JP4995412B2 - Piezoelectric ceramic composition and piezoelectric element using the same - Google Patents

Description

The present invention relates to a piezoelectric ceramic composition and a piezoelectric element. More specifically, the present invention relates to a piezoelectric ceramic composition and a piezoelectric element that are substantially free of lead, have excellent piezoelectric characteristics, and have excellent thermal durability.
The piezoelectric ceramic composition and piezoelectric element of the present invention are widely used for vibration detection applications, pressure detection applications, oscillation applications, piezoelectric device applications, and the like. For example, sensors for detecting various vibrations (knock sensors, combustion pressure sensors, etc.), piezoelectric devices such as vibrators, actuators, filters, etc., high voltage generators, micro power supplies, various driving devices, position control devices, vibration suppression devices, It can be used for fluid discharge devices (such as paint discharge and fuel discharge). In particular, it is suitable for applications requiring excellent thermal durability (for example, a knock sensor and a combustion pressure sensor).

Many piezoelectric ceramics that have been mass-produced in the past contain lead. However, the cost for processing so that lead does not affect the environment is enormous, and the development of lead-free piezoelectric ceramics is required. Currently, (Bi _0.5 Na _0.5 ) TiO ₃ -based compounds and bismuth layered compounds are known as piezoelectric ceramics not containing lead, but the piezoelectric strain constant is lower than that of leaded piezoelectric ceramics. There is a problem that the generated voltage with respect to the applied voltage or the distortion with respect to the applied voltage is small. Therefore, there is a problem that it is particularly difficult to use as an active element such as a vibrator. On the other hand, for example, the following Patent Document 1 and Patent Document 2 disclose a piezoelectric ceramic mainly composed of an alkali metal niobate compound.

Japanese Patent Publication No.56-12031 Japanese Patent Laid-Open No. 11-228227

The above-mentioned Patent Document 1 discloses a piezoelectric ceramic containing iron oxide and / or cobalt oxide in (K _x Na _1-x ) NbO ₃ , but there is a problem that it is difficult to obtain a sufficient dielectric constant. is there. On the other hand, in Patent Document 2, (K _1-xy Na _x Li _y ) (Nb _1-z Ta _z ) O ₃ -m1m2O ₃ (m1 is a divalent metal element, m2 is a tetravalent metal element) Is a piezoelectric ceramic composition having a main component as a main component and having an improved relative dielectric constant with respect to Patent Document 1 described above. However, since these alkali metal niobate oxides are extremely difficult to sinter, it is desired to be able to sinter more reliably and to further improve the piezoelectric characteristics such as piezoelectric strain constant and electromechanical coupling coefficient. ing.
Further, there is a need for a piezoelectric ceramic having sufficient thermal durability that can be used in applications exposed to high temperatures such as a knock sensor and a combustion pressure sensor.

  The present invention solves the above-mentioned problems, does not substantially contain lead, is excellent in sinterability, is excellent in any characteristics of an electromechanical coupling coefficient, a piezoelectric strain constant, and a relative dielectric constant, and An object of the present invention is to provide a piezoelectric ceramic composition and a piezoelectric element having excellent thermal durability.

The present invention is as follows.
(1) Metal element K, metal element Na, metal element Nb, divalent metal element or combination of metal elements equivalent to bivalent as a whole M1, and tetravalent metal element or totally equivalent to tetravalent A combination of metal elements M2, a metal element M3 constituting a sintering aid component, and a nonmetallic element O, and the K and Na are not substituted with other elements, or at least one of them In which M1 is at least one of Ca, Sr, and Ba, M2 is Ti, and M3 is Cu, Ni. is at least one of Zn and Mg, K, Na, Nb, the M1 and the M2, the composition formula _{[(1/2) aK 2 O- (} 1/2) bNa 2 O-cM1O- ( _{1/2) dNb 2 O 5 -eM2O 2} ] When represented, 0 <a <0.5, 0 <b <0.5, 0 <c <0.11, 0.4 <d <0.56, 0 <e <0.12, 0.4 <A + b + c ≦ 0.5, a + b + c + d + e = 1, (a + b) /d≦0.97 is satisfied, and the total mass in terms of oxides of K, Na, Nb, M1, and M2 is 100 parts by mass Further, the piezoelectric ceramic composition, wherein M3 is 5 parts by mass or less in terms of oxide.
(2) When the total mass in terms of oxides of K, Na, Nb, M1 and M2 is 100 parts by mass, M3 is 0.1 parts by mass or more in terms of oxides. 2. The piezoelectric ceramic composition according to 1.
( 3 ) The piezoelectric ceramic composition according to (1) or (2) , wherein M3 is a combination of Cu and Ni or Zn.
( 4 ) The piezoelectric ceramic composition according to any one of (1) to ( 3 ), wherein 0 <c / (a + b + c) ≦ 0.20.
( 5 ) The piezoelectric ceramic composition contains Ta as a metal element in addition to K, Na, Nb, M1, M2, and M3, and a part of Nb in the composition formula is contained in the Ta. The piezoelectric ceramic composition according to any one of (1) to ( 4 ), wherein the piezoelectric ceramic composition is replaced.
( 6 ) The piezoelectric ceramic composition contains Sb in addition to K, Na, Nb, M1, M2 and M3 as metal elements, and a part of Nb in the composition formula is contained in Sb. The piezoelectric ceramic composition according to any one of (1) to ( 4 ), wherein the piezoelectric ceramic composition is replaced.
( 7 ) The piezoelectric ceramic composition according to any one of (1) to ( 6 ), wherein the piezoelectric ceramic composition has a perovskite crystal structure.
( 8 ) The piezoelectric ceramic composition according to ( 7 ), wherein the perovskite crystal belongs to an orthorhombic system.
( 9 ) A piezoelectric element comprising: a piezoelectric body made of the piezoelectric ceramic composition according to any one of (1) to ( 8 ) above; and at least a pair of electrodes in contact with the piezoelectric body.

