JP5021595B2 - Piezoelectric / electrostrictive porcelain composition and piezoelectric / electrostrictive element - Google Patents

Description

  The present invention relates to a piezoelectric / electrostrictive porcelain composition and a piezoelectric / electrostrictive element using the piezoelectric / electrostrictive porcelain composition.

  Piezoelectric / electrostrictive actuators have the advantage that displacement can be precisely controlled on the order of submicrons. In particular, a piezoelectric / electrostrictive actuator using a sintered body of a piezoelectric / electrostrictive porcelain composition as a piezoelectric / electrostrictive body can precisely control displacement, and has high electromechanical conversion efficiency. It has the advantages of high power, fast response speed, high durability, and low power consumption. Taking advantage of these advantages, it is employed in inkjet printer heads, diesel engine injectors, and the like.

As a piezoelectric / electrostrictive porcelain composition for a piezoelectric / electrostrictive actuator, a Pb (Zr, Ti) O ₃ (PZT) -based piezoelectric / electrostrictive porcelain composition has been conventionally used. (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain compositions have been studied since the elution of lead in the environment is strongly concerned. .

For example, Non-Patent Document 1 discloses a (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain composition having a stoichiometric composition.

Further, in Patent Document 1, in the (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain composition, the number of atoms of the A site element is excessive than the number of atoms of the B site element. It has been shown that the piezoelectric / electrostrictive characteristics can be improved.

International Publication No. 2006/095716 Yasuyoshi Saito et al, "High Performance Lead-Free Piezoelectric Ceramics in the (K, Na) NbO3-LiTaO3 Solid Solution System", Ferroelectrics (United States of America), 2006, Volume 338, p.17-32

However, in the conventional (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain composition, unless the firing temperature is set to a very high temperature, the sintering does not proceed sufficiently and the sintering density is low. There is a problem that the electric field induced strain at the time of applying a high electric field, which is important for piezoelectric / electrostrictive actuators, is not always sufficient.

Further, in the conventional (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain composition, the oxygen concentration is increased more than the air atmosphere in order to suppress the volatilization of alkaline components such as Li. In some cases, it was necessary to perform firing in an oxygen atmosphere having an oxygen concentration of 100%. Such manufacturing constraints are undesirable because they increase manufacturing costs.

The (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain composition has an orthorhombic-tetragonal phase transition temperature (hereinafter simply referred to as “phase transition temperature”) T _OT . And electric field induced strain is maximized at a temperature near the phase transition temperature _TOT . However, depending on the composition, the phase transition temperature T _OT is outside the range of the actual use temperature, so that sufficient electric field induced strain cannot be obtained at the actual use temperature, or the phase transition temperature T _OT is within the range of the actual use temperature. However, since the maximum value of the electric field induced strain at a temperature in the vicinity of the phase transition temperature _TOT is not sufficiently increased, sufficient electric field induced strain may not be obtained at the actual use temperature.

The present invention has been made to solve this problem, and can be sintered at a low temperature and has a good electric field induced strain when a high electric field is applied at an actual use temperature (Li, Na, K) (Nb, Ta). ) An object of the present invention is to provide an O ₃ -based piezoelectric / electrostrictive porcelain composition.

In order to solve the above-mentioned problem, the invention of claim 1 includes Li, Na and K as the first element, Nb and Ta as the second element, O as the third element, The ratio of the total number of atoms of the first element to the total number of atoms of the element is greater than 1, and the number of Ta atoms in the total number of atoms of the second element is 30 mol% or more and 50 mol% or less; A piezoelectric / electrostrictive porcelain composition comprising a perovskite oxide in which one element is an A-site constituent element and the second element is a B-site constituent element.

The invention of claim 2 is represented by the general formula {Li _y (Na _1−x K _x ) _1−y } _a (Nb _1−z Ta _z ) O ₃ , wherein a, x, y and z are respectively 2. The piezoelectric element according to claim 1, having a composition satisfying 1 <a ≦ 1.05, 0.30 ≦ x ≦ 0.70, 0.02 ≦ y ≦ 0.10, and 0.3 ≦ z ≦ 0.5. An electrostrictive porcelain composition.

3. The piezoelectric / electrostrictive porcelain according to claim 1 or 2, further comprising 0.1 to 3 parts by weight of Li ₃ NbO ₄ with respect to 100 parts by weight of the perovskite oxide. It is a composition.

  According to a fourth aspect of the present invention, there is provided a piezoelectric / electrostrictive film that is a sintered body of the piezoelectric / electrostrictive porcelain composition according to any one of the first to third aspects, and the piezoelectric / electrostrictive film. And an electrode film on the main surface.

According to the present invention, a (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain that can be sintered at a low temperature and has a good electric field induced strain when a high electric field is applied at an actual use temperature. A composition can be provided.

  Hereinafter, a piezoelectric / electrostrictive ceramic composition according to a preferred embodiment of the present invention will be described, and then an actuator using the piezoelectric / electrostrictive ceramic composition will be described. However, the following description does not mean that the application of the piezoelectric / electrostrictive porcelain composition of the present invention is limited to an actuator. For example, the piezoelectric / electrostrictive ceramic composition of the present invention may be used for a piezoelectric / electrostrictive element such as a sensor.

<1 Piezoelectric / electrostrictive porcelain composition>
{composition}
The piezoelectric / electrostrictive porcelain composition according to a preferred embodiment of the present invention includes lithium (Li), sodium (Na), and potassium (K) as the first element A, and niobium (Nb) as the second element B. And a composition having an ABO ₃ type composition formula containing oxygen (O) as the third element, the total of the first element A with respect to the total number of atoms of the second element B The first element A has a composition in which the ratio of the number of atoms (so-called A / B ratio) is greater than 1, and the number of Ta atoms in the total number of atoms of the second element B is 10 mol% or more and 50 mol% or less. Is a perovskite type oxide having an A site constituent element and a second element B as a B site constituent element. The perovskite oxide may further contain a monovalent element such as silver (Ag) as the A site element, or may further contain a pentavalent element such as vanadium (V) as the B site element. Good.

