JP4868707B2 - Multilayer piezoelectric element and injection device - Google Patents

Description

  The present invention relates to a laminated piezoelectric element (hereinafter, also simply referred to as “element”) and an injection device, for example, a fuel injection device for an automobile engine, a liquid injection device such as an ink jet, a precision positioning device such as an optical device, and a vibration. Drive elements mounted on prevention devices, etc., and sensor elements mounted on combustion pressure sensors, knock sensors, acceleration sensors, load sensors, ultrasonic sensors, pressure sensitive sensors, yaw rate sensors, etc., and piezoelectric gyros, piezoelectric switches, piezoelectric elements The present invention relates to a multilayer piezoelectric element and a jetting device used for circuit elements mounted on transformers, piezoelectric breakers, and the like.

  2. Description of the Related Art Conventionally, a multilayer piezoelectric actuator in which piezoelectric bodies and internal electrodes are alternately stacked is known as a multilayer piezoelectric element. Multi-layer piezoelectric actuators are classified into two types: simultaneous firing type and stack type in which piezoelectric ceramics made of a single piezoelectric body and plate-like internal electrodes are stacked alternately. Low voltage and low manufacturing costs. In view of the above, the simultaneous firing type laminated piezoelectric actuator is showing superiority because it is advantageous for thinning and advantageous for durability.

  FIG. 2 shows a conventional multilayer piezoelectric element shown in Patent Document 1, and is composed of a multilayer body 200 and external electrodes 23 formed on a pair of side surfaces facing each other. The laminated body 200 is formed by alternately laminating the piezoelectric bodies 21 and the internal electrodes 22 constituting the laminated body 200, but the internal electrodes 22 are not formed on the entire main surface of the piezoelectric body 21, but have a so-called partial electrode structure. . The internal electrodes 22 of this partial electrode structure are alternately stacked on the left and right sides so as to be exposed on the side surfaces of different stacked bodies 200. Inactive layers 24 are stacked on both end surfaces of the stacked body 200 in the stacking direction. And the external electrode 23 is formed so that the said exposed internal electrodes 22 may be connected to a pair of mutually opposing side surface of the laminated body 200, and the internal electrodes 22 can be connected every other layer.

  As a conventional method for manufacturing a laminated piezoelectric element, an internal electrode paste is printed on a ceramic green sheet containing a raw material of the piezoelectric body 21 in a pattern having a predetermined electrode structure as shown in FIG. A laminated body obtained by laminating a plurality of applied green sheets is produced, and this is fired to produce a laminated body 200. Thereafter, the external electrodes 23 are formed by firing on the pair of side surfaces of the multilayer body 200 to obtain a multilayer piezoelectric element (see, for example, Patent Document 1).

  The internal electrode 22 is made of an alloy of silver and palladium. Further, in order to fire the piezoelectric body 21 and the internal electrode 22 at the same time, the metal composition of the internal electrode 22 is 70% by weight of silver and 30% by weight of palladium. (See, for example, Patent Document 2).

  As described above, the internal electrode 22 made of a metal composition containing a silver-palladium alloy containing palladium is used instead of the internal electrode 22 made of a metal composition containing only silver. This is because when a potential difference is applied between the opposing internal electrodes 22, a so-called silver migration phenomenon occurs in which silver in the electrode moves along the element surface from the positive electrode to the negative electrode of the pair of internal electrodes 22. This phenomenon occurred remarkably in a high temperature and high humidity atmosphere.

When a conventional multilayer piezoelectric element is used as a piezoelectric actuator, a lead wire is further fixed to the external electrode 23 by solder (not shown), and can be driven by applying a predetermined potential between the external electrodes 23. . In particular, in recent years, there is a demand for a small multilayer piezoelectric element to ensure a large amount of displacement under a large pressure, and therefore, a higher electric field is applied and driven continuously for a long time.
JP-A-61-133715 Japanese Utility Model Publication No. 1-130568

  The conventional co-fired multilayer piezoelectric element is required to match the sintering temperature of the internal electrode 22 and the sintering temperature of the piezoelectric body 21, and the material composition of the internal electrode 22 and the piezoelectric body 21 is examined. Things have been done. However, since the residual stress due to the difference in thermal expansion between the internal electrode 22 and the piezoelectric body 21 is concentrated on the crystal particles of the piezoelectric body 21 facing the internal electrode 22 only when this is used as an actuator, Further, there is a problem that so-called delamination occurs in which the internal electrode 22 peels from the piezoelectric body 21.

Especially among the crystal grains of the piezoelectric body 21, when the crystal grains of the piezoelectric body 21 which faces the inner electrode 22 is small, or dielectric constant smaller than the larger particles of the same composition by size effect, the amount of piezoelectric displacement is Tsu a small phenomenon you occurs or. Even if the average crystal particle size of the crystal particles of the piezoelectric body 21 is simply increased, if there are particles having a small piezoelectric displacement amount among the crystal particles of the piezoelectric body 21 facing the internal electrode 22, the displacement amount during driving is increased. Is smaller than the crystal grains of the other piezoelectric bodies 21, the residual stress due to the difference in thermal expansion between the internal electrode 22 and the piezoelectric body 21 is concentrated at one point, which causes the occurrence of cracks and delamination. there were.

  There is also a problem that the amount of displacement of the actuator changes due to the occurrence of this delamination. In particular, when the occurrence rate of delamination increases, the element temperature rises. When the element temperature exceeds the heat dissipation amount, a thermal runaway phenomenon occurs, leading to destruction, and the amount of displacement rapidly deteriorates. Therefore, an internal electrode having a small specific resistance has been demanded in order to suppress an increase in element temperature.

