WO2014025050A1 - 積層型圧電素子およびこれを備えた圧電アクチュエータ、噴射装置ならびに燃料噴射システム - Google Patents
積層型圧電素子およびこれを備えた圧電アクチュエータ、噴射装置ならびに燃料噴射システム Download PDFInfo
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- WO2014025050A1 WO2014025050A1 PCT/JP2013/071737 JP2013071737W WO2014025050A1 WO 2014025050 A1 WO2014025050 A1 WO 2014025050A1 JP 2013071737 W JP2013071737 W JP 2013071737W WO 2014025050 A1 WO2014025050 A1 WO 2014025050A1
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- Prior art keywords
- piezoelectric element
- laminated
- multilayer
- protrusion
- width direction
- Prior art date
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- 239000007924 injection Substances 0.000 title claims abstract description 62
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Images
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
- H10N30/80—Constructional details
- H10N30/87—Electrodes or interconnections, e.g. leads or terminals
- H10N30/872—Interconnections, e.g. connection electrodes of multilayer piezoelectric or electrostrictive devices
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B17/00—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups
- B05B17/04—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods
- B05B17/06—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations
- B05B17/0607—Apparatus for spraying or atomising liquids or other fluent materials, not covered by the preceding groups operating with special methods using ultrasonic or other kinds of vibrations generated by electrical means, e.g. piezoelectric transducers
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
- F02M—SUPPLYING COMBUSTION ENGINES IN GENERAL WITH COMBUSTIBLE MIXTURES OR CONSTITUENTS THEREOF
- F02M51/00—Fuel-injection apparatus characterised by being operated electrically
- F02M51/06—Injectors peculiar thereto with means directly operating the valve needle
- F02M51/0603—Injectors peculiar thereto with means directly operating the valve needle using piezoelectric or magnetostrictive operating means
-
- 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
- H10N30/06—Forming electrodes or interconnections, e.g. leads or terminals
- H10N30/063—Forming interconnections, e.g. connection electrodes of multilayered piezoelectric or electrostrictive parts
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/50—Piezoelectric or electrostrictive devices having a stacked or multilayer structure
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/88—Mounts; Supports; Enclosures; Casings
Definitions
- the present invention relates to a laminated piezoelectric element used as, for example, a piezoelectric driving element (piezoelectric actuator), a pressure sensor element, a piezoelectric circuit element, and the like, and a piezoelectric actuator, an injection device, and a fuel injection system including the same.
- a piezoelectric driving element piezoelectric actuator
- a pressure sensor element a piezoelectric sensor element
- a piezoelectric circuit element and the like
- a piezoelectric actuator an injection device, and a fuel injection system including the same.
- a laminated piezoelectric element a laminated body in which a piezoelectric layer and an internal electrode layer are laminated, and an external electrode provided on a side surface of the laminated body and electrically connected to the internal electrode layer via a conductive bonding material,
- the thing of the structure containing is known (refer patent document 1).
- the present invention has been devised in view of the above problems, and its purpose is to suppress the development of micro cracks generated at the interface between the piezoelectric layer and the internal electrode layer and the internal electrode layer. It is an object of the present invention to provide a multilayer piezoelectric element that can be used, a piezoelectric actuator including the same, an injection device, and a fuel injection system.
- the multilayer piezoelectric element of the present invention includes a laminate in which a piezoelectric layer and an internal electrode layer are laminated, and is electrically connected to the internal electrode layer via a conductive bonding material provided on a side surface of the laminate.
- An external electrode, and the external electrode has a protrusion protruding toward the laminated body.
- the present invention also provides a piezoelectric actuator comprising a laminated piezoelectric element and a case for accommodating the laminated piezoelectric element therein.
- the present invention includes a container having an injection hole and a multilayer piezoelectric element, and fluid stored in the container is discharged from the injection hole by driving the multilayer piezoelectric element. It is an injection device.
- the present invention also provides a common rail that stores high-pressure fuel, an injection device that injects the high-pressure fuel stored in the common rail, a pressure pump that supplies the high-pressure fuel to the common rail, and a drive signal to the injection device.
- a fuel injection system comprising an injection control unit.
- the external electrode has a protrusion protruding toward the multilayer body, so that the conductive bonding material penetrates from the interface between the piezoelectric layer and the internal electrode layer or from the internal electrode layer.