In addition, the piezoelectric / electrostrictive porcelain composition according to the preferred embodiment of the present invention is preferably 0.1 part by weight or more and 3 parts by weight or less of Li ₃ NbO with respect to a parent phase of 100 parts by weight of the perovskite oxide. _It further includes ₄ different phases. Thereby, the sinterability of the piezoelectric / electrostrictive porcelain composition can be improved. The reason why the amount of Li ₃ NbO ₄ is set to 0.1 parts by weight or more and 3 parts by weight or less is that when the amount of Li ₃ NbO ₄ falls below this range, the sinterability of the piezoelectric / electrostrictive porcelain composition is reduced and electric field induction is caused. This is because the strain becomes smaller and short-circuiting due to dielectric breakdown is likely to occur. If the amount of Li ₃ NbO ₄ exceeds this range, loss due to a different phase increases and electric field induced strain becomes smaller. This is because a short circuit is likely to occur.

The composition of the piezoelectric / electrostrictive porcelain composition according to the preferred embodiment of the present invention is represented by the general formula {Li _y (Na _1−x K _x ) _1−y } _a (Nb _1−z Ta _z ) O _3. , A, x, y and z are 1 <a ≦ 1.05, 0.30 ≦ x ≦ 0.70, 0.02 ≦ y ≦ 0.10 and 0.1 ≦ z ≦ 0.5, respectively. It is preferable to satisfy.

The reason for setting the A / B ratio to 1 <a is to improve the sinterability of the piezoelectric / electrostrictive porcelain composition. That is, a (Li, Na, K) (Nb, Ta) O ₃ -based piezoelectric / electrostrictive porcelain composition having a stoichiometric composition has a Ta amount increased to 0.1 ≦ z. As shown in Figure 1 of Fig. 1, the sintering temperature has to be lowered and the firing temperature has to be increased until just before melting, but by adopting a non-stoichiometric composition of 1 <a, The firing temperature can be lowered to 950 to 1050 ° C. Such an effect is particularly prominent within the range of 1.005 ≦ a. It is not desirable to increase the firing temperature. When the firing temperature is increased, the alkali component contained in the piezoelectric / electrostrictive porcelain composition evaporates, making it impossible to stably obtain good piezoelectric / electrostrictive characteristics. Because.

  On the other hand, the reason why the A / B ratio is set to a ≦ 1.05 is that if it exceeds this range, the dielectric loss increases and the electric field induced strain when applying a high electric field tends to be small.

The reason why the Ta amount is set to 0.1 ≦ z ≦ 0.5 is that the tetragonal-orthorhombic phase transition temperature (hereinafter simply referred to as “phase transition temperature”) in which the piezoelectric / electrostrictive characteristics become high within this range. the T _OT a vicinity of room temperature (-30 ℃ ~135 ℃), is because it is possible to increase the electric field induced strain during application of high electric field.

  The K and Li amounts were set to 0.30 ≦ x ≦ 0.70 and 0.02 ≦ y ≦ 0.10, respectively, so that a piezoelectric / electrostrictive porcelain composition suitable for an actuator can be obtained within this range. Because it can.

  For example, when x is less than this range, the piezoelectric / electrostrictive characteristics are rapidly lowered. On the other hand, if x exceeds this range, sintering becomes difficult and the firing temperature must be increased.

  If y is less than this range, sintering is still difficult, and the firing temperature must be increased. On the other hand, when y exceeds this range, precipitation of heterogeneous phases increases, and the insulation properties decrease.

It may be added Mn compound to the composition having the ABO ₃ type composition formula as the main component as an auxiliary component. When adding a Mn compound, it is desirable to add so that the addition amount in terms of Mn atom with respect to 100 mol parts of the main component is 3 mol parts or less. The reason why the amount of Mn compound added is 3 mol parts or less is that when the amount exceeds this range, the heterogeneous phase inside the sintered body increases, the dielectric loss increases, and the electric field induced strain when applying a high electric field tends to decrease. Because there is.

  Here, a very small amount of the Mn compound is sufficient. For example, even when only 0.001 mole part of Mn compound in terms of Mn atom is added to 100 mole parts of the main component, the polarization treatment of the sintered body is facilitated, and the electric field induced strain when a high electric field is applied. Can also be increased.

The Mn compound is desirably a compound of Mn whose valence is mainly divalent. For example, manganese oxide (MnO) or another compound in which manganese is dissolved is desirable, and a compound in which manganese is dissolved in trilithium niobate (Li ₃ NbO ₄ ) is particularly desirable. Here, “mainly divalent” may include a compound of Mn whose valence is other than divalent, and it means that the most contained valence may be divalent. The valence of Mn can be confirmed by an X-ray absorption near-edge structure (XANES). Further, it is desirable that Mn is present in the ceramic sintered body as an element constituting a heterogeneous phase of the manganese compound without being taken into the crystal lattice of the perovskite oxide that is the parent phase.

  By introducing such a Mn compound into the sintered body, hardening due to the addition of the Mn compound can be prevented, and the electric field induced strain can be increased.

{Phase transition temperature}
Generally speaking, (Li, Na, K) (Nb, Ta) O ₃ -based perovskite oxides and modified products thereof are sequentially formed in the order of cubic, tetragonal and orthorhombic from high temperature to low temperature. Although the phase transition occurs, in the piezoelectric / electrostrictive porcelain composition according to the preferred embodiment of the present invention, it is desirable to select the composition so that the phase transition temperature _TOT is _close to room temperature. This is because if the phase transition temperature _TOT is in the vicinity of room temperature, the electric field induced strain at the time of applying a high electric field can be increased at room temperature.