  However, the specific resistance value of the silver-palladium alloy conventionally used is significantly higher than the specific resistance of silver or palladium alone depending on the composition ratio, and is 70% by weight of silver and 30% by weight of silver-palladium. The alloy composition has a problem that the resistance is 1.5 times higher than that of palladium alone. Moreover, if the sintered density of the internal electrode 22 is lowered, there is a limit in obtaining the internal electrode 22 having a higher specific resistance and a small specific resistance.

  As described above, when the conventional multilayer piezoelectric element is used as an actuator used for a drive element such as a fuel injection device, a desired displacement amount gradually changes, causing a problem that the device malfunctions. There has been a demand for suppression of change in displacement amount and improvement in durability in continuous operation.

  The present invention has been made in view of the above-described problems. Even when a piezoelectric actuator is continuously driven for a long period of time under high voltage and high pressure, delamination that occurs during driving is suppressed and displacement is achieved. An object of the present invention is to provide a laminated piezoelectric element and a jetting device that do not change in quantity and have excellent durability.

The multilayer piezoelectric element of the present invention is a multilayer piezoelectric element including a multilayer body in which at least one piezoelectric body and a plurality of internal electrodes are alternately stacked, and the average crystal grain size of the piezoelectric body facing the internal electrode is , much larger than the average grain size of the other portions, of the piezoelectric body facing said inner electrode
The minimum crystal grain size is 0.5 μm or more and 5 μm or less, the metal composition in the internal electrode is mainly composed of a Group VIII metal and / or a Group Ib metal, and the content of the Group VIII metal in the internal electrode is M1 (Mass%) When the content of the group Ib metal is M2 (mass%), 0 <M1 ≦ 15, 85 ≦ M2 <100, and M1 + M2 = 100 are satisfied .

The multilayer piezoelectric element of the present invention is a multilayer piezoelectric element including a multilayer body in which at least one piezoelectric body and a plurality of internal electrodes are alternately stacked, and the minimum crystal grain size of the piezoelectric body facing the internal electrode is , much larger than the minimum grain size of the other locations, the minimum grain size of the piezoelectric body facing the inner electrode is at 0.5μm or more 5μm or less, the metal composition is a group VIII metal in the internal electrode And / or when the content of the Group VIII metal in the internal electrode is M1 (mass%) and the content of the Group Ib metal is M2 (mass%), 0 <M1 ≦ 15 85 ≦ M2 <100 and M1 + M2 = 100 are satisfied .

  The Group VIII metal is at least one of Ni, Pt, Pd, Rh, Ir, Ru, and Os, and the Group Ib metal is at least one of Cu, Ag, and Au.

  The group VIII metal is at least one of Pt and Pd, and the group Ib metal is at least one of Ag and Au.

  The Group VIII metal is Ni.

  The Ib group metal is Cu.

  An inorganic composition is added to the internal electrode together with the metal composition.

The inorganic composition is mainly composed of a perovskite oxide composed of PbZrO ₃ —PbTiO ₃ .

  The piezoelectric body has a perovskite oxide as a main component.

The piezoelectric material is mainly composed of a perovskite oxide made of PbZrO ₃ —PbTiO ₃ .

  The firing temperature of the laminate is 900 ° C. or higher and 1000 ° C. or lower.

  The composition deviation in the internal electrode is 5% or less before and after firing.

  The internal electrodes whose end portions are exposed on the side surfaces of the laminate and the internal electrodes whose end portions are not exposed are alternately configured, and the internal electrodes between which the end portions are not exposed and the external electrodes are formed. A groove is formed in the piezoelectric portion, and the groove is filled with an insulator having a Young's modulus lower than that of the piezoelectric body.

  The injection device of the present invention includes a storage container having an injection hole, a stacked piezoelectric element stored in the storage container, and a valve that ejects liquid from the injection hole by driving the stacked piezoelectric element. It is characterized by becoming.

According to the multilayer piezoelectric element of the present invention, the average crystal grain size of the piezoelectric body facing the internal electrode is larger than the average crystal grain size of the other portions, and the minimum crystal grain size of the piezoelectric body facing the internal electrode Is 0.5 μm or more and 5 μm or less, the metal composition in the internal electrode is mainly composed of a Group VIII metal and / or a Group Ib metal, and the content of the Group VIII metal in the internal electrode is M1 (mass%), Group Ib When the metal content is M2 (mass%), 0 <M1 ≦ 15, 85 ≦ M2 <100, and M1 + M2 = 100 are satisfied , resulting in a difference in thermal expansion between the internal electrode and the piezoelectric body. Since the residual stress can be uniformly dispersed in the piezoelectric particles at the electrode interface, the adhesion strength at the interface between the internal electrode and the piezoelectric material can be increased, so that delamination can be suppressed. Drive It is possible to provide a highly reliable piezoelectric actuator having excellent durability with a constant displacement amount.

  Therefore, even if the multilayer piezoelectric element is continuously driven, the desired displacement amount does not change effectively, so that the device does not malfunction, and a highly reliable injection device having excellent durability is provided. it can.

  The multilayer piezoelectric element of the present invention will be described in detail below. 1A and 1B show an embodiment of a laminated piezoelectric element according to the present invention. FIG. 1A is a perspective view, and FIG. 1B is a perspective development view showing a laminated state of a piezoelectric layer and an internal electrode layer.