- the crack that propagates to the interface with the external electrode stops at the protrusion, and since the conduction is always ensured between the external electrode and the conductive bonding material, the electrical connection is maintained and the durability is improved. .
- (A) is a schematic perspective view which shows an example of embodiment of the laminated piezoelectric element of this invention, (b) is a partially expanded view of the cross section cut
- (A) is a schematic perspective view which shows an example of embodiment of the laminated piezoelectric element of this invention, (b) is a partially expanded view of the cross section cut
- (A) is a partially expanded perspective view showing another example of the embodiment of the laminated piezoelectric element of the present invention, and (b) is an explanatory view of the external electrode shown in (a) as seen from the laminated body side.
- (A) is a partial expansion perspective view which shows the other example of embodiment of the lamination type piezoelectric element of this invention
- (b) is a schematic perspective view of the external electrode shown to (a).
- FIG. 1A is a schematic perspective view showing an example of an embodiment of a laminated piezoelectric element of the present invention
- FIG. 1B is a partially enlarged view of a cross section taken along line AA shown in FIG.
- a laminated piezoelectric element 1 shown in FIG. 1 includes a laminated body 4 in which a piezoelectric layer 2 and an internal electrode layer 3 are laminated, and is provided on a side surface of the laminated body 4 via an internal electrode layer 3 and a conductive bonding material 5.
- the external electrode 6 electrically connected to each other, and the external electrode 6 has a protrusion 61 protruding toward the laminate 4.
- a multilayer body 4 constituting the multilayer piezoelectric element 1 is formed by laminating piezoelectric layers 2 and internal electrode layers 3. For example, an active portion in which a plurality of piezoelectric layers 2 and internal electrode layers 3 are alternately stacked. And an inactive portion composed of the piezoelectric layer 2 provided at both ends in the stacking direction of the active portion, for example, in a rectangular parallelepiped shape having a length of 0.5 to 10 mm, a width of 0.5 to 10 mm, and a height of 1 to 100 mm. Is formed.
- the piezoelectric layer 2 constituting the multilayer body 4 is formed of ceramics having piezoelectric characteristics.
- ceramics for example, a perovskite oxide made of lead zirconate titanate (PbZrO 3 -PbTiO 3 ), Lithium niobate (LiNbO 3 ), lithium tantalate (LiTaO 3 ), or the like can be used.
- the thickness of the piezoelectric layer 2 is, for example, 3 to 250 ⁇ m.
- the internal electrode layer 3 constituting the laminated body 4 is formed by simultaneous firing with the ceramic forming the piezoelectric layer 2 and is alternately laminated with the piezoelectric layer 2 so as to sandwich the piezoelectric layer 2 from above and below.
- a driving voltage is applied to the piezoelectric layer 2 sandwiched between them.
- this forming material for example, a conductor mainly composed of a silver-palladium alloy having low reactivity with piezoelectric ceramics, or a conductor containing copper, platinum, or the like can be used. In the example shown in FIG.
- the internal electrode layer 3 has a thickness of 0.1 to 5 ⁇ m, for example.
- the external electrode 6 is provided on the side surface of the laminate 4 through the conductive bonding material 5 so as to be electrically connected to the internal electrode layer 3.
- the conductive bonding material 5 used here is preferably made of a conductive adhesive made of an epoxy resin or a polyimide resin containing a metal powder having good conductivity such as Ag powder or Cu powder.
- the conductive bonding material 5 is formed to a thickness of, for example, 5 to 500 ⁇ m.
- the external electrode 6 is a plate-like body made of a metal such as copper, iron, stainless steel, phosphor bronze, etc., and is formed to have a length of 20 to 80 mm, a width of 0.5 to 10 mm, and a thickness of 0.01 to 1.0 mm, for example. It has been done.
- the metal plate etc. which were made are mentioned. In the example shown in FIG.
- slits 62 are provided in the width direction, and holes 63 having a shape extending in the width direction are provided between the slits 62.
- the external electrode 6 may be longer than the above-described length and extend from the end face of the stacked body 4.
- the external electrode 6 may be directly bonded to the side surface along the stacking direction of the stacked body 4 via the conductive bonding material 5, and as shown in FIG. Even if the conductor layer 7 electrically connected to the internal electrode layer 3 is provided on the side surface of the multilayer body 4 and the external electrode 6 is bonded to the surface of the conductor layer 7 via the conductive bonding material 5. Good.