According to the piezoelectric ceramic composition of the present invention, excellent thermal durability can be exhibited. Moreover, since it contains the metal element M3 constituting the sintering aid, it is excellent in sinterability, while the total mass in terms of oxides of K, Na, Nb, M1 and M2 is 100 parts by mass. Sometimes, since this M3 is contained within a range of 5 parts by mass or less in terms of oxide, excellent performance is obtained without impairing piezoelectric properties such as electromechanical coupling coefficient, piezoelectric strain constant and relative dielectric constant. Can be balanced. Furthermore, since the piezoelectric ceramic composition of the present invention does not substantially contain lead (Pb), it is excellent from the viewpoint of environmental protection. “Substantially free of lead (Pb)” means that it does not contain the intentionally added metal element Pb, and contains trace amounts of lead (usually less than 1000 ppm) as inevitable impurities. Are allowed in the present invention. However, in order not to cause environmental problems with certainty, it is preferable not to contain lead.
When the total mass of each of K, Na, Nb, M1 and M2 in terms of oxide is 100 parts by mass, M3 is preferably contained in an amount of 0.1 parts by mass or more in terms of oxide. This is because sintering of the piezoelectric ceramic composition can be favorably promoted.
When 0 <c / (a + b + c) ≦ 0.20, more excellent piezoelectric characteristics are exhibited.
When a part of at least one of K and Na in the composition formula is substituted by Li, as in the case where it is not substituted, while maintaining excellent thermal durability and excellent sinterability, In any piezoelectric characteristics such as electromechanical coupling coefficient, piezoelectric strain constant and relative dielectric constant, excellent performance can be exhibited in a well-balanced manner.
When part of Nb in the composition formula is substituted with Ta, the electromechanical coupling coefficient, piezoelectric strain, and the like are maintained while maintaining excellent thermal durability and excellent sinterability, as in the case of not being substituted. Excellent performance can be exhibited in a well-balanced manner in any piezoelectric characteristics such as constant and dielectric constant.
When part of Nb in the composition formula is substituted with Sb, the electromechanical coupling coefficient, piezoelectric strain, and the like are maintained while maintaining excellent thermal durability and excellent sinterability as in the case of not being substituted. Not only can excellent performance be exhibited in a balanced manner in any piezoelectric characteristics such as constants and relative dielectric constants, but also the occurrence of leakage current during polarization processing can be greatly suppressed.
In the case of having a perovskite type crystal structure, further excellent piezoelectric characteristics can be exhibited. In particular, c / (a + b + c) is preferably adjusted to a range of 0 <c / (a + b + c) ≦ 0.20. Here, c / (a + b + c) indicates the ratio of M1 to the metal element constituting the A site of the perovskite crystal structure. By defining the ratio of the metal element M1 within a predetermined range, not only the improvement of piezoelectric characteristics but also the effect of imparting sufficient thermal durability that can be used even at high temperatures can be achieved.
Further, when the perovskite crystal belongs to the orthorhombic system, particularly excellent piezoelectric characteristics can be exhibited.
According to the piezoelectric element of the present invention, excellent thermal durability can be exhibited. In addition, excellent performance in piezoelectric properties such as electromechanical coupling coefficient, piezoelectric strain constant and relative dielectric constant can be exhibited in a well-balanced manner.

The present invention will be described in detail below.
[1] Piezoelectric Ceramic Composition The piezoelectric ceramic composition of the present invention includes a combination of a metal element K, a metal element Na, a metal element Nb, a divalent metal element, or a metal element equivalent to divalent as a whole M1. It contains a tetravalent metal element or a combination M2 of metal elements corresponding to tetravalent as a whole, a metal element M3 constituting a sintering aid component, and a nonmetallic element O.

The “M1” is a divalent metal element or a combination of divalent metal elements as a whole.
Here, as the “combination of metal elements corresponding to bivalent as a whole” (hereinafter, simply referred to as “divalent combination”), the following (1) to (4) can be mentioned, but in the present invention ( The combination of 2) can be adopted .
(1) The combination of non-divalent metal elements such as (Bi _0.5 Na _0.5 ), (Bi _0.5 K _0.5 ), and (Bi _0.5 Li _0.5 ) A combination corresponding to the price.
(2) By a combination of divalent metal elements such as (Ca _0.5 Sr _0.5 ), (Sr _0.5 Ba _0.5 ) and (Ca _1/3 Sr _1/3 Ba _1/3 ), As a whole, the combination is equivalent to bivalent.
(3) (Bi _0.5 Na _0.5 ) _0.5 Ca _0.5 , (Bi _0.5 Na _0.5 ) _0.5 Sr _0.5 , (Bi _0.5 Na _0.5 ) _{0 .5} Ba _0.5 , (Bi _0.5 K _0.5 ) _0.5 Ca _0.5 , (Bi _0.5 K _0.5 ) _0.5 Sr _0.5 and (Bi _0.5 K _{0 .5} ) A combination corresponding to divalent as a whole by a combination of a non-divalent metal element such as _0.5 Ba _0.5 and a divalent metal element.
(4) (Bi _0.5 Na _0.5 ) _0.5 (Ca _0.5 Sr _0.5 ) _0.5 , (Bi _0.5 Na _0.5 ) _0.5 (Sr _0.5 Ba _{0 .5) 0.5, (Bi 0.5 K} 0.5) 0.5 (Ca 0.5 Sr 0.5) 0.5, and _{(Bi 0.5 K 0.5) 0.5 (} Sr _0.5 Ba _0.5 ) A combination corresponding to divalent as a whole by further combining a combination of non-divalent metal elements such as _0.5 and a combination of divalent metal elements.