  As shown in FIG. 1, the multilayer piezoelectric element of the present invention has end portions where the internal electrodes 12 are exposed on a pair of opposing side surfaces of a multilayer body 13 in which piezoelectric bodies 11 and internal electrodes 12 are alternately laminated. The external electrodes 15 that are electrically conductive are joined every other layer. In addition, an inactive layer 14 formed of the piezoelectric body 11 is stacked on both ends of the stacked body 13 in the stacking direction. Here, when the multilayer piezoelectric element of the present invention is used as a multilayer piezoelectric actuator, a lead wire may be connected and fixed to the external electrode 15 by soldering, and the lead wire may be connected to an external voltage supply unit.

  An internal electrode 12 is arranged between the piezoelectric bodies 11. Since the internal electrode 12 is formed of a metal material such as silver-palladium, a predetermined voltage is applied to each piezoelectric body 11 through the internal electrode 12. The piezoelectric body 11 has a function of causing displacement due to the reverse piezoelectric effect.

On the other hand, since the inert layer 14 is a layer of a plurality of piezoelectric bodies 11 in which the internal electrode 12 is not disposed, no displacement occurs even when a voltage is applied.

  The present invention is characterized in that the average crystal grain size of the piezoelectric body 11 facing the internal electrode 12 is larger than the average crystal grain size at other locations. Here, the region of the piezoelectric body 11 facing the internal electrode 12 refers to the region of the piezoelectric body 11 that is in contact with the internal electrode 12, but is not limited to this region, and includes a region in the vicinity of the outer periphery of the internal electrode 12. It doesn't matter.

  In particular, the average crystal grain size of the piezoelectric body 11 facing the internal electrode 12 is preferably 1 μm or more and 8 μm or less.

  If the size is smaller than 1 μm, the problem that the piezoelectric displacement becomes smaller due to the size effect occurs. At the same time, the bending strength, so-called porcelain strength, becomes smaller. This is not preferable because bending strength, so-called porcelain strength, is reduced.

  Further, in the present invention, the minimum crystal grain size of the piezoelectric body 11 facing the internal electrode 12 may be made larger than the minimum crystal grain size of other portions.

  Here, the minimum crystal grain size is that the residual stress due to the difference in thermal expansion between the internal electrode 12 and the piezoelectric body 11 is concentrated because of the crystal grain size among the crystal grains at the interface of the internal electrode 12. This is because they are small crystal grains.

  In particular, the minimum crystal grain size in contact with the internal electrode 12 is preferably 0.5 μm or more and 5 μm or less. If it is smaller than 0.5 μm, the problem that the piezoelectric displacement becomes smaller due to the size effect occurs, and at the same time, the bending strength, so-called porcelain strength, becomes small. Due to the change, the bending strength, so-called porcelain strength, becomes small, which is not preferable.

  An SEM (scanning electron microscope) is used to measure such an average crystal grain size and minimum crystal grain size. Specifically, the average crystal grain size of the piezoelectric body 11 facing the internal electrode 12 is measured. In this case, a straight line is drawn on the crystal particle image portion of the piezoelectric body 11 facing the internal electrode 12 on the image obtained by SEM, and a total of 50 crystal particles are selected at arbitrary locations. The average value across the length is defined as the average crystal grain size. Furthermore, in the present invention, the average crystal grain size of the portion other than the average crystal grain size of the piezoelectric body 11 facing the internal electrode 12 is specified. The measurement of the average crystal grain size also faces the measurement region to the internal electrode 12. Measurement is performed in the same manner as described above except that measurement is performed by drawing a straight line at an arbitrary position in a different region other than the piezoelectric body 11 to be measured.

  The minimum crystal grain size is the largest crystal grain size among the crystal grains at the same image location as the average crystal grain size measured at the two locations described above (the piezoelectric body region facing the internal electrode 12 and other areas). It was small.

  As a manufacturing method in which the average crystal grain size of the piezoelectric body 11 facing the internal electrode 12 of the present invention is larger than the average crystal grain size at other locations, the sintering start temperature at which the internal electrode 12 starts to sinter The material composition is selected so that the temperature is lower than the sintering start temperature at which the piezoelectric body 11 starts sintering.

  Specifically, for example, the internal electrode 12 is configured so that a liquid phase lower in temperature than the sintering start temperature at which the piezoelectric body 11 starts sintering can be formed at the interface between the piezoelectric body 11 and the internal electrode 12. An electrode pattern is printed by adding the metal oxide powder together with the metal powder.

  In this way, by setting the sintering start temperature at which the internal electrode 12 starts sintering to be lower than the sintering start temperature at which the piezoelectric body 11 starts sintering, the internal electrode 12 portion is first formed at the time of simultaneous firing. As a result, a liquid phase is generated, and sintering of the internal electrode 12 proceeds.

  Further, when the internal electrode 12 is sintered, a liquid phase is generated, so that the piezoelectric body 11 and the internal electrode 12 are liquid phase sintered.

  That is, at the same time as the liquid phase is positively formed at the electrode interface, the sintering of the piezoelectric ceramic in the portion in contact with the internal electrode 12 proceeds, and the portion having a small ceramic particle diameter disappears from the electrode interface as the sintering proceeds. Thus, the porcelain particle size in the portion in contact with the internal electrode 12 is increased, and the adhesion at the electrode interface is strengthened.

  Also, a manufacturing method for making the minimum crystal grain size of the piezoelectric body 11 facing the internal electrode 12 larger than that of other portions is the same manufacturing method as described above. However, in order to increase the minimum crystal grain size of the piezoelectric body 11 facing the internal electrode 12, the liquid phase formed when the electrode is sintered needs to diffuse into the piezoelectric body 11. After maintaining the firing temperature at the formation temperature, the temperature is set to a temperature at which the piezoelectric body 11 is sintered.