- the pair of conductor layers 7 provided on the side surfaces of the laminate 4 and electrically connected to the internal electrode layer 3 are formed by applying and baking a paste made of, for example, silver and glass. Therefore, each of the internal electrode layers 3 is joined to the side surface of the multilayer body 4 and alternately led to the opposite side surfaces of the multilayer body 4.
- the thickness of the conductor layer 7 is, for example, 5 to 500 ⁇ m.
- the external electrode 6 has a protrusion 61 that protrudes toward the laminate 4.
- the micro crack generated inside the multilayer body 4 when the multilayer piezoelectric element 1 is driven passes through the conductive bonding material 5 and progresses to the interface with the external electrode 6, Since it stops by the protrusion 61 in the middle of the path
- the protrusion 61 always ensures conduction between the external electrode 6 and the conductive bonding material 5. Therefore, electrical connection with the external electrode 6 is maintained, and durability is improved.
- the protrusion amount (length) of the protrusion 61 is preferably at least 0.01 mm, and is preferably a protrusion amount of 10% or more with respect to the thickness of the conductive bonding material 5.
- the shape of the protrusion 61 is such that the cross-sectional shape becomes narrower toward the tip (for example, a V-shaped cross-section), conversely, the shape whose cross-sectional shape becomes thicker toward the tip, or the anchor shape (eg, the cross-section L).
- the cross-sectional shape becomes narrower toward the tip (for example, a V-shaped cross-section), while the anchor effect is reversed.
- a shape such that the cross-sectional shape becomes thicker toward the tip, an anchor shape (for example, an L-shaped cross-section), and the like can be preferably employed.
- the protrusion 61 extends in the width direction of the external electrode 6 perpendicular to the stacking direction.
- extending in the width direction means that the shape is elongated in the width direction.
- blocks the progress of the crack of a lamination direction extends in the width direction, and can suppress the progress of the crack of a lamination direction more effectively.
- the external electrode 6 has at least one of a plurality of slits 62 alternately provided from both ends in the width direction toward the center portion and a plurality of holes 63 extending in the width direction. It is preferable that there is a protrusion on the periphery of the slit 62 or the hole 63.
- the protrusion 61 is continuous from the end of the slit 62 or the hole 63 in the width direction of the external electrode 6.
- the present invention can be applied to a case where the slit 62 and the hole 63 are rectangular when viewed from the front (in a direction perpendicular to the side surface). According to this configuration, it is possible to completely block the cracks penetrating the conductive bonding material 5 from extending toward the slit 62 or the hole 63 in the stacking direction.
- the length at which the protrusion 61 protrudes at the end in the width direction is longer than the length at the center portion in the width direction.
- the conductor layer 7 electrically connected to the internal electrode layer 3 is provided on the side surface of the multilayer body 4, that is, the side surface 4 of the multilayer body and the conductive bonding material 5.
- the conductor layer 7 is provided between the protrusions 61, it is preferable that the protrusions 61 bite into the conductor layer 7 at the end in the width direction. Since the protrusion 61 penetrates through the conductive bonding material 5 and reaches the conductor layer 7, the conductor layer 7 and the external electrode 6 move simultaneously following the expansion and contraction of the laminated body 4 at the time of driving. The reliability of mechanical joining is improved.
- the protrusion amount (length) of the protrusion 61 at the end in the width direction is preferably at least 0.05 mm, and protrudes through the conductive bonding material 5 to a position of 80% of the thickness of the conductor layer 7. It is effective.
- the protrusion 61 may penetrate through the conductive bonding material 5 and penetrate into the conductor layer 7 not only at the end in the width direction but also at other parts.
- the protrusion 61 may penetrate through the conductive bonding material 5 to the conductor layer 7 at the center in the width direction.
- the protrusion 61 may bite into the conductor layer in the entire region in the width direction, whereby the reliability of further electrical joining can be improved.
- the protrusion 61 bites into the conductor layer 7, so that the electrical connection between the external electrode 6 and the conductor layer 7 is achieved. Bonding is maintained and durability is improved.
- the conductive bonding material 5 is obtained by dispersing metal particles 51 in a resin 52, and the metal particles 51 contain at least the metal component on the surface of the protrusion 61.
- the metal particles 51 may include 50 to 90% of a silver component.
- gold, copper, nickel, and the like can be used similarly.