Among these M1, those containing at least one of Ca, Sr, Ba, (Bi _0.5 Na _0.5 ) and (Bi _0.5 K _0.5 ) {ie, Ca, Sr , Ba, (Bi _0.5 Na _0.5 ) or (Bi _0.5 K _0.5 ), and Ca, Sr, Ba, (Bi _0.5 Na _0.5 ) and (Bi _0.5 K _0.5) which includes at least two or more of} is rather preferable, in the present invention can be adopted Ca, Sr, at least one of Ba. This is because the effect of improving the piezoelectric characteristics is high.

The “M2” is a combination of a tetravalent metal element or a metal element corresponding to tetravalent as a whole. Examples of the “tetravalent metal element” include Ti, Zr, Sn, and Hf . In the present invention, Ti can be employed . In addition, examples of “a combination of metal elements corresponding to tetravalent as a whole” (hereinafter simply referred to as “tetravalent combination”) include the following (1) to (4).
(1) (Ti _0.5 Zr _0.5 ), (Ti _0.5 Sn _0.5 ), (Zr _0.5 Sn _0.5 ) and (Ti _1/3 Zr _1/3 Sn _1/3 ) A combination corresponding to tetravalent as a whole by a combination of tetravalent metal elements such as
(2) A combination of non-tetravalent metal elements such as (Mg _0.33 Ta _0.67 ), (Al _0.5 Ta _0.5 ), (Zn _0.5 W _0.5 ), etc. A combination corresponding to the price.
(3) Combination of non-tetravalent metal elements such as Ti _0.5 (Mg _0.33 Ta _0.67 ) _0.5 , Ti _0.5 (Al _0.5 Ta _0.5 ) _0.5 and 4 A combination corresponding to tetravalent as a whole by combination with a valent metal element.
(4) (Ti _0.5 Zr _0.5 ) _0.5 (Mg _0.33 Ta _0.67 ) _0.5 , (Ti _0.5 Zr _0.5 ) (Al _0.5 Ta _0.5 ) The combination of tetravalent metal elements such as _0.5 and non-tetravalent metal elements is a combination corresponding to tetravalent as a whole.
Among these M2, Ti is adopted . This is because the effect of improving the piezoelectric characteristics is high.

The “M3” is a metal element constituting a sintering aid component. The sintering aid component is a component containing M3. For example, the sintering aid is composed of a compound such as an oxide, carbonate or hydroxide of M3. By containing this component, sintering is promoted, and easy sintering of the piezoelectric body made of the piezoelectric ceramic composition can be realized. M3 is a metal element excluding a metal element applied as K, Na, Nb, and M1, and a metal element applied as M2, and is usually a transition metal element, and among them, Fe, Co, Ni Mg, Zn and Cu are preferred, but Ni, Mg, Zn and Cu can be employed in the present invention . This is because these are particularly excellent in the densifying action of the obtained piezoelectric ceramic composition. These metal elements may be used alone or in combination of two or more, and in the case of two or more, a combination with Cu is preferable. Ni is particularly preferable as the metal element used in combination with Cu.

This M3 is contained in an amount of 5 parts by mass or less in terms of oxide when the total mass of each of K, Na, Nb, M1 and M2 in terms of oxide is 100 parts by mass. This is because if the content exceeds 5 parts by mass, the piezoelectric characteristics may be deteriorated. In this oxide conversion, M3 is converted as M3On (n is an integer or a fraction determined according to the valence of M3). For example, Fe is converted as FeO _3/2 , Co as CoO _4/3 , Ni as NiO, Cu as CuO, Zn as ZnO, and Mg as MgO. The lower limit of the content of M3 can be 0.1 parts by mass in terms of oxide. If M3 is contained in an amount of 0.1 parts by mass or more, the piezoelectric body made of the piezoelectric ceramic composition can be used. It is preferable for obtaining easy sinterability effectively. Further, the more preferable range of M3 is 0.1 to 3.5 mass in terms of oxide when the total mass in terms of oxide of each of K, Na, Nb, M1 and M2 is 100 mass parts. Parts, particularly 0.1 to 2.0 parts by mass.

  The combination of M1, M2, and M3 is not particularly limited, but M1 includes at least one of Ca, Sr, and Ba as described above, and M2 includes Ti as described above. In addition, as described above, it is preferable to use at least one of Ni, Mg, Zn and Cu as M3, in particular, a combination of Cu and Ni. When M1, M2, and M3 are used in such a combination, the piezoelectric characteristics can be further improved.