  In the present invention, the metal composition in the internal electrode 12 is preferably composed mainly of a Group VIII metal and / or a Group Ib metal. This is because the above-described metal composition has high heat resistance, so that the piezoelectric body 11 and the internal electrode 12 having a high firing temperature can be fired simultaneously.

  Further, when the metal composition in the internal electrode 12 has a group VIII metal content of M1 (wt%) and a group Ib metal content of M2 (wt%), 0 <M1 ≦ 15, 85 ≦ M2 < It is preferable that the main component is a metal composition satisfying 100 and M1 + M2 = 100. This is because when the Group VIII metal exceeds 15% by weight, the specific resistance of the internal electrode 12 increases, and the internal electrode 12 may generate heat when the stacked piezoelectric element is continuously driven. Further, in order to suppress migration of the group Ib metal in the internal electrode 2 to the piezoelectric body 11, the group VIII metal is preferably made 0.001 wt% or more and 15 wt% or less. Further, from the viewpoint of improving the durability of the multilayer piezoelectric element, it is preferably 0.1% by weight or more and 10% by weight or less. Moreover, when it is excellent in heat conduction and higher durability is required, 0.5 wt% or more and 9.5 wt% or less are more preferable. Further, when higher durability is required, the content is more preferably 2% by weight or more and 8% by weight or less.

  Here, when the group Ib metal content is less than 85% by weight, the specific resistance of the internal electrode 12 increases, and the internal electrode 12 may generate heat when the stacked piezoelectric element is continuously driven. In order to suppress migration of the group Ib metal in the internal metal 12 to the piezoelectric body 11, the group Ib metal is preferably 85 wt% or more and 99.999 wt% or less. Moreover, 90 weight% or more and 99.9 weight% or less are preferable at the point of improving the durability of a laminated piezoelectric element. Moreover, when higher durability is required, 90.5 weight% or more and 99.5 weight% or less are more preferable. Moreover, when higher durability is calculated | required, 92 to 98 weight% is further more preferable.

  The Group VIII metal and the Group Ib metal indicating the weight percentage of the metal component in the internal electrode 12 can be specified by an analysis method such as an EPMA (Electron Probe Micro Analysis) method.

  Furthermore, the metal component in the internal electrode 12 of the present invention is such that the group VIII metal is at least one of Ni, Pt, Pd, Rh, Ir, Ru, and Os, and the group Ib metal is Cu, Ag, or Au. Of these, at least one is preferable. This is because the metal composition has excellent mass productivity in recent alloy powder synthesis techniques.

  Furthermore, it is preferable that the metal component in the internal electrode 12 is a group VIII metal of at least one of Pt and Pd and a group Ib metal of at least one of Ag and Au. Thereby, there is a possibility that the internal electrode 12 having excellent heat resistance and small specific resistance can be formed.

  Further, the metal component in the internal electrode 12 is preferably a group VIII metal Ni. Thereby, the internal electrode 12 excellent in heat resistance may be formed.

  Further, the metal component in the internal electrode 12 is preferably a group Ib metal of Cu. Thereby, there is a possibility that the internal electrode 12 having excellent thermal conductivity can be formed.

Furthermore, it is preferable to add an inorganic composition to the internal electrode 12 together with the metal composition. Accordingly, there is a possibility that the internal electrode 12 and the piezoelectric body 11 can be firmly bonded, and it is preferable that the inorganic composition contains a perovskite oxide composed of PbZrO ₃ —PbTiO ₃ as a main component.

Furthermore, it is preferable that the piezoelectric body 11 has a perovskite oxide as a main component. This is because, for example, when formed of a perovskite type piezoelectric ceramic material typified by barium titanate (BaTiO ₃ ) or the like, the piezoelectric strain constant d ₃₃ indicating the piezoelectric characteristics is high, so that the amount of displacement can be increased. Further, the piezoelectric body 11 and the internal electrode 12 can be fired simultaneously. The piezoelectric body 11 described above preferably contains a perovskite oxide composed of PbZrO ₃ —PbTiO ₃ having a relatively high piezoelectric strain constant d ₃₃ as a main component.

  Furthermore, it is preferable that a calcination temperature is 900 degreeC or more and 1000 degrees C or less. This is because when the firing temperature is 900 ° C. or lower, the firing temperature is low, so firing is insufficient, and it becomes difficult to manufacture the dense piezoelectric body 11. Further, if the firing temperature exceeds 1000 ° C., the stress due to the difference between the shrinkage of the internal electrode 12 and the shrinkage of the piezoelectric body 11 during firing becomes large, and cracks may occur during continuous driving of the multilayer piezoelectric element. Because there is.

  Further, the compositional deviation in the internal electrode 12 is preferably 5% or less before and after firing. This is because when the compositional deviation in the internal electrode 12 exceeds 5% before and after firing, the metal material in the internal electrode 12 is more migrated to the piezoelectric body 11, and the expansion and contraction due to the driving of the multilayer piezoelectric element is prevented. The internal electrode 12 may not be able to follow.

  Here, the deviation of the composition in the internal electrode 12 indicates the rate of change in which the composition of the internal electrode 12 changes as the elements constituting the internal electrode 12 evaporate or diffuse into the piezoelectric body 11 by firing.

