WO2014192164A1 - Composition de céramique piézoélectrique et son procédé de production - Google Patents

Composition de céramique piézoélectrique et son procédé de production Download PDF

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WO2014192164A1
WO2014192164A1 PCT/JP2013/065922 JP2013065922W WO2014192164A1 WO 2014192164 A1 WO2014192164 A1 WO 2014192164A1 JP 2013065922 W JP2013065922 W JP 2013065922W WO 2014192164 A1 WO2014192164 A1 WO 2014192164A1
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component
piezoelectric ceramic
piezoelectric
ceramic composition
electrode
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Japanese (ja)
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究 田上
佳信 久保
福島　利博
加藤　和昭
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株式会社富士セラミックス
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
    • C04B35/475—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on bismuth titanates
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/01—Manufacture or treatment
    • H10N30/09—Forming piezoelectric or electrostrictive materials
    • H10N30/093—Forming inorganic materials
    • H10N30/097—Forming inorganic materials by sintering
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N30/00—Piezoelectric or electrostrictive devices
    • H10N30/80—Constructional details
    • H10N30/85—Piezoelectric or electrostrictive active materials
    • H10N30/853—Ceramic compositions
    • H10N30/8542—Alkali metal based oxides, e.g. lithium, sodium or potassium niobates
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    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
    • C04B2235/3213—Strontium oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO

Definitions

  • the present invention relates to a piezoelectric ceramic composition and a manufacturing method thereof, and more particularly to a piezoelectric ceramic composition suitable for pressure detection having a low hysteresis of a generated charge amount with respect to pressure and a large equivalent piezoelectric constant, and a manufacturing method thereof.
  • "having equivalent piezoelectric constant within a certain range" in the present invention is defined as at least 20 pC / N or more 35pC / N or less as the equivalent piezoelectric constant d 33.
  • quartz or a piezoelectric ceramic composition having ferroelectric characteristics has been used as a pressure detection material.
  • the former crystal has a hysteresis of “0” (hereinafter referred to as “zero”), but the equivalent piezoelectric constant (d 33 ) is extremely low (about 2 pC / N), and cannot be said to be a material suitable for pressure detection.
  • the latter piezoelectric ceramic composition having ferroelectric characteristics has a large equivalent piezoelectric constant (d 33 ) in a composition such as that of the present invention described later, and Patent Documents 1 to 4 and Non-Patent Document focusing on low hysteresis characteristics. Document 1 is known. However, in these prior arts, a piezoelectric ceramic composition having the effects as in the present invention has not been obtained.
  • Patent Document 1 Patent Document 2 is a corresponding US application
  • the description “No hysteresis” (0011) is recognized for the amount of charge generated with respect to pressure.
  • FIG. 3 the effect of Mn is given for the magnitude of hysteresis (0018). “There is a sharp drop in sensitivity when the amount of Mn is less than 0.02% by weight, and the amount of Mn. It is clear that hysteresis is abruptly caused when the amount exceeds 0.25% by weight.
  • a bismuth layered compound characterized by containing manganese in an amount of 0.02 to 0.25 wt% as MnO is recited in the claims.
  • the ferroelectric composition comprising not only Mn but also other components (Sr 1-2x Na x Bi 4 + x ) Ti 4 O 15 has inherent hysteresis and its crystal structure changes depending on the amount of x. As a result, hysteresis and sensitivity also change. Hysteresis and sensitivity are also characteristics determined in the state of the constituent composition including the influence of internal diffusion of the constituent material of the electrode material provided for the evaluation. Therefore, low hysteresis and high sensitivity can be achieved by the effects including these, and the problem can be solved only by the present invention.
  • the problem of piezoelectric characteristics is defined by a composition formula [Bi 4 Ti 3 O 12 ⁇ ⁇ [(1- ⁇ ) MTiO 3 + ⁇ BiFeO 3 ] different from the composition formula of the present invention by defining hysteresis. It is stated that it has been resolved.
  • Problem solution according to the patent document 3 the amount of "Mn is the amount of Mn is preferably .mno 2 converted more than 0.1 parts by MnO 2 in terms of is more than 0.1 part by weight, the hysteresis is large "0033" is also accepted.
  • the amount of Mn is zwt% (z is limited to 0.2 wt%) (the main component of the bismuth layered compound [(Na 0.5 , Bi 0.5 ) 1-x M x Bi 4 Ti 4 O 15 ] is defined as wt% with respect to 100 parts by mass.
  • This range is intended to solve the problem within the range denied by the patent document, and the problem can be solved only by the present invention.
  • the difference in the main composition means that the crystal structure is also different. Therefore, it cannot be said that the effect of Mn is the same as that of the present invention.
  • Patent Document 4 with respect to hysteresis, a composition formula different from the composition formula of the present invention.
  • the problem of piezoelectric characteristics has been solved.