- the metal component 51 contains at least the same metal component as the metal component on the surface of the protrusion 61, the displacement between the surface of the protrusion 61 and the metal particle 51 due to thermal expansion can be reduced, and the external electrode 6 can be reduced. And the bonding strength between the conductive bonding material 5 can be increased.
- a ceramic green sheet to be the piezoelectric layer 2 is produced. Specifically, a ceramic slurry is prepared by mixing a calcined powder of piezoelectric ceramic, a binder made of an organic polymer such as acrylic or butyral, and a plasticizer. And a ceramic green sheet is produced using this ceramic slurry by using tape molding methods, such as a doctor blade method and a calender roll method.
- the piezoelectric ceramic any material having piezoelectric characteristics may be used.
- a perovskite oxide made of lead zirconate titanate (PbZrO 3 -PbTiO 3 ) can be used.
- the plasticizer dibutyl phthalate (DBP), dioctyl phthalate (DOP), or the like can be used.
- a conductive paste to be the internal electrode layer 3 is produced.
- a conductive paste is prepared by adding and mixing a binder and a plasticizer to a metal powder of a silver-palladium alloy. This conductive paste is applied on the ceramic green sheet in the pattern of the internal electrode layer 3 using a screen printing method. Further, a plurality of ceramic green sheets on which the conductive paste is printed are laminated, subjected to binder removal treatment at a predetermined temperature, fired at a temperature of 900 to 1200 ° C., and then subjected to a predetermined grinding using a surface grinder or the like.
- a laminated body 4 including the piezoelectric layers 2 and the internal electrode layers 3 that are alternately laminated is manufactured by performing a grinding process so as to have a shape.
- the laminate 4 is not limited to the one produced by the above manufacturing method, and any laminate 4 can be produced as long as the laminate 4 formed by laminating a plurality of piezoelectric layers 2 and internal electrode layers 3 can be produced. It may be produced by a manufacturing method.
- a silver glass-containing conductive paste prepared by adding a binder, a plasticizer, and a solvent to a mixture of conductive particles mainly composed of silver and glass is used to form a laminate with a conductive layer pattern.
- baking treatment is performed at a temperature of 650 to 750 ° C. to form the conductor layer 7.
- the external electrode 6 is bonded to the side surface of the multilayer body 4 through the conductive bonding material 5.
- the conductor layer 7 is formed on the side surface of the multilayer body 4, the external electrode 6 is bonded to the surface of the conductor layer 7.
- the conductive bonding material 5 uses an adhesive made of epoxy resin or polyimide resin containing good conductive metal powder such as Ag powder or Cu powder, solder, etc., and has a predetermined thickness and width by screen printing or dispensing method. It can be formed in a controlled manner.
- the external electrode 6 is made of a metal flat plate such as copper, iron, stainless steel, phosphor bronze or the like.
- a die having a shape corresponding to the protrusion 61 is used, and the protrusion is formed on the metal flat plate after punching by the mold or simultaneously with punching. Can be formed.
- the protrusion 61 can be formed at a predetermined position by punching with a pair of male and female dies processed into a desired shape and adjusting the clearance of the pair of dies at this time. Further, it may be formed by file processing after being once punched with a mold, or formed by welding.
- a DC electric field of 0.1 to 3 kV / mm is applied to the external electrodes 6 respectively connected to the side surfaces 4 (surfaces of the pair of conductor layers 7) of the pair of laminates, and the piezoelectric layer 2 constituting the laminate 4 Is completed, the laminated piezoelectric element 1 is completed.
- the conductor layer 7 is connected to an external power source via the external electrode 6 and a voltage is applied to the piezoelectric layer 2 to make each piezoelectric layer 2 large by the inverse piezoelectric effect. Can be displaced. This makes it possible to function as an automobile fuel injection valve that injects and supplies fuel to the engine, for example.
- FIG. 7 is a schematic sectional view showing an example of the embodiment of the piezoelectric actuator of the present invention.
- the piezoelectric actuator 11 of this example is obtained by housing the multilayer piezoelectric element 1 in a case 13.
- the case 13 includes a case body 15 whose upper end is closed and whose lower end is opened, and a lid member 17 attached to the case body 15 so as to close the opening of the case body 15.
- the multilayer piezoelectric element 1 is enclosed and accommodated in the case 13 together with, for example, an inert gas so that both end faces of the element 1 are brought into contact with the upper end inner wall and the lower end inner wall of the case 13, respectively.