  In addition, the internal electrodes 12 whose end portions are exposed on the side surfaces of the multilayer piezoelectric element of the present invention and the internal electrodes 12 whose end portions are not exposed are alternately configured, and the internal electrodes 12 whose end portions are not exposed and A groove is formed in the piezoelectric portion between the external electrodes 15, and an insulator having a Young's modulus lower than that of the piezoelectric body 12 is preferably formed in the groove. As a result, in such a multilayer piezoelectric element, stress generated by displacement during driving can be relieved, so that heat generation of the internal electrode 12 can be suppressed even when continuously driven.

  Next, a method for producing the multilayer piezoelectric element of the present invention will be described.

The multilayer piezoelectric element of the present invention includes a calcined powder of a perovskite oxide piezoelectric ceramic made of PbZrO ₃ —PbTiO ₃ , a binder made of an acrylic or butyral organic polymer, and DBP (phthalate). A ceramic green sheet that is made into a piezoelectric body 11 by mixing with a plasticizer such as dibutyl acid or DOP (diethyl phthalate) to produce a slurry, and then forming the slurry by a tape molding method such as a known doctor blade method or calendar roll method. Is made.

  Next, a metal paste such as silver-palladium and the like constituting the internal electrode 12 is mixed with a metal oxide such as silver oxide, a binder, a plasticizer, and the like to prepare a conductive paste. Printing on the upper surface to a thickness of 1 to 40 μm by screen printing or the like.

  Then, a plurality of green sheets with conductive paste printed on the upper surface are laminated, the binder is debindered at a predetermined temperature, and then fired at 900 to 1200 ° C., whereby the laminate 13 is produced.

At this time, when the metal powder constituting the internal electrode 12 such as silver-palladium is added to the green sheet of the inert layer 14 or when the green sheet of the inert layer 14 is laminated, the silver- the metal powder and an inorganic compound and a slurry comprising a binder and a plasticizer constituting the internal electrode such as palladium by or printed on the green sheet, at the time of sintering of the other portions and the inactive layer 14 shrink behavior and shrinkage Since the rates can be matched, a dense laminate can be formed.

  In addition, the laminated body 13 is not limited to what is produced by the said manufacturing method, What is necessary if the laminated body 13 which laminates | stacks alternately the several piezoelectric body 11 and the some internal electrode 12 is producible. It may be formed by any manufacturing method.

  Thereafter, the internal electrodes 12 whose ends are exposed and the internal electrodes 12 whose ends are not exposed are alternately formed on the side surfaces of the multilayer piezoelectric element, and the internal electrodes 12 and the external electrodes 15 whose ends are not exposed are formed alternately. A groove is formed in the piezoelectric portion, and an insulator such as resin or rubber having a Young's modulus lower than that of the piezoelectric body 11 is formed in the groove. Here, the groove is formed on the side surface of the laminate 13 by an internal dicing device or the like.

  The external electrode 15 is preferably made of silver having a low Young's modulus or an alloy containing silver as a main component because the conductive material constituting the external electrode 15 sufficiently absorbs stress generated by expansion and contraction of the actuator.

  A silver glass conductive paste is prepared by adding a binder to glass powder, and this is formed into a sheet, and the green density of the dried (spattered solvent) is controlled to 6-9 g / cm 3. Is transferred to the external electrode forming surface of the columnar laminate 13, and is a temperature higher than the softening point of the glass, a temperature not higher than the melting point of silver (965 ° C.), and not higher than 4/5 of the firing temperature (° C.). By baking, the binder component in the sheet produced using the silver glass conductive paste is scattered and disappeared, and the external electrode 15 made of a porous conductor having a three-dimensional network structure can be formed.

  The baking temperature of the silver glass conductive paste effectively forms a neck portion, diffuses and joins silver in the silver glass conductive paste and the internal electrode 12, and effectively creates voids in the external electrode 15. The temperature is preferably 550 to 700 ° C. from the viewpoint that the external electrode 15 and the side surface of the columnar laminate 13 are partially joined. The softening point of the glass component in the silver glass conductive paste is preferably 500 to 700 ° C.

  When the baking temperature is higher than 700 ° C., the sintering of the silver powder of the silver glass conductive paste proceeds too much, so that a porous conductor having an effective three-dimensional network structure cannot be formed, and the external electrode 15 May become too dense, and as a result, the Young's modulus of the external electrode 15 may become too high to absorb the stress during driving sufficiently and the external electrode 15 may be disconnected. Preferably, baking should be performed at a temperature within 1.2 times the softening point of the glass.

  On the other hand, when the baking temperature is lower than 550 ° C., since the diffusion bonding is not sufficiently performed between the end portion of the internal electrode 12 and the external electrode 15, the neck portion is not formed, and the internal electrode 12 and the external electrode are not driven. There is a possibility of causing a spark between the electrodes 15.

  Note that the thickness of the silver glass conductive paste sheet is preferably thinner than the thickness of the piezoelectric body 11. More preferably, it is 50 μm or less from the viewpoint of following the expansion and contraction of the actuator.

  Next, the laminated body 13 on which the external electrode 15 is formed is immersed in a silicone rubber solution, and the silicone rubber solution is vacuum degassed to fill the groove of the laminated body 13 with silicone rubber. The laminated body 13 is pulled up, and the side surface of the laminated body 13 is coated with silicone rubber. Thereafter, the silicone rubber coated inside the grooves and coated on the side surfaces of the columnar laminate 13 is cured to complete the multilayer piezoelectric element of the present invention.