In the piezoelectric ceramic composition of the present invention, K, Na, Nb, M1 and M2 in the combination of the metal element and the metal element contained above are represented by the composition formula [(1/2) aK ₂ O— ( _{1/2) bNa 2 O-cM1O- (} 1/2) dNb 2 O 5 when expressed in -eM2O _2], a representative of the molar ratio of an oxide in terms of the combination of these metal elements or metal elements, b , C, d, and e are important to satisfy the following predetermined conditions.

The “a” represents a molar ratio of K in terms of oxide {1/2 (K ₂ O)}, and 0 <a <0.5 (preferably 0.2 ≦ a ≦ 0.25). If a is 0.5 or more, the sinterability may decrease, which is not preferable.
The “b” represents a molar ratio of Na oxide in terms of {1/2 (Na ₂ O)}, and 0 <b <0.5 (preferably 0.2 ≦ b ≦ 0.25). If b is 0.5 or more, the sinterability may decrease, which is not preferable.
The “c” represents a molar ratio of M1 in terms of oxide (M1O), and 0 <c <0.11 (preferably 0.01 ≦ c ≦ 0.1). If c is 0.11 or more, the piezoelectric characteristics may be greatly deteriorated, which is not preferable.
The “d” represents a molar ratio of Nb oxide in terms of {1/2 (Nb ₂ O ₅ )}, 0.4 <d <0.56 (preferably 0.4 <d <0.5). It is. If d is 0.4 or less, the piezoelectric characteristics may not be obtained. If d is 0.56 or more, the piezoelectric characteristics are likely to deteriorate, which is not preferable.
The “e” represents a molar ratio of M2 in terms of oxide (M2O ₂ ), and 0 <e <0.12 (preferably 0 <e <0.1). If e is 0.12 or more, piezoelectric characteristics may not be obtained, which is not preferable.

The above “a + b + c” represents the total molar ratio of K, Na, and M1, and 0.4 <a + b + c ≦ 0.5. When a + b + c is 0.4 or less or exceeds 0.5, the piezoelectric characteristics may be greatly deteriorated, which is not preferable.
The above “c / (a + b + c)” represents the ratio of the molar ratio of M1 to the total molar ratio of K, Na and M1. That is, when K, Na, Nb, M1 and M2 constituting the piezoelectric ceramic composition of the present invention are expressed as (K _a Na _b M1 _c ) (Nb _d M2 _e ) O ₃ , they are included in the A site. It is the molar ratio of M1 among metal elements. This molar ratio is preferably 0 <c / (a + b + c) ≦ 0.20. This is because particularly excellent piezoelectric characteristics can be obtained when c / (a + b + c) is 0.20 or less, particularly 0.15 or less.

Moreover, K and Na (including K and Na contained as M1) among the metal elements contained in the piezoelectric ceramic composition of the present invention may be partially replaced by Li. The amount of substitution with Li is not particularly limited, but it is 0.3 or less (preferably 0.2 or less, more preferably 0.15 or less, usually 0 or less) in terms of a molar ratio {Li / (K + Na)} to the total amount of K and Na. 001 or more). If it is 0.3 or less, an excellent piezoelectric ceramic composition can be obtained without deteriorating sinterability and piezoelectric characteristics.
Similarly, Nb of the metal elements contained in the piezoelectric ceramic composition of the present invention may be partially substituted with Ta. The amount of substitution of Ta is not particularly limited, but is 0.4 or less (more preferably 0.3 or less, still more preferably 0.25 or less, usually 0.001 or more) in terms of a molar ratio (Ta / Nb) to Nb. If it is 0.4 or less, an excellent piezoelectric ceramic composition can be obtained without deteriorating sinterability and piezoelectric characteristics.
A part of Nb among the metal elements contained in the piezoelectric ceramic composition of the present invention may be replaced by Sb. Although the substitution amount of Sb is not particularly limited, it is 0.025 or less in terms of a molar ratio to Sb (Sb / Nb). If it is 0.025 or less, the dielectric constant can be improved, and the generation of leakage current during the polarization treatment can be effectively suppressed.

  The crystal structure of the piezoelectric ceramic composition of the present invention is not particularly limited, but usually exhibits a perovskite crystal structure. Further, this perovskite crystal may be any of orthorhombic, cubic and tetragonal, and two or more of these are included, one of which is included as the main crystal phase, The other may be included as a subcrystalline phase or the like. Of these crystal phases, an orthorhombic system is particularly preferable. This is because particularly excellent piezoelectric characteristics can be obtained when an orthorhombic perovskite phase is included. Further, all of the perovskite phase may be orthorhombic perovskite.

The method for obtaining the piezoelectric ceramic composition of the present invention is not particularly limited, but usually the following raw material preparation step, calcination step, molding step, firing step, and polarization step are performed.
The raw material preparation step uses a compound containing K, Na, Nb, M1, M2 and M3, and the molar ratio of each metal element contained in the compound is a, b, c, d and e in the above composition formula. It is a process of satisfy | filling and preparing so that M3 may contain 5 mass parts or less in conversion of an oxide with respect to the total mass of 100 mass parts which converted each oxide of K, Na, Nb, M1, and M2. However, the compound to be used may be one containing M1 in a divalent combination and M2 in a tetravalent combination, but each of M1 and M2 can be used as long as the above molar ratio can be satisfied. A compound containing only one kind of metal elements constituting the combination may be used.
The compound used in this raw material preparation step is not particularly limited, and examples thereof include oxides, carbonates, hydroxides, hydrogen carbonates, nitrates, and organometallic compounds of each metal element. The form of these compounds is also not particularly limited, and may be powdery or liquid. Furthermore, each said metal element contained in a compound may be only 1 type, and 2 or more types may be sufficient as it.