{Manufacture of raw material powder}
In producing the raw material powder of the piezoelectric / electrostrictive porcelain composition, first, a dispersion medium is added to the raw material of the constituent elements (Li, Na, K, Nb, Ta, Mn, etc.) of the piezoelectric / electrostrictive porcelain composition. Mix with a ball mill. Compounds such as oxides, carbonates and tartrates can be used as the raw material, and organic solvents such as ethanol, toluene and acetone can be used as the dispersion medium. Then, the dispersion medium is removed from the obtained mixed slurry by a technique such as evaporation drying or filtration to obtain a mixed raw material. Subsequently, the raw material powder can be obtained by calcining the mixed raw material at 600 to 1300 ° C. In addition, in order to obtain the raw material powder of a desired particle diameter, you may grind | pulverize with a ball mill etc. after calcination. Further, the raw material powder may be produced by an alkoxide method or a coprecipitation method instead of the solid phase reaction method. Further, a raw material of Mn for supplying Mn constituting the Mn compound may be added after the perovskite oxide is synthesized. In this case, it is desirable to add to the perovskite oxide synthesized with manganese dioxide (MnO ₂ ) as a raw material for Mn. The tetravalent Mn constituting the manganese dioxide added in this way is reduced during firing to divalent Mn, contributing to the improvement of the electric field induced strain. Alternatively, a perovskite oxide may be synthesized through a B-site element columbite compound.

  The average particle diameter of the raw material powder is preferably 0.07 to 10 μm, and more preferably 0.1 to 3 μm. Moreover, you may heat-process raw material powder at 400-850 degreeC in order to adjust the particle diameter of raw material powder. Finer particles are easier to be integrated with other particles. Therefore, when this heat treatment is performed, a raw material powder having a uniform particle size can be obtained, and a sintered body having a uniform particle size can be obtained.

<2 Piezoelectric / electrostrictive actuator>
{Overall structure}
1 and 2 are schematic views of structural examples of the piezoelectric / electrostrictive actuators 1 and 2 using the above-described piezoelectric / electrostrictive porcelain composition, and FIG. 1 shows a single-layer piezoelectric / electrostrictive actuator 1. FIG. 2 is a sectional view of the multilayer piezoelectric / electrostrictive actuator 2.

  As shown in FIG. 1, the piezoelectric / electrostrictive actuator 1 has a structure in which an electrode film 121, a piezoelectric / electrostrictive film 122, and an electrode film 123 are stacked in this order on the upper surface of a substrate 11. The electrode films 121 and 123 on both main surfaces of the piezoelectric / electrostrictive film 122 are opposed to each other with the piezoelectric / electrostrictive film 122 interposed therebetween. The laminate 12 in which the electrode film 121, the piezoelectric / electrostrictive film 122 and the electrode film 123 are laminated is fixed to the substrate 11.

  As shown in FIG. 2, the piezoelectric / electrostrictive actuator 2 has an electrode film 221, a piezoelectric / electrostrictive film 222, an electrode film 223, a piezoelectric / electrostrictive film 224, and an electrode film 225 on the upper surface of the substrate 21. Are stacked in this order. The electrode films 221 and 223 on both main surfaces of the piezoelectric / electrostrictive film 222 are opposed to each other with the piezoelectric / electrostrictive film 222 interposed therebetween, and the electrode films on both main surfaces of the piezoelectric / electrostrictive film 224 are disposed. 223 and 225 are opposed to each other with the piezoelectric / electrostrictive film 224 interposed therebetween. The laminate 22 in which the electrode film 221, the piezoelectric / electrostrictive film 222, the electrode film 223, the piezoelectric / electrostrictive film 224 and the electrode film 225 are laminated is fixed to the substrate 21. 2 shows a case where the piezoelectric / electrostrictive film has two layers, the piezoelectric / electrostrictive film may have three or more layers.

  Here, “adhesion” means that the laminates 12 and 22 are bonded to the substrates 11 and 21 by a solid-phase reaction at the interface between the substrates 11 and 21 and the laminates 12 and 22 without using an organic adhesive or an inorganic adhesive. It means joining. The laminate may be bonded to the substrate by a solid phase reaction at the interface between the substrate and the piezoelectric / electrostrictive film at the bottom layer of the laminate.

  In the piezoelectric / electrostrictive actuators 1 and 2, when a voltage is applied, the piezoelectric / electrostrictive bodies 122, 222, and 224 expand and contract in a direction perpendicular to the electric field according to the applied voltage, and as a result, bending displacement is caused. Arise.

{Piezoelectric / electrostrictive film}
The piezoelectric / electrostrictive films 122, 222, and 224 are sintered bodies of the above-described piezoelectric / electrostrictive ceramic composition.

  The film thickness of the piezoelectric / electrostrictive films 122, 222, and 224 is preferably 0.5 to 50 μm, more preferably 0.8 to 40 μm, and particularly preferably 1 to 30 μm. This is because if it falls below this range, densification tends to be insufficient. Further, if it exceeds this range, the shrinkage stress at the time of sintering increases, so that it is necessary to increase the thickness of the substrates 11 and 21, and it becomes difficult to miniaturize the piezoelectric / electrostrictive actuators 1 and 2. is there.

{Electrode film}
The material of the electrode films 121, 123, 221, 223, and 225 is a metal such as platinum, palladium, rhodium, gold, silver, or an alloy thereof. Among these, platinum or an alloy containing platinum as a main component is preferable in terms of high heat resistance during firing. Also, depending on the firing temperature, an alloy such as silver-palladium can be suitably used.

  The film thicknesses of the electrode films 121, 123, 221, 223, and 225 are preferably 15 μm or less, and more preferably 5 μm or less. This is because exceeding this range, the electrode films 121, 123, 221, 223, and 225 function as relaxation layers, and the flexural displacement tends to decrease. Moreover, in order for the electrode films 121, 123, 221, 223, and 225 to appropriately fulfill their roles, the film thickness is preferably 0.05 μm or more.

  The electrode films 121, 123, 221, 223, and 225 are preferably formed so as to cover regions that substantially contribute to the bending displacement of the piezoelectric / electrostrictive films 122, 222, and 224. For example, it is preferable that the piezoelectric / electrostrictive films 122, 222, and 224 are formed so as to cover regions of 80% or more of both main surfaces of the piezoelectric / electrostrictive films 122, 222, and 224, including the central portion.