  Then, a lead wire is connected to the external electrode 15, a direct current voltage of 0.1 to 3 kV / mm is applied to the pair of external electrodes 15 via the lead wire, and the laminate 13 is subjected to polarization treatment. When a multilayer piezoelectric actuator using the multilayer piezoelectric element is completed, a lead wire is connected to an external voltage supply unit, and a voltage is applied to the internal electrode 12 via the lead wire and the external electrode 15, each piezoelectric The body 11 is largely displaced by the inverse piezoelectric effect, and thereby functions as an automobile fuel injection valve that injects and supplies fuel to the engine, for example.

  Furthermore, a conductive auxiliary member made of a conductive adhesive in which a metal mesh or a mesh-like metal plate is embedded on the outer surface of the external electrode 15 may be formed. In this case, even when a large current is input to the actuator by providing a conductive auxiliary member on the outer surface of the external electrode 15 and the actuator is driven at a high speed, a large current can flow through the conductive auxiliary member. For the reason that the current flowing through 15 can be reduced, the external electrode 15 can be prevented from causing local heat generation and disconnection, and the durability can be greatly improved. Furthermore, since a metal mesh or a mesh-like metal plate is embedded in the conductive adhesive, it is possible to prevent the conductive adhesive from cracking.

  The metal mesh is a braided metal wire, and the mesh metal plate is a mesh formed by forming holes in a metal plate.

  Furthermore, the conductive adhesive constituting the conductive auxiliary member is preferably made of a polyimide resin in which silver powder is dispersed. That is, by dispersing silver powder having a low specific resistance in a polyimide resin having high heat resistance, a conductive auxiliary member having a low resistance value and maintaining a high adhesive strength can be formed even when used at high temperatures. . More preferably, the conductive particles are non-spherical particles such as flakes or needles. This is because the entanglement between the conductive particles can be strengthened by making the shape of the conductive particles non-spherical particles such as flakes and needles, and the shear strength of the conductive adhesive can be further increased. This is because it can be increased.

  The multilayer piezoelectric element of the present invention is not limited to these, and various modifications can be made without departing from the gist of the present invention.

  Moreover, although the example which formed the external electrode 15 in the side surface which the laminated body 13 opposes above was demonstrated, in this invention, you may form a pair of external electrode in the side surface provided adjacently, for example.

  FIG. 3 shows an injection device according to the present invention. An injection hole 33 is provided at one end of the storage container 31, and a needle valve 35 that can open and close the injection hole 33 is stored in the storage container 31. Has been.

  A fuel passage 37 is provided in the injection hole 33 so as to be able to communicate. The fuel passage 37 is connected to an external fuel supply source, and fuel is always supplied to the fuel passage 37 at a constant high pressure. Therefore, when the needle valve 35 opens the injection hole 33, the fuel supplied to the fuel passage 37 is formed to be injected into a fuel chamber (not shown) of the internal combustion engine at a constant high pressure.

  Further, the upper end portion of the needle valve 35 has a large diameter, and serves as a piston 41 slidable with a cylinder 39 formed in the storage container 31. In the storage container 31, the piezoelectric actuator 43 described above is stored.

  In such an injection device, when the piezoelectric actuator 43 is extended by applying a voltage, the piston 41 is pressed, the needle valve 35 closes the injection hole 33, and the supply of fuel is stopped. When the application of voltage is stopped, the piezoelectric actuator 43 contracts, the disc spring 45 pushes back the piston 41, and the injection hole 33 communicates with the fuel passage 37 so that fuel is injected.

  Further, the present invention relates to a multilayer piezoelectric element and an injection device, but is not limited to the above-described embodiments. For example, a fuel injection device for an automobile engine, a liquid injection device such as an ink jet, an optical device, etc. Drive elements mounted on precision positioning devices, vibration prevention devices, etc., or sensor elements mounted on combustion pressure sensors, knock sensors, acceleration sensors, load sensors, ultrasonic sensors, pressure sensors, yaw rate sensors, and piezoelectric elements Needless to say, the present invention can be applied to elements other than circuit elements mounted on a gyroscope, a piezoelectric switch, a piezoelectric transformer, a piezoelectric breaker, or the like as long as the elements use piezoelectric characteristics.

  A multilayer piezoelectric actuator comprising the multilayer piezoelectric element of the present invention was produced as follows.

First, a slurry in which 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 μm, a binder, and a plasticizer is prepared, and a doctor blade method is used. A ceramic green sheet to be the piezoelectric body 11 having a thickness of 150 μm was produced.

  On one side of this ceramic green sheet, 300 sheets of a conductive paste made of silver-palladium alloy formed with an arbitrary composition ratio and added with silver oxide and a binder were formed to a thickness of 3 μm by screen printing. Baked. Firing was carried out at 1000 ° C. after holding at 800 ° C.

  Thereafter, a groove having a depth of 50 μm and a width of 50 μm was formed at every other end of the internal electrode on the side surface of the laminate by a dicing apparatus.

Next, a mixture of 90% by volume of flaky silver powder having an average particle diameter of 2 μm and 10% by volume of amorphous glass powder having a remaining softening point of 640 ° C. mainly composed of silicon having an average particle diameter of 2 μm. In addition, 8 parts by mass of the binder was added to 100 parts by mass of the total weight of the silver powder and the glass powder, and mixed sufficiently to prepare a silver glass conductive paste. The silver glass conductive paste thus produced was formed on a release film by screen printing, dried and then peeled off from the release film to obtain a sheet of silver glass conductive paste. The raw density of this sheet was measured by the Archimedes method and found to be 6.5 g / cm ³ .

  Then, the sheet of silver glass paste was transferred to the surface of the external electrode 15 of the laminate 13 and baked at 650 ° C. for 30 minutes to form the external electrode 15 made of a porous conductor having a three-dimensional network structure. The porosity of the external electrode 15 at this time was 40% when measured using an image analysis device for a cross-sectional photograph of the external electrode 15.

