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JP2013501490A (ja) * | 2009-08-07 | 2013-01-10 | バイヤー・マテリアルサイエンス・アーゲー | 電気機械変換器を製造するための方法 |
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CN101390228B (zh) | 2010-12-08 |
EP1998383B1 (en) | 2016-12-28 |
US20090220765A1 (en) | 2009-09-03 |
EP1998383A1 (en) | 2008-12-03 |
EP1998383A4 (en) | 2012-10-24 |
JP5537586B2 (ja) | 2014-07-02 |
JPWO2007097460A1 (ja) | 2009-07-16 |
US8007903B2 (en) | 2011-08-30 |
CN101390228A (zh) | 2009-03-18 |
JP4987847B2 (ja) | 2012-07-25 |
JP2012209554A (ja) | 2012-10-25 |
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