{Substrate}
Although the material of the base | substrates 11 and 21 is ceramics, there is no restriction | limiting in the kind. However, from the viewpoint of heat resistance, chemical stability, and insulation, ceramics including at least one selected from the group consisting of stabilized zirconium oxide, aluminum oxide, magnesium oxide, mullite, aluminum nitride, silicon nitride, and glass. Is preferred. Among these, stabilized zirconium oxide is more preferable from the viewpoint of mechanical strength and toughness. Here, “stabilized zirconium oxide” refers to zirconium oxide in which the phase transition of the crystal is suppressed by addition of a stabilizer, and includes partially stabilized zirconium oxide in addition to stabilized zirconium oxide.

  Examples of the stabilized zirconium oxide include zirconium oxide containing 1 to 30 mol% of calcium oxide, magnesium oxide, yttrium oxide, ytterbium oxide, cerium oxide, or a rare earth metal oxide as a stabilizer. it can. Of these, zirconium oxide containing yttrium oxide as a stabilizer is preferred because of its particularly high mechanical strength. The content of yttrium oxide is preferably 1.5 to 6 mol%, and more preferably 2 to 4 mol%. In addition to yttrium oxide, it is more preferable to contain 0.1 to 5 mol% of aluminum oxide. The stabilized zirconium oxide crystal phase is a mixed crystal of cubic and monoclinic, a mixed crystal of tetragonal and monoclinic, or a mixed crystal of cubic, tetragonal and monoclinic, etc. However, it is preferable from the viewpoint of mechanical strength, toughness, and durability that the main crystal phase is a mixed crystal of tetragonal crystals and cubic crystals or a tetragonal crystal.

  The plate thickness of the substrates 11 and 21 is preferably 1 to 1000 μm, more preferably 1.5 to 500 μm, and particularly preferably 2 to 200 μm. This is because the mechanical strength of the piezoelectric / electrostrictive actuators 1 and 2 tends to be lower than this range. Further, if the range is exceeded, the rigidity of the substrates 11 and 21 is increased, and the bending displacement due to expansion / contraction of the piezoelectric / electrostrictive films 122, 222, and 224 when a voltage is applied tends to decrease.

  The surface shape of the substrates 11 and 21 (the shape of the surface to which the laminate is fixed) is not particularly limited, and may be a triangle, a rectangle (rectangle or square), an ellipse, or a circle. Rounding may be performed. It is good also as a compound form which combined these basic forms.

  The plate thickness of the substrate 11 of the single-layer piezoelectric / electrostrictive actuator 1 is uniform. In contrast, the thickness of the base 21 of the multilayer piezoelectric / electrostrictive actuator 2 is such that the central portion 215 to which the laminate 22 is bonded is thinner than the peripheral portion 216. This is to increase the bending displacement while maintaining the mechanical strength of the base 21. The substrate 21 may be used for the single-layer piezoelectric / electrostrictive actuator 1.

  As shown in the sectional view of FIG. 3, the base body 21 shown in FIG. 2 may be used as a unit structure, and a base body 31 in which the unit structure is repeated may be used. In this case, the piezoelectric / electrostrictive actuator 3 is configured by fixing the laminated body 32 on each of the unit structures.

{Manufacture of piezoelectric / electrostrictive actuators}
In manufacturing the single-layer piezoelectric / electrostrictive actuator 1, first, the electrode film 121 is formed on the substrate 11. The electrode film 121 is formed by a method such as ion beam, sputtering, vacuum deposition, PVD (Physical Vapor Deposition), ion plating, CVD (Chemical Vapor Deposition), plating, aerosol deposition, screen printing, spraying or dipping. Can do. Among these, from the viewpoint of bonding properties with the substrate 11 and the piezoelectric / electrostrictive film 122, a sputtering method or a screen printing method is preferable. The formed electrode film 121 can be fixed to the substrate 11 and the piezoelectric / electrostrictive film 122 by heat treatment. The temperature of the heat treatment is approximately 500 to 1400 ° C., although it varies depending on the material of the electrode film 121 and the formation method.

  Subsequently, a piezoelectric / electrostrictive film 122 is formed on the electrode film 121. The piezoelectric / electrostrictive film 122 is formed by ion beam, sputtering, vacuum deposition, PVD (Physical Vapor Deposition), ion plating, CVD (Chemical Vapor Deposition), plating, sol-gel, aerosol deposition, screen printing, spraying, dipping, or the like. It can form by the method of. Among them, the screen printing method is preferable in that the accuracy of the planar shape and the film thickness is high and the piezoelectric / electrostrictive film can be continuously formed.

  Subsequently, an electrode film 123 is formed on the piezoelectric / electrostrictive film 122. The electrode film 123 can be formed in the same manner as the electrode film 121.

  Thereafter, the substrate 11 on which the laminate 12 is formed is integrally fired. By this firing, the piezoelectric / electrostrictive film 122 is sintered and the electrode films 121 and 123 are heat-treated. The firing temperature of the piezoelectric / electrostrictive film 122 is preferably 800 to 1250 ° C, and more preferably 900 to 1200 ° C. Below this range, densification of the piezoelectric / electrostrictive film 122 becomes insufficient, and adhesion between the substrate 11 and the electrode film 121 and adhesion between the electrode films 121 and 123 and the piezoelectric / electrostrictive film 122 are not achieved. This is because they tend to be perfect. In addition, if it exceeds this range, the piezoelectric / electrostrictive characteristics of the piezoelectric / electrostrictive film 122 tend to deteriorate. The maximum temperature holding time during firing is preferably 1 minute to 10 hours, and more preferably 5 minutes to 4 hours. This is because if the thickness falls below this range, the piezoelectric / electrostrictive film 122 tends to be insufficiently densified. In addition, if it exceeds this range, the piezoelectric / electrostrictive characteristics of the piezoelectric / electrostrictive film 122 tend to deteriorate.

  Note that the heat treatment of the electrode films 121 and 123 is preferably performed together with the firing from the viewpoint of productivity, but this does not prevent the heat treatment from being performed every time the electrode films 121 and 123 are formed. However, when the piezoelectric / electrostrictive film 122 is fired before the heat treatment of the electrode film 123, the electrode film 123 is heat treated at a temperature lower than the firing temperature of the piezoelectric / electrostrictive film 122.