  • Table 1 of Patent Document 4 d 33 is 20 or more and hysteresis is 0.11 in samples 26 and 47, and d 33 is 16, 19 and hysteresis is close to 7 and 18 near this. The description of about 0.12 is recognized.
  • the amount of "Mn is the amount of Mn is preferably .mno 2 converted more than 0.1 parts by MnO 2 in terms of is more than 0.1 part by weight, the hysteresis is large (0033) is recognized, and a compositional formula different from the compositional formula of the present invention. Vanadium oxide is essential, and Mn is higher than that of the patent document. It is what
  • Non-Patent Document 1 a ceramic composition similar to the piezoelectric ceramic composition of the present invention is specified.
  • This reference is a reference for evaluating the pyro effect, and the manganese characteristics are added in the section of the conclusion (Conclusion) regarding the piezoelectric characteristics (Na 0.5 , Bi 0.5 ) 1-x Ca x Bi 4 Ti 4 O 15 system.
  • the piezoelectric characteristics Na 0.5 , Bi 0.5 ) 1-x Ca x Bi 4 Ti 4 O 15 system.
  • high piezoelectric characteristics were obtained compared to quartz, there is no description regarding hysteresis.
  • the description about the bismuth layered compound modified especially with calcium is recognized.
  • the manufacturing methods of the above three cases are almost the same. Moreover, there is no mention about the influence which it has on the hysteresis by the spreading
  • the present invention provides a material composition of a piezoelectric ceramic composition including these diffusion states and means for producing the piezoelectric ceramic composition.
  • the electrode material and its application method greatly affect the piezoelectric ceramic composition.
  • the composition of the electrode material changes the properties of the porcelain composition by its application conditions and diffusion into the material.
  • This composition changes the hysteresis and the insulation resistance.
  • the manufacturing method in consideration of the influence of diffusion is important and is provided by the present invention.
  • a physical fixing method such as plating, sputtering, and vapor deposition has been generally used for the electrode material and the application method thereof.
  • the present invention has been made in view of such circumstances, and a piezoelectric ceramic composition and a manufacturing method thereof, particularly a piezoelectric ceramic suitable for pressure detection having a low hysteresis of a generated charge amount with respect to pressure and an equivalent piezoelectric constant within a specific range. It is an object of the present invention to provide a composition and a method for producing the composition. More specifically, attention was paid to a porcelain composition composed of two types of A and B components having different charge generation tendencies. In particular, the problem is solved by controlling the blending ratio of the two A components and the B component within a certain range.
  • a composition formula of a porcelain composition comprising two types of A component and B component having different charge generation tendencies with respect to applied pressure and decompression force, (1-y) ⁇ (Na 0.5 , Bi 0.5 ) 0.95 Ca 0.05 Bi 4 Ti 4 O 15 +0.2 Wt% Mn ⁇ as component A, (y) SrBi 4 Ti 4 O 15
  • the range of y that determines the blending ratio of the A component and the B component is 0.05 ⁇ y ⁇ 0.4.
  • This is a calcined powder in which the A component and the B component are each calcined powder, and the calcined powder is prepared, mixed, sized, molded and fired at a blending ratio of y.
  • a piezoelectric ceramic composition within ⁇ 0.1%.
  • composition formula of the porcelain composition which consists of 2 types of A component and B component from which the generation
  • the range of y that determines the blending ratio of the A component and the B component is 0.05 ⁇ y ⁇ 0.4.
  • the y is effectively provided by the piezoelectric ceramic composition as described above, wherein the y is 0.05 ⁇ y ⁇ 0.25.
  • the composition formula of the porcelain composition comprising two types of A component and B component, which have different charge generation tendencies with respect to the applied pressure and the reduced pressure, (1-y) ⁇ (Na 0.5 , Bi 0.5 ) 0.95 Ca 0.05 Bi 4 Ti 4 O 15 +0.2 Wt% Mn ⁇ as component A, (y) SrBi 4 Ti 4 O 15
  • the range of y that determines the blending ratio of the A component and the B component is 0.05 ⁇ y ⁇ 0.4.
  • the y is effectively provided by the method for producing a piezoelectric ceramic composition as described above, wherein the y is 0.05 ⁇ y ⁇ 0.25.
  • the above-described piezoelectric ceramic composition and the method for producing the same are effectively provided.
  • it is effectively provided by the method for producing a piezoelectric ceramic composition as described above, which comprises a step of forming an electrode using a conductive resin for preventing diffusion of a constituent of the electrode material in the post-firing polarization.
  • the electrode material is water-soluble with silver powder as a baked type electrode material that can be baked at a heat-resistant Curie temperature or lower that does not deteriorate the performance of the polarization state. It is effectively provided by the method for producing a piezoelectric ceramic composition as described above, which comprises a step of using a conductive resin material.