- the case body 15 and the lid member 17 are made of a metal material such as SUS304 or SUS316L.
- the case main body 15 is a cylindrical body whose upper end is closed and whose lower end is open, and has, for example, a bellows (bellows) shape so as to be expandable and contractable in the stacking direction of the stacked body 7.
- the lid member 17 is formed in a plate shape, for example, so as to close the opening of the case body 15.
- the lid member 17 has two through holes into which the external lead member 8 can be inserted.
- the external lead member 8 is inserted into the through hole to electrically connect the external electrode 6 and the outside.
- the gap between the through holes is filled with soft glass or the like to fix the external lead member 8 and prevent the outside air from entering.
- the piezoelectric actuator 11 of this example can be driven stably for a long period of time.
- FIG. 8 is a schematic sectional view showing an example of the embodiment of the injection device of the present invention.
- the multilayer piezoelectric element 1 of the above example is accommodated in a storage container (container) 23 having an injection hole 21 at one end.
- a needle valve 25 capable of opening and closing the injection hole 21 is disposed.
- a fluid passage 27 is disposed in the injection hole 21 so as to be able to communicate with the movement of the needle valve 25.
- the fluid passage 27 is connected to an external fluid supply source, and fluid is constantly supplied to the fluid passage 27 at a high pressure. Therefore, when the needle valve 25 opens the injection hole 21, the fluid supplied to the fluid passage 27 is discharged from the injection hole 21 to the outside or an adjacent container, for example, a fuel chamber (not shown) of the internal combustion engine. It is configured.
- the upper end portion of the needle valve 25 has a large inner diameter, and is a piston 31 slidable with a cylinder 29 formed in the storage container 23.
- the multilayer piezoelectric element 1 of the above-described example is stored in contact with the piston 31.
- the fluid passage 27 may be opened by applying a voltage to the multilayer piezoelectric element 1 and the fluid passage 27 may be closed by stopping the application of the voltage.
- the injection device 19 of this example includes a container 23 having an injection hole 21 and the multilayer piezoelectric element 1 of the above example, and the fluid filled in the container 23 is ejected by driving the multilayer piezoelectric element 1. You may be comprised so that it may discharge from the hole 21.
- the multilayer piezoelectric element 1 does not necessarily need to be inside the container 23, and may be configured to apply pressure for controlling the ejection of fluid to the inside of the container 23 by driving the multilayer piezoelectric element 1. Good.
- the fluid includes various liquids and gases such as conductive paste in addition to fuel, ink, and the like.
- the injection device 19 of the present example employing the multilayer piezoelectric element 1 of the above example is used for an internal combustion engine, the fuel is accurately injected into the combustion chamber of the internal combustion engine such as an engine over a longer period of time compared to the conventional injection device. Can be made.
- FIG. 9 is a schematic view showing an example of an embodiment of the fuel injection system of the present invention.
- the fuel injection system 35 of the present example includes a common rail 37 that stores high-pressure fuel as a high-pressure fluid, and a plurality of injection devices 19 of the above-described examples that inject the high-pressure fluid stored in the common rail 37.
- a pressure pump 39 for supplying a high-pressure fluid to the common rail 37 and an injection control unit 41 for supplying a drive signal to the injection device 19 are provided.
- the injection control unit 41 controls the amount and timing of high-pressure fluid injection based on external information or an external signal. For example, if the fuel injection system 35 of this example is used for engine fuel injection, the amount and timing of fuel injection can be controlled while sensing the state of the combustion chamber of the engine with a sensor or the like.
- the pressure pump 39 serves to supply fluid fuel from the fuel tank 43 to the common rail 37 at a high pressure. For example, in the case of the fuel injection system 35 of the engine, the fluid fuel is fed into the common rail 37 at a high pressure of 1000 to 2000 atmospheres (about 101 MPa to about 203 MPa), preferably 1500 to 1700 atmospheres (about 152 MPa to about 172 MPa).
- the high-pressure fuel sent from the pressure pump 39 is stored and sent to the injection device 19 as appropriate.
- the ejection device 19 ejects a certain fluid from the ejection holes 21 to the outside or an adjacent container.
- the target for injecting and supplying fuel is an engine
- high-pressure fuel is injected from the injection hole 21 into the combustion chamber of the engine in the form of a mist.