  After firing is complete, polarization treatment is performed under appropriate conditions. The polarization treatment can be performed by a well-known method, and although it depends on the Curie temperature of the piezoelectric / electrostrictive film 122, it is preferably performed by heating to 40 to 200 ° C.

  The multilayer piezoelectric / electrostrictive actuator 2 is manufactured in the same manner as the single-layer piezoelectric / electrostrictive actuator 1 except that the number of piezoelectric / electrostrictive films and electrode films to be formed is increased. Can do.

  The piezoelectric / electrostrictive actuator 1 can also be manufactured by a green sheet laminating method that is commonly used in the production of multilayer ceramic electronic components. In the green sheet laminating method, first, a binder, a plasticizer, a dispersant and a dispersion medium are added to the raw material powder and mixed by a ball mill or the like. And the obtained slurry is shape | molded by the doctor blade method etc. in a sheet shape, and a molded object is obtained.

  Subsequently, a film of electrode paste is printed on both main surfaces of the molded body by a screen printing method or the like. The electrode paste used here is obtained by adding a solvent, vehicle, glass frit, or the like to the above-described metal or alloy powder.

  Subsequently, the molded body on which the electrode paste film is printed on both main surfaces is bonded to the substrate.

  Thereafter, the substrate on which the laminate is formed is integrally fired, and after the firing is finished, polarization treatment is performed under appropriate conditions.

<3 Another example of piezoelectric / electrostrictive actuator>
4 to 6 are schematic views of structural examples of the piezoelectric / electrostrictive actuator 4 using the piezoelectric / electrostrictive porcelain composition described above. FIG. 4 is a perspective view of the piezoelectric / electrostrictive actuator 4, FIG. FIG. 6 is a longitudinal sectional view of the piezoelectric / electrostrictive actuator 4, and FIG. 6 is a transverse sectional view of the piezoelectric / electrostrictive actuator 4.

  As shown in FIGS. 4 to 6, the piezoelectric / electrostrictive actuator 4 includes the piezoelectric / electrostrictive film 402 and the internal electrode film 404 that are alternately stacked in the direction of the axis A. It has a structure in which external electrode films 416 and 418 are formed on end faces 412 and 414 of a laminate 410 in which an internal electrode film 404 is laminated. As shown in the exploded perspective view of FIG. 7 showing a state in which a part of the piezoelectric / electrostrictive actuator 4 is disassembled in the direction of the axis A, the internal electrode film 404 reaches the end surface 412 but reaches the end surface 414. There is a first internal electrode film 406 that does not reach, and a second internal electrode film 408 that reaches the end face 414 but does not reach the end face 412. The first internal electrode films 406 and the second internal electrode films 408 are provided alternately. The first internal electrode film 406 is in contact with the external electrode film 416 at the end surface 412 and is electrically connected to the external electrode film 416. The second internal electrode film 408 is in contact with the external electrode film 418 at the end face 414 and is electrically connected to the external electrode film 418. Therefore, when the external electrode film 416 is connected to the positive side of the drive signal source and the external electrode film 418 is connected to the negative side of the drive signal source, the first internal electrode film facing the piezoelectric / electrostrictive film 402 is sandwiched. A drive signal is applied to 406 and the second internal electrode film 408, and an electric field is applied in the thickness direction of the piezoelectric / electrostrictive film 402. As a result, the piezoelectric / electrostrictive film 402 expands and contracts in the thickness direction, and the laminated body 410 as a whole is deformed into a shape indicated by a broken line in FIG.

  Unlike the piezoelectric / electrostrictive actuators 1 to 3 already described, the piezoelectric / electrostrictive actuator 4 does not have a base to which the multilayer body 410 is fixed. The piezoelectric / electrostrictive actuator 4 is also referred to as an “offset type piezoelectric / electrostrictive actuator” because the first internal electrode film 406 and the second internal electrode film 408 having different patterns are alternately provided.

  The piezoelectric / electrostrictive film 402 is a sintered body of the above-described piezoelectric / electrostrictive ceramic composition. The film thickness of the piezoelectric / electrostrictive film 402 is preferably 5 to 500 μm. This is because, if it falls below this range, it will be difficult to produce a green sheet described later. Further, if it exceeds this range, it is difficult to apply a sufficient electric field to the piezoelectric / electrostrictive film 402.

  The material of the internal electrode film 404 and the external electrode films 416 and 418 is a metal such as platinum, palladium, rhodium, gold or silver, or an alloy thereof. Among these, the material of the internal electrode film 404 is preferably platinum or an alloy containing platinum as a main component from the viewpoint of high heat resistance during firing and easy co-sintering with the piezoelectric / electrostrictive film 402. . However, depending on the firing temperature, an alloy such as silver-palladium can also be suitably used.

  The film thickness of the internal electrode film 402 is preferably 10 μm or less. This is because if the thickness exceeds this range, the internal electrode film 402 functions as a relaxation layer and the displacement tends to be small. In order for the internal electrode film 402 to properly fulfill its role, the film thickness is preferably 0.1 μm or more.

  4 to 6 show the case where the piezoelectric / electrostrictive film 402 has 10 layers, the piezoelectric / electrostrictive film 402 may have 9 layers or less or 11 layers or more. .

  In manufacturing the piezoelectric / electrostrictive actuator 4, first, a binder, a plasticizer, a dispersant, and a dispersion medium are added to the raw material powder of the above-described piezoelectric / electrostrictive porcelain composition and mixed by a ball mill or the like. Then, the obtained slurry is formed into a sheet shape by a doctor blade method or the like to obtain a green sheet.

  Subsequently, the green sheet is punched using a punch or die to form alignment holes or the like in the green sheet.

  Subsequently, an electrode paste is applied to the surface of the green sheet by screen printing or the like to obtain a green sheet on which an electrode paste pattern is formed. There are two types of electrode paste patterns: a first electrode paste pattern that becomes the first internal electrode film 406 after firing and a second electrode paste pattern that becomes the second internal electrode film 408 after firing. . Of course, the internal electrode films 406 and 408 may be obtained after firing by using only one type of electrode paste pattern and rotating the orientation of the green sheets every other 180 °.