  Thereafter, a lead wire is connected to the external electrode 15, a 3 kV / mm direct current electric field is applied to the positive and negative external electrodes 15 through the lead wire for 15 minutes, and polarization is performed. As shown in FIG. A multilayer piezoelectric actuator using a piezoelectric element was produced.

  As a result of applying a DC voltage of 170 V to the obtained multilayer piezoelectric element, a displacement of 45 μm was obtained in the stacking direction. Furthermore, a drive test was performed by applying an AC voltage of 0 to +170 V at a frequency of 150 Hz to the multilayer piezoelectric element at room temperature.

Next, for the laminated piezoelectric element of Tables 1 and 2, the laminated piezoelectric element after driving 1 × 10 ⁹ times was processed into 3 mm × 4 mm × 36 mm, and bending strength was obtained by 4-point bending according to JIS R1601. Was measured. At this time, when the electrode surface of the internal electrode 12 was made substantially perpendicular to the longitudinal direction of the test piece, it was confirmed that all the test pieces were broken at the interface between the internal electrode 12 and the piezoelectric body 11.

  Further, with respect to the samples shown in Table 1, the relationship between the average crystal grain size of the piezoelectric body 11 in contact with the internal electrode 12 and the average crystal grain size at other locations was measured by SEM, and the relationship between the bending strength and the sample was measured. As a measuring method, a straight line was drawn at the image portion of the piezoelectric particle facing the internal electrode on the image obtained by SEM, and a total of 50 particles were selected at any portion, and the length of the crossing of the straight line at each particle was The average value was taken as the average crystal grain size.

  Further, the other region is a straight line drawn at an arbitrary image location other than the piezoelectric body facing the internal electrode, a total of 50 particles are selected, and the average value of the length of each particle across the straight line is the average crystal grain. The diameter.

  The minimum crystal grain size is the smallest among the crystal grains at the same image location where the average crystal grain size was measured.

  For comparison, the relationship with the bending strength when the average crystal grain size of the piezoelectric body 11 in contact with the internal electrode 12 is the same as or larger than that of other portions by a conventional manufacturing method is also described.

Further, for the samples shown in Table 2, the minimum crystal grain size and the maximum crystal grain size of the piezoelectric body 11 in contact with the internal electrode 12 were measured by SEM, and the minimum crystal grain size and the maximum crystal grain size at other locations were measured. The relationship with bending strength was measured. The measurement method used was the same as in Table 1. For comparison, the bending strength when the minimum crystal grain size and the maximum crystal grain size of the piezoelectric body 11 in contact with the internal electrode 12 and the minimum crystal grain size and the maximum crystal grain size of other portions are substantially the same or larger is used. Showed the relationship. The results are shown in Tables 1 and 2 below.

  From Table 1, when the average crystal grain size of the piezoelectric body 11 facing the internal electrode 12 is smaller than or the same as the average crystal grain size of other portions (Sample Nos. 1 and 8), sufficient bending strength is obtained. However, the bending strength can be improved by making the average crystal grain size of the piezoelectric body 11 facing the internal electrode 11 larger than the average crystal grain size at other locations (Sample Nos. 2 to 7). I can confirm that.

  Further, from Table 2, the maximum crystal grain size of the piezoelectric body 11 facing the internal electrode 12 in any sample is substantially the same as or larger than the maximum crystal grain size in other parts. ing. However, when this is compared between the minimum crystal grain sizes, sufficient bending strength is obtained when the minimum crystal grain size of the piezoelectric body 11 facing the internal electrode 12 is smaller than the minimum crystal grain size at other locations. Is not obtained (Samples 9 and 16), the bending strength is increased by making the minimum crystal grain size of the piezoelectric body 11 facing the internal electrode 12 larger than the minimum crystal grain size of other portions. (Samples 10 to 14) can be confirmed.

  Further, from Table 2, it can be confirmed that the bending strength is improved by setting the minimum crystal grain size of the piezoelectric body 11 facing the internal electrode 12 to 0.5 μm or more and 5 μm or less.

  In any case, since all the test pieces were broken at the interface between the internal electrode 12 and the piezoelectric body 11, the crystal grain size (average crystal grain size, minimum crystal grain size) of the piezoelectric body 11 facing the internal electrode 12 was It can be confirmed that the adhesion strength at the interface between the internal electrode 12 and the piezoelectric body 11 is improved by making it larger than the crystal grain size (average crystal grain size, minimum crystal grain size) at other locations.

Next, using a laminated piezoelectric element having a different material composition of the internal electrode 12, the minimum crystal grain size and the maximum crystal grain size of the piezoelectric body in contact with the electrode under the same conditions as described above and the minimum crystal grain at other locations The diameter and the maximum crystal grain size were measured, and the relationship with the bending strength is shown in Table 3. In addition, the change rate of the displacement amount of each sample was also measured. As the rate of change, the displacement amount (μm) when the multilayer piezoelectric element of each sample reaches 1 × 10 ⁹ times of driving and the displacement amount (μm) in the initial state of the multilayer piezoelectric element before starting the continuous driving. ) And the degree of deterioration of the multilayer piezoelectric element. The results are shown in Table 3.