- desired injection of high-pressure fuel can be stably performed over a long period of time.
- the external electrodes 6 in the multilayer piezoelectric element 1 are formed on the two opposite side surfaces of the multilayer body 4 in the above example, but the two external electrodes 6 are formed on adjacent side surfaces of the multilayer body 4. Alternatively, they may be formed on the same side surface of the laminate 4.
- the cross-sectional shape in the direction orthogonal to the stacking direction of the stacked body 4 is not limited to the quadrangular shape which is an example of the above embodiment, but a polygonal shape such as a hexagonal shape or an octagonal shape, a circular shape, or a straight line and an arc. You may be the shape which combined.
- a piezoelectric actuator provided with the multilayer piezoelectric element of this example was manufactured as follows. First, a ceramic slurry was prepared by mixing a calcined powder of a piezoelectric ceramic mainly composed of lead zirconate titanate (PbZrO 3 —PbTiO 3 ) having an average particle size of 0.4 ⁇ m, a binder, and a plasticizer. Using this ceramic slurry, a ceramic green sheet serving as a piezoelectric layer having a thickness of 50 ⁇ m was prepared by a doctor blade method.
- a ceramic slurry was prepared by mixing a calcined powder of a piezoelectric ceramic mainly composed of lead zirconate titanate (PbZrO 3 —PbTiO 3 ) having an average particle size of 0.4 ⁇ m, a binder, and a plasticizer.
- a ceramic green sheet serving as a piezoelectric layer having a thickness of 50 ⁇ m was prepared by a doctor blade method.
- a binder was added to the silver-palladium alloy to produce a conductive paste to be an internal electrode layer.
- a conductive paste serving as an internal electrode layer was printed on one side of the ceramic green sheet by a screen printing method, and 200 ceramic green sheets printed with the conductive paste were laminated. Further, a total of 15 ceramic green sheets not printed with the conductive paste serving as the internal electrode layer were laminated on the top and bottom of the 200 ceramic green sheets printed with the conductive paste serving as the internal electrode layer. .
- the laminate was fired at 980 to 1100 ° C. and ground to a 5 mm square shape using a surface grinder.
- a conductive paste in which a binder is mixed with silver and glass is printed by screen printing on the conductor layer forming portion on the side surface along the stacking direction of the laminate, and a baking process is performed at 700 ° C. Formed.
- a conductive bonding material in which Ag powder and polyimide resin are mixed and pasted is applied to the surface of the conductor layer with a dispenser, and an external electrode is placed on the surface of the laminate to cure the conductive bonding material. Fixed.
- a phosphor bronze flat plate having a width of 1.5 mm and a thickness of 0.1 mm was subjected to silver plating with a thickness of 1 to 15 ⁇ m, and then a plurality of rectangular slits were provided in the width direction. It was formed by punching with a pair of male and female molds. Then, by adjusting the clearance of the punching die, an external electrode in which a continuous protrusion having a height of 0.01 mm was formed from the edge of the slit to the edge parallel to the width direction.
- the external electrode as a comparative example was obtained by performing silver plating with a thickness of 1 to 15 ⁇ m on a phosphor bronze flat plate with a width of 1.5 mm and a thickness of 0.1 mm.
- the laminated piezoelectric element of the comparative example was 1 ⁇ 10 4.
- the multilayer piezoelectric element of this example can suppress the progress of cracks even after the continuous driving of 1 ⁇ 10 7 times and can drive stably.