  Next, the green sheet on which the pattern of the first electrode paste is formed and the green sheet on which the pattern of the second electrode paste is formed are alternately stacked, and the green sheet on which the electrode paste is not applied is placed on the top. After further overlapping, the stacked green sheets are pressed in the thickness direction and pressure bonded. At this time, the positions of the alignment holes formed in the green sheet are aligned. Further, when the stacked green sheets are pressure-bonded, it is also desirable to heat the mold used for pressure bonding so that the green sheets are pressure-bonded while being heated.

  The laminate 410 can be obtained by firing the pressure-bonded green sheet thus obtained and processing the obtained sintered body with a dicing saw or the like. The piezoelectric / electrostrictive actuator 4 can be obtained by forming the external electrode films 416 and 418 on the end faces 412 and 414 of the laminated body 410 by baking, vapor deposition, sputtering, or the like and performing polarization treatment.

  Below, Examples 1-42 regarding the piezoelectric / electrostrictive ceramic composition of the present invention and Comparative Examples 1-9 regarding the piezoelectric / electrostrictive ceramic composition outside the scope of the present invention will be described. However, the examples described below do not limit the scope of the present invention.

{Manufacture of piezoelectric / electrostrictive element for evaluation}
In producing a piezoelectric / electrostrictive element for evaluation, first, lithium carbonate (Li ₂ CO ₃ ), sodium tartrate monohydrate (C ₄ H ₅ O ₆ Na.H ₂ O), potassium tartrate (C ₄ H) Raw materials such as ₅ O ₆ K), niobium oxide (Nb ₂ O ₅ ), and tantalum oxide (Ta ₂ O ₅ ) were weighed so as to have the compositions shown in Tables 1 to 5. X, y, z and a in the lists of Tables 1 to 5 are parameters in the general formula {Li _y (Na _1−x K _x ) _1−y } _a (Nb _1−z Ta _z ) O _3. The amount of Mn is the amount added relative to 100 mol parts of the main component represented by the general formula.

Subsequently, alcohol was added to the raw material as a dispersion medium and mixed for 16 hours by a ball mill. Subsequently, the obtained mixed raw material was dried, calcined at 800 ° C. for 5 hours, and pulverized with a ball mill twice to obtain a raw material powder of a piezoelectric / electrostrictive ceramic composition. At this time, in Examples 8, 9, 21 to 33 and Comparative Examples 3 and 4, MnO ₂ was added to the raw material powder so as to have the addition amounts shown in Tables 1 to 5.

  Next, the raw material powder was coarsely pulverized and then passed through a 500 mesh sieve to adjust the particle size.

The raw material powder thus obtained was compacted into a disc shape having a diameter of 18 mm and a plate thickness of 5 mm at a pressure of 2.0 × 10 ⁸ Pa. And the compacting body was accommodated in the alumina container, and it baked at 950-1050 degreeC for 3 hours, and obtained the sintered compact (piezoelectric / electrostrictive body).

  Subsequently, the sintered body was processed into a rectangular shape having a long side of 12 mm, a short side of 3 mm, and a thickness of 1 mm, and heat treatment was performed at 600 to 900 ° C. Thereafter, gold electrodes were formed by sputtering on both main surfaces of the rectangular sample. This was immersed in silicon oil at room temperature, and a voltage of 5 kV / mm was applied to the gold electrodes on both main surfaces for 15 minutes to perform polarization treatment in the thickness direction.

<Examples 1 to 9 and Comparative Examples 1 and 2>
{Electrical and temperature characteristics}
Using the piezoelectric / electrostrictive elements for evaluation of Examples 1 to 9 and Comparative Examples 1 and 2 fired at 970 ° C., in the vicinity of piezoelectric constant d ₃₁ (pm / V), room temperature, and phase transition temperature T _OT The distortion rate S ₄₀₀₀ (ppm) of was measured. The measurement results are shown in Table 1. The piezoelectric constant d ₃₁ is a fundamental wave of the longitudinal vibration of the long side direction by measuring the frequency-impedance characteristics and capacitance of the piezoelectric / electrostrictive element with an impedance analyzer, and measuring the dimensions of the piezoelectric / electrostrictive element with a micrometer. It was obtained by calculating from the resonance frequency and antiresonance frequency, capacitance, and dimensions. Strain ratio S ₄₀₀₀ was obtained by measuring a strain gauge affixed to the electrode with an adhesive field induced strain of the long side direction when a voltage of 4 kV / mm to the gold electrode on both main surfaces. A method for measuring the phase transition temperature _TOT will be described later.

As apparent from comparison of Examples 1 to 7 with Comparative Examples 1 and 2 with reference to Table 1, when the amount of Ta is in the range of 0.1 ≦ z ≦ 0.5, the general formula {Li _0.06 In the composition represented by (Na _0.55 K _0.45 ) _0.94 } _1.03 (Nb _{1 -z} Ta _z ) O ₃ , a good distortion rate S ₄₀₀₀ can be obtained, but if the amount of Ta falls below this range, or If it exceeds the upper _limit , it becomes impossible to obtain a good distortion rate _S4000 . Further, as apparent from reference to Examples 8 and 9, the compositional formula {Li _0.06 (Na _0.55 K _0.45 ) _0.94 } _1.03 (Nb _0.70 Ta _0.30 ) O ₃ is added to 100 mol parts of the main component. By adding 02 or 0.10 mol part (0.02 or 0.10 mol part in terms of Mn atom) of the Mn compound, the strain ratio S ₄₀₀₀ can be further improved.

{X-ray diffraction pattern}
FIG. 8 shows the X of the sintered body used in the piezoelectric / electrostrictive elements of Examples 2 to 6 in which the Ta amount is z = 0.15, 0.20, 0.25, 0.30, 0.40. It is a figure which shows a line (CuK (alpha) ray) diffraction pattern. FIG. 8 also shows an X-ray diffraction pattern of a sintered body having a Ta amount of z = 0.08.