  The calcining step is a step of calcining the porcelain raw material obtained in the raw material preparation step. The calcining temperature, calcining time, calcining atmosphere, etc. are not particularly limited. For example, the calcination temperature is usually lower than the firing temperature described later, and is 600 to 1000 ° C. The calcining time can be 1 to 10 hours. The calcination environment is usually an air atmosphere.

  The forming step is a step of forming the calcined product obtained in the calcining step after making it ready for molding. Usually, after calcination, the calcined product is pulverized, further mixed with an organic binder, a dispersant, a solvent, and the like, then dried and granulated to obtain a granulated powder. Thereafter, the obtained granulated powder is compacted into a desired shape. In this case, pressure molding is usually performed. The method of pressure molding is not particularly limited. For example, after primary molding by a uniaxial pressing method, secondary molding such as cold isostatic pressing (CIP) treatment can be further performed.

  A baking process is a process of baking the molded object obtained at the formation process. The firing temperature, firing time, firing atmosphere and the like in this firing step are not particularly limited. For example, the firing temperature is usually 900 to 1300 ° C. The firing time can be 1 to 10 hours. The firing environment is usually an air atmosphere.

  The polarization process is a process for causing the porcelain obtained through the firing process to exhibit piezoelectric characteristics. Usually, the porcelain having electrodes formed after the firing step is placed in an insulating environment maintained at a predetermined temperature (for example, in a highly insulating liquid), and a DC voltage of 0.5 to 5 kV / mm is applied between the electrodes. It can be performed by applying for 30 minutes. In addition, the above-mentioned electrode is subjected to parallel polishing on the upper and lower surfaces of the porcelain obtained through the firing step, and then a conductive paste is applied to the upper and lower surfaces after polishing and held at 600 to 800 ° C. for 10 minutes for baking. Can be formed.

[2] Piezoelectric element The piezoelectric element of the present invention includes a piezoelectric body made of the piezoelectric ceramic composition of the present invention and at least a pair of electrodes in contact with the piezoelectric body.
The “piezoelectric body” is a portion that exhibits piezoelectric characteristics in the piezoelectric element. The shape and size of the piezoelectric body are not particularly limited, and it is preferable that the piezoelectric body be appropriately selected according to vibration detection use, pressure detection use, oscillation use, piezoelectric device use, and the like. The shape of the piezoelectric body can be various shapes such as a flat plate shape such as a square shape or a circular shape in a planar shape, a flat plate shape in which a through hole is provided in the thickness direction in the central portion, a prismatic shape, or a cylindrical shape. The piezoelectric element may be configured by laminating a plurality of piezoelectric bodies having these shapes.
The “pair of electrodes” is a conductor layer formed on the surface of the piezoelectric body. Each of the electrodes may be formed on one surface and the other surface of the piezoelectric body, and each electrode may be formed on the same surface of the piezoelectric body. Further, the shape, size, material, and the like of the electrode are not particularly limited, and it is preferable that the electrode be appropriately selected depending on the size, application, and the like of the piezoelectric body. The shape of this electrode may be flat, and in particular, when each of the pair of electrodes is formed on the same surface of the piezoelectric body, it may be comb-shaped. The method for forming this electrode is not particularly limited, but it is usually obtained by applying a conductive paste to a desired surface of a piezoelectric body and then baking it.
Here, as an example of the piezoelectric element, a piezoelectric element 1 used in a non-resonant knock sensor is shown in FIG. The piezoelectric element 100 is formed in a disk shape, and has a piezoelectric body 1 having a through hole 11 in the center, and a conductive layer formed by applying and baking a conductive paste on each of the front and back surfaces of the piezoelectric body 1. 21 and 22 (a pair of electrodes).

The conductive paste can be prepared using glass frit, a conductive component, and an organic medium.
As the glass frit, for _example, it is possible to use those containing such _{SiO 2, Al 2 O 3,} ZnO and TiO _2. With this glass frit, the bonding strength between the piezoelectric body made of the piezoelectric ceramic composition and the pair of electrodes can be improved.
As the conductive component, a powder made of a noble metal such as silver, gold, palladium, or platinum, a mixed powder containing two or more of these powders, a powder made of an alloy of two or more noble metals, or the like can be used. In addition, powders made of copper, nickel, etc., or mixed powders thereof, and powders made of alloys of these metals can also be used. As the conductive component, powders of silver, palladium, and silver-palladium alloy are particularly preferable. The average particle size of the conductive powder is preferably 20 μm or less (more preferably 1 to 5 μm). When the thickness is 20 μm or less, an unfired electrode can be formed using a screen printing method. This conductive component is usually blended so as to be 70 to 99% by mass of the solid content contained in the conductive paste.
As an organic medium, what is generally used for preparation of this kind of paste, such as alcohol, ester, ethers, can be used, for example. This organic medium is usually blended in an amount of about 10 to 40% by mass when the conductive paste is 100% by mass.