- Laminated piezoelectric element 2 Piezoelectric layer 3: Internal electrode layer 4: Laminated body 5: Conductive bonding material 6: External electrode 61: Protrusion 7: Conductive layer 11: Piezoelectric actuator 13: Case 15: Case body 17: Lid member 8: External lead member 19 ... injection device 21 ... injection hole 23 ... storage container (container) 25 ... Needle valve 27 ... Fluid passage 29 ... Cylinder 31 ... Piston 33 ... Belleville spring 35 ... Fuel injection system 37 ... Common rail 39 ... Pressure pump 41 ... Injection control unit 43 ... Fuel tank
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Fuel-Injection Apparatus (AREA)
Abstract
Description
なお、銀の他にも、金、銅、ニッケルなども同様に用いることができる。
2:圧電体層
3:内部電極層
4:積層体
5:導電性接合材
6:外部電極
61:突起
7:導体層
11:圧電アクチュエータ
13:ケース
15:ケース本体
17:蓋部材
8:外部リード部材
19・・・噴射装置
21・・・噴射孔
23・・・収納容器(容器)
25・・・ニードルバルブ
27・・・流体通路
29・・・シリンダ
31・・・ピストン
33・・・皿バネ
35・・・燃料噴射システム
37・・・コモンレール
39・・・圧力ポンプ
41・・・噴射制御ユニット
43・・・燃料タンク
Claims (11)
- 圧電体層および内部電極層が積層された積層体と、該積層体の側面に設けられて前記内部電極層と導電性接合材を介して電気的に接続された外部電極とを含み、前記外部電極には前記積層体に向けて突出する突起があることを特徴とする積層型圧電素子。
- 前記突起が積層方向に垂直な前記外部電極の幅方向に延びていることを特徴とする請求項1に記載の積層型圧電素子。
- 前記外部電極は前記幅方向の両端から中央に向かって交互に設けられた複数のスリットおよび前記幅方向に延びる複数の孔の少なくとも一方を有しており、前記スリットまたは前記孔の周縁に前記突起があることを特徴とする請求項1または請求項2に記載の積層型圧電素子。
- 前記突起が前記スリットまたは前記孔における前記幅方向の端から端にかけて連続していることを特徴とする請求項3に記載の積層型圧電素子。
- 前記突起は前記幅方向の端において突出する長さが前記幅方向の中央部において突出する長さよりも長くなっていることを特徴とする請求項4に記載の積層型圧電素子。
- 前記積層体の側面には前記内部電極層と電気的に接続された導体層が設けられ、前記突起は前記幅方向の端において前記導体層に食い込んでいることを特徴とする請求項5に記載の積層型圧電素子。
- 前記積層体の側面には前記内部電極層と電気的に接続された導体層が設けられ、前記突起が前記導体層に食い込んでいることを特徴とする請求項1乃至請求項4のうちのいずれかに記載の積層型圧電素子。
- 前記導電性接合材は金属粒子が樹脂の中に分散されてなるものであり、前記突起の少なくとも表面の金属成分が前記金属粒子に含まれていることを特徴とする請求項1乃至請求項7のうちのいずれかに記載の積層型圧電素子。
- 請求項1乃至請求項8のうちのいずれかに記載の積層型圧電素子と、該積層型圧電素子を内部に収容するケースとを備えていることを特徴とする圧電アクチュエータ。
- 噴射孔を有する容器と、請求項1乃至請求項8のいずれかに記載の積層型圧電素子とを備え、前記容器内に蓄えられた流体が前記積層型圧電素子の駆動により前記噴射孔から吐出されることを特徴とする噴射装置。
- 高圧燃料を蓄えるコモンレールと、該コモンレールに蓄えられた前記高圧燃料を噴射する請求項10に記載の噴射装置と、前記コモンレールに前記高圧燃料を供給する圧力ポンプと、前記噴射装置に駆動信号を与える噴射制御ユニットとを備えたことを特徴とする燃料噴射システム。
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CN201380019353.XA CN104247065B (zh) | 2012-08-10 | 2013-08-10 | 层叠型压电元件及具备该层叠型压电元件的压电致动器、喷射装置以及燃料喷射*** |
US14/397,570 US9525120B2 (en) | 2012-08-10 | 2013-08-10 | Multi-layer piezoelectric element and piezoelectric actuator, injection device and fuel injection system including the same |
EP13828433.6A EP2889926B1 (en) | 2012-08-10 | 2013-08-10 | Laminated piezoelectric element, piezoelectric actuator provided with same, injection apparatus, and fuel injection system |
JP2014529588A JP5813235B2 (ja) | 2012-08-10 | 2013-08-10 | 積層型圧電素子およびこれを備えた圧電アクチュエータ、噴射装置ならびに燃料噴射システム |
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Publication number | Priority date | Publication date | Assignee | Title |
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JP2019040948A (ja) * | 2017-08-23 | 2019-03-14 | 京セラ株式会社 | 積層型圧電素子 |
WO2024080279A1 (ja) * | 2022-10-14 | 2024-04-18 | 京セラ株式会社 | 圧電素子 |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005223014A (ja) | 2004-02-03 | 2005-08-18 | Denso Corp | 積層型圧電素子及びその製造方法 |