  In measuring the X-ray diffraction pattern, the sample is set so that X-rays are irradiated onto the 12 mm × 3 mm surface of the processed sample, and the X-ray diffraction pattern of the sample is 20 ° to 60 ° by the 2θ / θ method. Measured in range. The X-ray diffraction pattern was measured using an X-ray diffractometer with a Cu-Kα ray as a radiation source and a graphite monochromator installed in front of the detector. The X-ray generation conditions were measured as 35 kV-30 mA, scan width 0.02 °, scan speed 2 ° / min, diverging slit 1 °, and light receiving slit 0.3 mm.

  As shown in FIG. 8, when the Ta amount is z = 0.15, 0.20, 0.25, an X-ray diffraction pattern specific to the orthorhombic crystal of perovskite is observed, and the crystal system of the sintered body is oblique. It turns out that it is a tetragonal crystal. On the other hand, when the amount of Ta is z = 0.30 and 0.40, an X-ray diffraction pattern specific to the tetragonal perovskite is observed, indicating that the crystal system of the sintered body is tetragonal.

Further, as shown in FIG. 8, peaks derived from the different phases indicated by arrows are observed in the X-ray diffraction patterns of the sintered bodies used in the piezoelectric / electrostrictive elements of Examples 2 to 6. This heterogeneous phase is considered to be Li ₃ NbO ₄ .

Further, the amount of Li ₃ NbO ₄ was quantified from the X-ray diffraction patterns of the sintered bodies used in the piezoelectric / electrostrictive elements of Examples 1 to 9 and Comparative Examples 1 and 2. The amount of Li ₃ NbO ₄ is the integrated intensity of the diffraction peak of the (211) plane of Li ₃ NbO ₄ and the integrated intensity of the diffraction peaks of the (101) plane and the (110) plane of perovskite in the X-ray diffraction pattern of the sintered body. Calculated from the ratio with the sum. The quantitative results are shown in Table 1. The amount of Li ₃ NbO ₄ shown in Table 1 is a weight ratio with respect to 100 mol parts of the perovskite oxide. As shown in Table 1, in Examples 1 to 9 and Comparative Examples 1 and 2, the amount of Li ₃ NbO ₄ is in the range of 1.0 to 1.5 parts by weight, and Example 1 having a desirable composition In .about.9, a good distortion rate _S4000 was obtained at a firing temperature of 970.degree.

{Phase transition temperature T _OT }
Next, the phase transition temperature _TOT of the sintered bodies used in the piezoelectric / electrostrictive elements of Examples 1 to 9 and Comparative Examples 1 and 2 was measured. The phase transition temperature T _OT was determined by measuring the temperature dependence of the relative dielectric constant ε / ε ₀ with an impedance analyzer. The measurement results are shown in Table 1. As is apparent from this measurement result, the phase transition temperature T _OT decreases as the amount of Ta increases. When the amount of Ta falls within the range of 0.1 ≦ z ≦ 0.5, the phase transition temperature T _OT is the actual use temperature. As a result, the strain rate S ₄₀₀₀ at room temperature is also higher than 250 ppm. However, when the amount of Ta falls below this range, the phase transition temperature _TOT does not sufficiently decrease, and as a result, a good strain rate S ₄₀₀₀ cannot be obtained at room temperature, and when the amount of Ta exceeds this range. As a result, the phase transition temperature T _OT is remarkably lowered, and as a result, a good strain rate S ₄₀₀₀ cannot be obtained at room temperature and in the vicinity of the phase transition temperature T _OT .

<Examples 5 and 10-13>
Next, using the piezoelectric / electrostrictive element for evaluation of Examples 5 and 10-13 fired at 950, 970, 1000, 1030, and 1050 ° C., the piezoelectric constant d ₃₁ (pm / V), the distortion rate S ₄₀₀₀ (ppm) and the sintered density (g / cm ³ ) were measured at room temperature. The measurement results are shown in Table 2. The measuring method of the piezoelectric constant d ₃₁ and the distortion rate S _{4000 is} the same as the measuring method described above. The sintered density was measured by the Archimedes method.

As is clear from comparison between Examples 5 and 10 to 13 with reference to Table 2, any practically sufficient strain rate S ₄₀₀₀₀ or sintered density is obtained within the range of the firing temperature of 950 to 1050 ° C. When the firing temperature is 970 ° C., the strain rate S ₄₀₀₀ and the sintered density are maximized. That is, in the piezoelectric / electrostrictive porcelain compositions of Examples 5 and 10 to 13, the sinterability is good even though the Ta amount is z = 0.3.

<Examples 14 to 20>
Next, the piezoelectric constant d ₃₁ (pm / V), room temperature, and phase were evaluated using the piezoelectric / electrostrictive elements for evaluation of Examples 14 to 20 in which the composition of the main component was variously changed without adding MnO _2. The strain rate S ₄₀₀₀ (ppm) in the vicinity of the transition temperature T _{OT and} the phase transition temperature T _OT (° C.) were measured. The measurement results are shown in Table 3. The measuring method of the piezoelectric constant d ₃₁ and the distortion rate S _{4000 is the same as} the measuring method described above. Further, the amount of Li ₃ NbO ₄ was quantified from the X-ray diffraction patterns of the sintered bodies used in the piezoelectric / electrostrictive elements of Examples 14 to 20. The quantitative results are shown in Table 3. The method for quantifying the amount of Li ₃ NbO ₄ is the same as that described above.

As shown in Table 3, even when the composition of the main component is changed, the phase transition temperature T _OT is within the range of the actual use temperature within the range of Ta ≦ 0.1 ≦ 0.5. Therefore, a good distortion rate S ₄₀₀₀ can be obtained.

In Examples 14 to 20, Li ₃ NbO ₄ amount is 0.1 to 0.5 parts by weight (Example 14), 1.0 to 1.5 parts by weight (Example 15 to 18), 2. Within the range of 0 to 3.0 parts by weight (Examples 19 and 20), a good distortion rate S ₄₀₀₀ was obtained at a firing temperature of 970 to 1000 ° C.