  From Table 3, Sample No. When 17 internal electrodes 12 were made of 100% silver, the multilayer piezoelectric element was damaged by silver migration, and continuous driving was impossible. Sample No. Except for the sample No. 17, the average particle size of the piezoelectric body 11 facing the internal electrode 12 is larger than the average crystal particle size of the piezoelectric body 11 at other locations. Nos. 31 and 32 have a group VIII metal content of more than 15% by weight in the metal composition in the internal electrode 12 and a group Ib metal content of less than 85% by weight. Since this occurs, it can be seen that the durability of the multilayer piezoelectric actuator decreases. Therefore, it can be seen that the bending strength in this case is also low.

  In contrast, no. 18 to 30 and 33 to 35 are formed such that the average grain size of the piezoelectric body 11 facing the internal electrode 12 is larger than the average crystal grain size of other portions, and the metal composition in the internal electrode 12 is VIII. The main component is a metal composition satisfying 0 ≦ M1 ≦ 15, 85 ≦ M2 ≦ 100, and M1 + M2 = 100 mass% when the content of the metal group is M1 mass% and the content of the group Ib metal is M2 mass%. Therefore, sufficient bending strength can be obtained to improve the adhesion between the internal electrode 12 and the piezoelectric body 11, and the specific resistance of the internal electrode 12 can be reduced. It can be seen that a stacked actuator with a stable element displacement can be manufactured because the heat generated in the above can be suppressed.

  It should be noted that the present invention is not limited to the above-described embodiments, and various modifications may be made without departing from the scope of the present invention.

1A and 1B show a laminated piezoelectric element of the present invention, in which FIG. 1A is a perspective view, and FIG. 1B is a perspective developed view showing a laminated state of a piezoelectric layer and an internal electrode layer. It is a perspective view which shows the conventional multilayer capacitor. It is sectional drawing which shows the injection apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 11 ... Piezoelectric body 13 ... Laminated body 12 ... Internal electrode 21 ... Piezoelectric body 22 ... Internal electrode 23 ... External electrode 31 ... Storage container 33 ... Injection hole 35. ..Valve 43 ... Piezoelectric actuator

Claims (15)

In a multilayer piezoelectric element including a multilayer body in which at least one piezoelectric body and a plurality of internal electrodes are alternately stacked, the average crystal grain size of the piezoelectric body facing the internal electrode is equal to the average crystal grain size in other locations. much larger than the diameter, the minimum grain size of the piezoelectric body facing the inner electrode is at 0.5μm or more 5μm or less, the main component metal composition a group VIII metal and / or group Ib metal in the internal electrode When the content of the group VIII metal in the internal electrode is M1 (mass%) and the content of the group lb metal is M2 (mass%), 0 <M1 ≦ 15, 85 ≦ M2 <100, M1 + M2 = 100. A laminated piezoelectric element satisfying 100 . In a multilayer piezoelectric element including a multilayer body in which at least one piezoelectric body and a plurality of internal electrodes are alternately stacked, the minimum crystal grain size of the piezoelectric body facing the internal electrode is the minimum crystal grain at other locations. much larger than the diameter, the minimum grain size of the piezoelectric body facing the inner electrode is at 0.5μm or more 5μm or less, the main component metal composition a group VIII metal and / or group Ib metal in the internal electrode When the content of the group VIII metal in the internal electrode is M1 (mass%) and the content of the group lb metal is M2 (mass%), 0 <M1 ≦ 15, 85 ≦ M2 <100, M1 + M2 = 100. A laminated piezoelectric element satisfying 100 .   3. The multilayer piezoelectric element according to claim 1, wherein crystal grains of the piezoelectric material facing the internal electrode are in contact with the internal electrode. The group VIII metal is at least one of Ni, Pt, Pd, Rh, Ir, Ru, and Os, and the group Ib metal is at least one of Cu, Ag, and Au. Item 4. The multilayer piezoelectric element according to any one of Items 1 to 3 . The Group VIII metal is Pt, and at least one or more of Pd, Ib group metals Ag, stacked according to any one of claims 1 to 4, characterized in that at least one of Au Piezoelectric element. The multi-layer piezoelectric element according to any one of claims 1 to 5, wherein the Group VIII metal is Ni. The multi-layer piezoelectric element according to any one of claims 1 to 6, wherein the group Ib metal is Cu. The multi-layer piezoelectric element according to any one of claims 1 to 7, characterized in that the addition of the inorganic composition together with the metal composition in the inner electrode. 9. The multilayer piezoelectric element according to claim 8 , wherein the inorganic composition contains a perovskite oxide composed of PbZrO ₃ —PbTiO ₃ as a main component. The multi-layer piezoelectric element according to any one of claims 1 to 9 wherein the piezoelectric material, characterized in that the main component a perovskite-type oxide. The multilayer piezoelectric element according to claim 10 , wherein the piezoelectric body contains a perovskite oxide composed of PbZrO ₃ —PbTiO ₃ as a main component. The multi-layer piezoelectric element according to any one of claims 1 to 11 firing temperature of the laminate is characterized in that at 900 ° C. or higher 1000 ° C. or less. The multi-layer piezoelectric element according to any one of claims 1 to 12, wherein the deviation of the composition in the internal electrode is not more than 5% before and after firing. The internal electrodes whose end portions are exposed on the side surfaces of the laminate and the internal electrodes whose end portions are not exposed are alternately configured, and the internal electrodes between which the end portions are not exposed and the external electrodes are formed. grooves in the piezoelectric portion is formed, the laminated piezoelectric element according to any one of claims 1 to 13 lower insulator Young's modulus than the piezoelectric body groove is characterized in that it is filled . A container having an injection hole, a valve for ejecting the laminated piezoelectric element according to any one of claims 1 to 14 housed in the container, the liquid from the ejection hole by a drive of the laminated piezoelectric element An injection device comprising:

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