Hereinafter, the present invention will be described specifically by way of examples.
[1] Production of piezoelectric body (Experimental examples 1 to 20 shown in Table 1)
Using the commercially available K ₂ CO ₃ powder, Na ₂ CO ₃ powder, CaCO ₃ powder, SrCO ₃ powder, BaCO ₃ powder, Bi ₂ O ₃ powder, Nb ₂ O ₅ powder, and TiO ₂ powder, the composition Each of a, b, c, d and e in the formula was weighed so as to have the quantitative ratio shown in Table 1. Furthermore, using each of commercially available Fe ₂ O ₃ powder, Co ₃ O ₄ powder, and CuO powder, in terms of oxide of M3 with respect to the total mass in terms of oxide of each of K, Na, Nb, M1, and M2, Weighing was performed so that the mass was α part shown in Table 1. Ethanol was added to these powders and wet mixed in a ball mill for 15 hours to obtain a slurry. Thereafter, the mixed powder obtained by drying the slurry was calcined at 600 to 1000 ° C. for 1 to 10 hours in an air atmosphere to obtain a calcined product. Next, this calcined product was pulverized and mixed with a ball mill by adding a dispersant, a binder and ethanol to obtain a slurry. Then, this slurry was dried, granulated, uniaxially pressed at a pressure of 20 MPa, and formed into two types of shapes, a disc shape (diameter 20 mm, thickness 2 mm) and a cylindrical shape (diameter 3 mm, height 8 mm). .
Then, CIP processing was performed at a pressure of 150 MPa, and the obtained CIP press body was fired by holding at 900 to 1300 ° C. in an air atmosphere for 1 to 10 hours.
As a result, all those containing M3 could be sintered, but could not be sintered in Experimental Examples 1-3, 12 and 13 which did not contain M3.

尚、実験例１〜２０では（ａ＋ｂ）／ｄは全て１．００であるため、表１には（ａ＋ｂ）／ｄの値は記載しなかった。また、表１中、実験例の欄に付した＊印は比較品であることを意味する。更に、ａ〜ｅ及びαの各欄に付した＊印は各値が本発明の範囲から外れることを意味する。

In Experimental Examples 1 to 20, since (a + b) / d is all 1.00, the value of (a + b) / d is not described in Table 1. In Table 1, the * mark attached to the column of the experimental example means that it is a comparative product. Furthermore, * mark attached | subjected to each column of ae and (alpha) means that each value remove | deviates from the range of this invention.

[2] Fabrication of piezoelectric body (Experimental examples 21 to 39 shown in Table 2)
Using each of commercially available K ₂ CO ₃ powder, Na ₂ CO ₃ powder, CaCO ₃ powder, SrCO ₃ powder, BaCO ₃ powder, Nb ₂ O ₅ powder, and TiO ₂ powder, a, b, c in the above composition formula , D and e were weighed so that the quantitative ratios in Table 2 were obtained.

Note that the experimental examples 21,24,26,27 and 30 shown in Table 2, the composition formula of the piezoelectric ceramic composition _{[(1/2) aK 2 O- (} 1/2) bNa 2 O-cM1O- ( 1/2) When using dNb ₂ O ₅ -eM2O ₂ ], Sb ₂ O ₃ powder was used so that a part of Nb was replaced with Sb, and d ′ (Sb) was a quantitative ratio of Table 2. [The quantitative ratio of d in Table 2 shows the final quantitative ratio including the quantitative ratio of d ′ (Sb) and Nb ₂ O ₅ powder. ]. For Experimental Example 31 shown in Table 2, Ta ₂ O ₅ powder was used so that part of Nb was replaced by Ta when the composition formula of the piezoelectric ceramic composition was expressed as described above, and d '(Ta) was weighed so as to have the quantitative ratio of Table 2 [The quantitative ratio of d in Table 2 shows the final quantitative ratio including the quantitative ratio of d' (Ta) and Nb ₂ O ₅ powder. ing. ]. Furthermore, for Experimental Examples 37 to 39 shown in Table 2, when the composition formula of the piezoelectric ceramic composition is expressed as described above, Li ₂ CO ₃ powder is used so that a part of K or Na is replaced with Li. And Li were weighed so as to have the quantitative ratios in Table 2 (Li is replaced by a part of K or Na, but in this example all Li is replaced by Na, and the quantitative ratio of b The amount ratio of b in Table 2 indicates the final amount ratio including the amount ratio of Li and the amount ratio of Na ₂ CO ₃ powder. ])].

Next, using commercially available Co ₃ O ₄ powder, MgO powder, NiO powder, ZnO powder, and CuO powder, the oxide of M3 with respect to the total mass in terms of oxides of each of K, Na, Nb, M1, and M2 It measured so that the mass in conversion might be the (alpha) part shown in Table 2. Ethanol was added to these powders and wet mixed in a ball mill for 15 hours to obtain a slurry. Thereafter, the mixed powder obtained by drying the slurry was calcined at 600 to 1000 ° C. for 1 to 10 hours in an air atmosphere to obtain a calcined product. Next, this calcined product was pulverized and mixed with a ball mill by adding a dispersant, a binder and ethanol to obtain a slurry. Then, this slurry was dried, granulated, uniaxially pressed at a pressure of 20 MPa, and formed into two types of shapes, a disc shape (diameter 20 mm, thickness 2 mm) and a cylindrical shape (diameter 3 mm, height 8 mm). .
Then, CIP processing was performed at a pressure of 150 MPa, and the obtained CIP press body was fired by holding at 900 to 1300 ° C. in an air atmosphere for 1 to 10 hours.
Since all of Experimental Examples 21 to 39 contained M3, they could all be sintered.