<Examples 21 to 33 and Comparative Examples 3 and 4>
Next, piezoelectrics for evaluation in Examples 21 to 33 and Comparative Examples 3 and 4 in which 0.02 mol part (0.02 mol part in terms of Mn atom) was added and the composition of the main component was variously changed. / The piezoelectric constant d ₃₁ (pm / V), room temperature, and the strain rate S ₄₀₀₀ (ppm) in the vicinity of the phase transition temperature T _{OT and} the phase transition temperature (° C.) were measured using an electrostrictive element. The measurement results are shown in Table 4. The measuring method of the piezoelectric constant d ₃₁ and the distortion rate S _{4000 is the same as} the measuring method described above. Further, the amount of Li ₃ NbO ₄ was quantified from the X-ray diffraction patterns of the sintered bodies used in the piezoelectric / electrostrictive elements of Examples 21 to 33 and Comparative Examples 3 and 4. The quantitative results are shown in Table 4. The method for quantifying the amount of Li ₃ NbO ₄ is the same as that described above.

As shown in Table 4, even when the composition of the main component is changed when the Mn compound is added, the phase transition temperature T _OT is within the range of 0.1 ≦ z ≦ 0.5. Is in the range of the actual use temperature, and a good distortion rate S ₄₀₀₀ is obtained.

As evident from comparison between Examples 1 to 7 and Example 26 to 33, by addition of the Mn compound can improve the strain ratio S _4000.

Furthermore, as shown in Table 4, in Examples 21 to 33 and Comparative Examples 3 and 4, the amount of Li ₃ NbO ₄ was 0.1 to 0.5 parts by weight (Examples 21 to 23), 1.0 to Examples 21 to 21 having a desirable composition within the range of 1.5 parts by weight (Examples 24, 26 to 33, Comparative Examples 3 and 4) and 2.0 to 3.0 parts by weight (Example 25) In No. 33, a good distortion rate S ₄₀₀₀ was obtained at a firing temperature of 970 to 1000 ° C.

<Examples 5, 10-14, 20, 34-42 and Comparative Examples 5-9>
Next, the firing temperature was changed while keeping the composition of the main component constant (a) Comparative Examples 5 to 9, (b) Examples 14, 34 to 37, (c) Examples 5, 10 to 13, ( D) The sintered density of the sintered bodies used in the piezoelectric / electrostrictive elements of Examples 20, 38, 39 and (E) Examples 40 to 42 were measured, and the X-ray diffraction pattern of the sintered bodies was measured. The amount of Li ₃ NbO ₄ was quantified. The measurement results and quantitative results are shown in Table 5. The method for measuring the sintered density and the method for determining the amount of Li ₃ NbO ₄ are the same as those described above.

As shown in Table 5, in Comparative Examples 5 to 9, the amount of Li ₃ NbO ₄ is less than 0.1 parts by weight, and even if the firing temperature is increased to 1050 ° C., the sintered density is not saturated, and the firing temperature Even if the temperature is raised to 1050 ° C., it cannot be said that the sintering is sufficiently advanced. On the other hand, in Examples 5, 10 to 14, 20, and 34 to 42, the amount of Li ₃ NbO ₄ is 0.1 to 0.5 parts by weight (Examples 14, 34 to 37), 1.0 to 1.5 parts by weight (Examples 5, 10-13), 2.0-3.0 parts by weight (Examples 20, 38, 39), more than 3 parts by weight (Examples 40-42), Sintering density is saturated at a firing temperature of 1050 ° C. or lower, and sintering is sufficiently advanced at a firing temperature of 1050 ° C. or lower. However, in Examples 40 to 42 in which the amount of Li ₃ NbO ₄ was more than 3 parts by weight, a short circuit due to dielectric breakdown was likely to occur during polarization treatment or driving.

  The above description is illustrative in all aspects, and the present invention is not limited thereto. It is understood that countless variations that are not illustrated can be envisaged without departing from the scope of the present invention.

It is sectional drawing of a piezoelectric / electrostrictive actuator. It is sectional drawing of a piezoelectric / electrostrictive actuator. It is sectional drawing of a piezoelectric / electrostrictive actuator. It is a perspective view of a piezoelectric / electrostrictive actuator. It is a longitudinal cross-sectional view of a piezoelectric / electrostrictive actuator. It is a cross-sectional view of a piezoelectric / electrostrictive actuator. It is a disassembled perspective view of a part of a piezoelectric / electrostrictive actuator. It is a figure which shows the X-ray-diffraction pattern of a sintered compact.

Explanation of symbols

1, 2, 3, 4 Piezoelectric / electrostrictive actuators 122, 222, 224, 402 Piezoelectric / electrostrictive film 121, 123, 221, 223, 225 Electrode film 404 Internal electrode film

Claims (4)

The first element includes Li, Na, and K, the second element includes Nb and Ta, the third element includes O, and the total number of atoms of the first element relative to the total number of atoms of the second element The ratio of is greater than 1 and the number of Ta atoms in the total number of atoms of the second element is 30 mol% or more and 50 mol% or less,
A piezoelectric / electrostrictive porcelain composition comprising a perovskite oxide having a first element as an A-site constituent element and a second element as a B-site constituent element. Is represented by the general formula _{{Li y (Na 1-x} K x) 1-y} a (Nb 1-z Ta z) O 3, a, x, y and z are, respectively, 1 <a ≦ 1.05 , 0.30 ≦ x ≦ 0.70, 0.02 ≦ y ≦ 0.10, and 0.3 ≦ z ≦ 0.5. _3. The piezoelectric / electrostrictive ceramic composition according to claim 1, further comprising 0.1 to 3 parts by weight of Li ₃ NbO ₄ with respect to 100 parts by weight of the perovskite oxide. A piezoelectric / electrostrictive film, which is a sintered body of the piezoelectric / electrostrictive ceramic composition according to any one of claims 1 to 3,
Electrode films on both principal surfaces of the piezoelectric / electrostrictive film;
A piezoelectric / electrostrictive element comprising:

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