JP2006303319A (ja) * | 2005-04-22 | 2006-11-02 | Tdk Corp | 積層型圧電素子 |
JP2010114620A (ja) * | 2008-11-06 | 2010-05-20 | Epson Toyocom Corp | 圧電素子、圧電デバイスおよび圧電素子製造方法 |
WO2011093293A1 (ja) * | 2010-01-26 | 2011-08-04 | 京セラ株式会社 | 積層型圧電素子およびその製造方法、ならびにこの積層型圧電素子を備えた噴射装置、燃料噴射システム |
Family Cites Families (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05335643A (ja) * | 1992-06-04 | 1993-12-17 | Nec Corp | 電歪効果素子 |
DE19917728A1 (de) | 1999-04-20 | 2000-10-26 | Bosch Gmbh Robert | Piezoelektrischer Aktor |
JP4158338B2 (ja) * | 2000-06-06 | 2008-10-01 | 株式会社デンソー | インジェクタ用圧電体素子 |
EP2012374B1 (en) * | 2003-09-24 | 2012-04-25 | Kyocera Corporation | Multi-layer piezoelectric element |
US8669694B2 (en) * | 2005-11-29 | 2014-03-11 | Kyocera Corporation | Multi-layer electronic component and method for manufacturing the same |
JP5201646B2 (ja) | 2006-01-13 | 2013-06-05 | 日本碍子株式会社 | 積層型圧電素子 |
CN101390228B (zh) * | 2006-02-27 | 2010-12-08 | 京瓷株式会社 | 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*** |
WO2008047460A1 (en) * | 2006-10-20 | 2008-04-24 | Kyocera Corporation | Piezoelectric actuator unit and method for manufacturing the same |
EP2190042A4 (en) * | 2007-09-18 | 2012-04-11 | Kyocera Corp | STACKED PIEZOELECTRIC ELEMENT, SPRAY DEVICE AND FUEL JET SYSTEM EQUIPPED WITH SAME |
WO2009041476A1 (ja) * | 2007-09-27 | 2009-04-02 | Kyocera Corporation | 積層型圧電素子、これを備えた噴射装置及び燃料噴射システム |
CN103094469B (zh) * | 2007-12-26 | 2015-07-08 | 京瓷株式会社 | 层叠型压电元件、利用该元件的喷射装置及燃料喷射*** |
EP2511968B1 (en) | 2009-11-26 | 2015-04-22 | Kyocera Corporation | Stacked piezoelectric element, injection device using same, and fuel injection system |
-
2013
- 2013-08-10 EP EP13828433.6A patent/EP2889926B1/en active Active
- 2013-08-10 WO PCT/JP2013/071737 patent/WO2014025050A1/ja active Application Filing
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- 2013-08-10 JP JP2014529588A patent/JP5813235B2/ja active Active
- 2013-08-10 CN CN201380019353.XA patent/CN104247065B/zh active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005223014A (ja) | 2004-02-03 | 2005-08-18 | Denso Corp | 積層型圧電素子及びその製造方法 |
JP2006303319A (ja) * | 2005-04-22 | 2006-11-02 | Tdk Corp | 積層型圧電素子 |
JP2010114620A (ja) * | 2008-11-06 | 2010-05-20 | Epson Toyocom Corp | 圧電素子、圧電デバイスおよび圧電素子製造方法 |
WO2011093293A1 (ja) * | 2010-01-26 | 2011-08-04 | 京セラ株式会社 | 積層型圧電素子およびその製造方法、ならびにこの積層型圧電素子を備えた噴射装置、燃料噴射システム |
Non-Patent Citations (1)
Title |
---|
See also references of EP2889926A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019040948A (ja) * | 2017-08-23 | 2019-03-14 | 京セラ株式会社 | 積層型圧電素子 |
WO2024080279A1 (ja) * | 2022-10-14 | 2024-04-18 | 京セラ株式会社 | 圧電素子 |
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US9525120B2 (en) | 2016-12-20 |
JP5813235B2 (ja) | 2015-11-17 |
US20150122908A1 (en) | 2015-05-07 |
EP2889926B1 (en) | 2017-03-29 |
EP2889926A1 (en) | 2015-07-01 |
EP2889926A4 (en) | 2016-04-06 |
CN104247065A (zh) | 2014-12-24 |
CN104247065B (zh) | 2017-04-05 |
JPWO2014025050A1 (ja) | 2016-07-25 |
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