表２中、実験例の欄に付した＊印は比較品であることを意味する。また、（ａ＋ｂ）／（ｄ＋ｄ’）の欄及びαの欄に付した＊印は各値が本発明の範囲から外れることを意味する。

In Table 2, an asterisk (*) attached to the column of the experimental example means that it is a comparative product. In addition, the * mark attached to the column (a + b) / (d + d ′) and the column α means that each value is out of the scope of the present invention.

[3] Fabrication of piezoelectric element (electrode formation)
The upper and lower surfaces of each piezoelectric body (disk and columnar) of the experimental examples shown in Table 1 and Table 2 that could be sintered as described above were polished in parallel. Next, a conductive paste prepared using glass frit, silver powder and an organic medium containing SiO ₂ , Al ₂ O ₃ , ZnO and TiO ₂ is applied to the upper and lower surfaces after polishing by screen printing, and 600 to 800 ° C. Were baked for 10 minutes to form an electrode. The sintered body on which the electrode is formed is immersed in insulating oil (silicone oil) kept at 20 to 200 ° C., and is subjected to polarization treatment by applying a direct current of 0.5 to 5 kV / mm for 1 to 30 minutes. Got.

[4] Measurement of piezoelectric characteristics According to the EMAS6000 series, the piezoelectric characteristics obtained in [3] above were measured using the piezoelectric body obtained in [1], and are shown in Table 3. Each characteristic in Table 3 is as follows.
ε ₃₃ ^T / ε ₀ : relative dielectric constant _kr : electromechanical coupling coefficient before heating (spreading vibration mode of disk-shaped element)
k _r *: Electromechanical coupling coefficient after heating (spreading vibration mode of the disk-shaped element)
.Delta.k _{r: k r} deterioration rate _{{(k r -k r *)} / k r × 100, Unit:%}
k ₃₃ : electromechanical coupling coefficient before heating (longitudinal vibration mode of cylindrical element)
k ₃₃ *: Electromechanical coupling coefficient after heating (longitudinal vibration mode of cylindrical element)
Δk ₃₃ : k ₃₃ deterioration rate {(k ₃₃ −k ₃₃ *) / k ₃₃ × 100, unit:%}
d ₃₃ : piezoelectric strain constant before heating (unit: pC / N)
d ₃₃ *: Piezoelectric strain constant after heating (unit: pC / N)
Δd ₃₃ : d ₃₃ deterioration rate {(d ₃₃ −d ₃₃ *) / d ₃₃ × 100, unit:%}
In addition, according to the EMAS6000 series, the piezoelectric characteristics obtained in the above [3] were measured using the piezoelectric body obtained in the above [2], and are shown in Table 4. Each characteristic in Table 4 was measured for three types of ε ₃₃ ^T / ε ₀ , k _r , and d ₃₃ , which can be said to be particularly important properties among the ten types of properties described above.
Among these, the relative dielectric constant was calculated from the value of capacitance at 1 kHz using an impedance analyzer (manufactured by Hewlett-Packard Company, model “HP4194A”). Further, the electromechanical coupling coefficient was obtained by a resonance antiresonance method, and the piezoelectric strain constant was calculated from these obtained numerical values. Further, “after heating” indicates each characteristic after being held at 200 ° C. for 1 hour.

表３中、実験例の欄に付した＊印は比較品であることを意味する。

In Table 3, an asterisk (*) attached to the column of the experimental example means that it is a comparative product.

表４中、実験例の欄に付した＊印は比較品であることを意味する。

In Table 4, an asterisk (*) in the column of experimental examples means that the product is a comparative product.

[3] Identification of Crystal Phase The crystal phase of each sintered body and each fired body obtained in the above [1] and [2] was identified using an X-ray diffractometer. As a result, it was found that all the experimental examples contained a perovskite crystal. Further, when this perovskite crystal is orthorhombic, it is described as “oblique” in the column of “perovskite crystal” in Tables 3 and 4, and when it is cubic, it is described as “standing”.

[4] Results (1) Sinterability Although all the samples containing M3 could be sintered, Experimental Examples 1-3, 12 and 13 not containing M3 could not be sintered. That is, from the results of Experimental Examples 1 to 3, it can be seen that, regardless of the presence or absence of M1 and M2, even if the molar ratio of K and Na is changed, sintering cannot be performed unless M3 is contained. Further, Experimental Example 12 differs from Experimental Example 8 in that Experimental Example 13 differs from Experimental Example 10 only in that M3 is not contained, but it can be seen that sintering was caused by the inclusion of M3.

(2) Piezoelectric properties In Comparative Examples 4 to 6, which are comparative products not containing M1 and M2, the relative dielectric constant ε ₃₃ ^T / ε ₀ is as low as 250 to 440, and c, d, and e are within the scope of the present invention. In Experimental Example 16, which was outside, no piezoelectric characteristics were observed. Furthermore, even in the case of a piezoelectric element (piezoelectric body) that has been sintered by containing M3, the content of M3 is an oxide with respect to the total mass in terms of oxides of K, Na, Nb, M1, and M2. In Experimental Example 36 in which the conversion exceeded 5 parts by mass, piezoelectric characteristics were not recognized.
On the other hand, in Experimental Examples 7 to 11, 14, 15, 17 to 20, ₃₃ to 34, and Experimental Examples 21 to 32, 35, and 37 to 39 which are products of the present invention , the relative dielectric constant ε ₃₃ ^T / ε ₀ Is 590 to 1535, particularly 1000 or more in Experimental Examples 7, 8, 10, 11, 17, 18, 20, 32, 35 and 37 to 39, and in particular, Experimental Example 24 shows a very large value of 1535. It was.

In Experimental Examples 7 to 11, 14, 15, 17 to 20, 33 to 34, and Experimental Examples 21 to 32, 35, and 37 to 39 which are products of the present invention, the electromechanical coupling coefficient k _r before heating is 0. 150 to 0.415, and in Experimental Examples 8, 9, 14, 17, 18, 20, 22, 25 to 27, 33, and 38, 0.300 or more, especially in Experimental Examples 14 and 26, 0.400 or more. And it showed a very large value. Similarly, the electromechanical coupling coefficient k ₃₃ is 0.274 to 0.530, and particularly in the experimental example excluding the experimental example 7, a large value of 0.307 to 0.530 is shown (for the experimental examples 21 to 39). , K ₃₃ has not been evaluated.) Further, the piezoelectric strain constant d ₃₃ before heating is 50 to 200 pC / N. In Experimental Examples 18, 20, 26 and 27, it exceeds 150 pC / N, and in Experimental Example 26, it shows a very large value of 200 pC / N. It was.

(3) In Example 4-6 is a thermally durable comparative, .DELTA.k _r, decreasing rate in all .DELTA.k ₃₃ and [Delta] d ₃₃ is greater than 30%, the heat resistance is lowered.
In contrast, in Examples 7～11,14,15 and 17 to 20, .DELTA.k _r, was suppressed the decrease rate below 28% in all .DELTA.k ₃₃ and [Delta] d _33. In particular, excluding Experimental Example 7 (that is, if M1 is other than Ca), it is 24.4% or less in Experimental Examples, and further, 20% or less was achieved in Experimental Examples 8-11, 14, 15 and 19 Thus, it can be seen that extremely excellent thermal durability can be exhibited (Experimental Examples 21 to 39 are not evaluated after heating).

(4) Crystal Phase Experimental Examples 1 to 15 , 17 to 20, 33 to 34, and the crystal phases of Experimental Examples 21 to 32, 35, and 37 to 39 which are products of the present invention are all attributed to orthorhombic perovskite. I understood that.

It is a perspective view of an example of the piezoelectric element of the present invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 100; Piezoelectric element, 1; Piezoelectric body, 11; Through-hole, 21, 22;

Claims (9)

Metal element K;
Metal element Na,
A metal element Nb;
A combination M1 of divalent metal elements or metal elements corresponding to divalent as a whole,
A combination M2 of tetravalent metal elements or metal elements corresponding to tetravalent as a whole,
A metal element M3 constituting a sintering aid component;
A non-metallic element O,
The K and Na are not substituted with other elements, or at least one part thereof is substituted only with the metal element Li,
M1 is at least one of Ca, Sr and Ba,
M2 is Ti,
M3 is at least one of Cu, Ni, Zn and Mg,
K, Na, Nb, the M1 and the M2,
Composition formula _{[(1/2) aK 2 O- (} 1/2) bNa 2 O-cM1O- (1/2) dNb 2 O 5 -eM2O 2]
When expressed in
0 <a <0.5,
0 <b <0.5,
0 <c <0.11,
0.4 <d <0.56,
0 <e <0.12,
0.4 <a + b + c ≦ 0.5,
a + b + c + d + e = 1,
(A + b) /d≦0.97 is satisfied,
When the total mass in terms of oxides of K, Na, Nb, M1 and M2 is 100 parts by mass,
The piezoelectric ceramic composition, wherein M3 is 5 parts by mass or less in terms of oxide.   The said M3 is 0.1 mass part or more in conversion of an oxide, when the total mass in each oxide conversion of K, Na, Nb, said M1, and said M2 is 100 mass parts. Piezoelectric ceramic composition. The piezoelectric ceramic composition according to claim 1 or 2 , wherein M3 is a combination of Cu and Ni or Zn. 0 <c / (a + b + c) piezoelectric ceramic composition according to any of ≦ 0.20 in which the first to third aspects. The piezoelectric ceramic composition contains Ta as a metal element in addition to K, Na, Nb, M1, M2, and M3, and a part of Nb in the composition formula is replaced with Ta. The piezoelectric ceramic composition according to any one of claims 1 to 4 . The piezoelectric ceramic composition contains Sb in addition to K, Na, Nb, M1, M2, and M3 as metal elements, and a part of Nb in the composition formula is replaced with Sb. The piezoelectric ceramic composition according to any one of claims 1 to 4 . The piezoelectric ceramic composition according to any one of claims 1 to 6 , having a perovskite crystal structure. The piezoelectric ceramic composition according to claim 7 , wherein the perovskite crystal belongs to an orthorhombic system. A piezoelectric element comprising: a piezoelectric body comprising the piezoelectric ceramic composition according to any one of claims 1 to 8 ; and at least a pair of electrodes in contact with the piezoelectric body.

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