  • a composition formula of a porcelain composition composed of two types of A component and B component having different charge generation tendencies with respect to the applied pressure and the reduced pressure force (1-y) ⁇ (Na 0.5 , Bi 0.5 ) 0.95 Ca 0.05 Bi 4 Ti 4 O 15 +0.2 Wt% Mn ⁇ as component A, (y) SrBi 4 Ti 4 O 15
  • the range of y that determines the blending ratio of the A component and the B component is 0.05 ⁇ y ⁇ 0.4.
  • a conductive resin material is printed and applied, dried, and after the element is subjected to polarization treatment, the resin is removed with water, an organic solvent or the like, and a new electrode is provided to impart heat resistance of the electrode.
  • the material below the Curie temperature of the piezoelectric ceramic composition it was possible to eliminate the modification of the piezoelectric ceramic composition due to the electrode composition.
  • after firing it is possible to roughen the electrode surface portion of the fired body without using an electrode, and to perform polarization treatment from the surface, thereby generating a pressure with an equivalent piezoelectric constant within a specific range. It has become possible to minimize the hysteresis of the porcelain composition in which the hysteresis of the charge amount is within ⁇ 0.1%.
  • the generated charge amount hysteresis may differ in magnitude relationship between the generated charge amount when the pressure is increased and when the pressure is decreased.
  • Porcelain compositions composed of two types of component A and component B, which have different charge generation tendencies with respect to the applied pressure and the reduced pressure, are calcined powders with the respective components, and the calcined powders are blended at a blending ratio y.
  • a piezoelectric ceramic composition having a hysteresis of ⁇ 0.1% or less and a method for producing the same were provided.
  • FIG. 1 is an explanatory diagram of the concept of hysteresis of the present invention.
  • FIG. 2 is an explanatory diagram showing the state of the amount of charge generated by pressure.
  • FIG. 3 is an explanatory diagram showing an enlarged portion of the explanatory diagram of FIG.
  • FIG. 4 is an explanatory diagram showing the state of the amount of charge generated by pressure.
  • FIG. 5 is an explanatory diagram showing an enlarged portion of the explanatory diagram of FIG.
  • FIG. 6 is an explanatory diagram of a hysteresis value measuring apparatus diagram.
  • FIG. 7 is an explanatory diagram showing hysteresis values with respect to changes in drive frequency.
  • FIG. 1 is a diagram for explaining the definition of the hysteresis value of the present invention.
  • FIG. 5 is a relationship diagram of pressure-generated charge amount with pressure (Force) P on the horizontal axis and generated charge amount (Electric Charge Output) Q on the vertical axis.
  • Pressure P (N) and generated charge amount Q (pC) are their zero origin a, and maximum points b of both pressure P (N) and generated charge amount Q are shown. Is drawn between the origin a and the maximum point b. These two curves represent the state of hysteresis found in so-called piezoelectric ceramic compositions and magnetic materials.
  • the lower curve 1 shows the relationship between the origin a, the intermediate point d of the pressure, and the generated charge amount Q generated by increasing the pressure P (upward arrow 3 in the figure).
  • the upper curve 2 shows the relationship between the maximum point b, the intermediate point c of the pressure, and the generated charge amount Q generated when the pressure P is reduced (downward arrow 4 in the figure).
  • Hysteresis is obtained as the magnitude between the midpoints c and d of these pressures (up and down in the figure). In examples such as quartz, this hysteresis width is represented as zero. However, in general, a piezoelectric ceramic has a unique hysteresis phenomenon and the width is large.
  • the hysteresis value in the present invention is defined as follows.
  • the pressure P (N) at the maximum point b is Fmax, and the generated charge amount Q (pC) is Qmax.
  • the generated charge amount Q (pC) at the intermediate point of the pressure P (N) is Qdown at the intermediate point c of the upper curve 2 and Qup at the intermediate point d of the lower curve 1
  • the hysteresis value HyQ (%) Is represented by the following equation (1).
  • HyQ (%) ⁇
  • HyQ (%) is expressed as a plus and minus range in equation (2), When subtracting Qup from Qdown, if it is positive, it is positive, that is, Qdown> Qup. If it is negative, the opposite is the case (minus Qdown ⁇ Qup).
  • FIG. 3 and FIG. 5 show how the hysteresis value (HyQ) increases or decreases.
  • FIG. 2 and FIG. 4 are explanatory views showing the state of the charge amount Q (pC) generated by the pressure P (N).
  • the hysteresis value (HyQ) is extremely small, the upper and lower curves overlap and exhibit a substantially linear state.
  • the generated charge amount Q is obtained at a pressure of 50 N.
  • FIG. 3 shows the case where the vicinity of the intermediate point of the pressure in FIG. 2 is enlarged and displayed near the intermediate point of the enlarged display (expa.part expansion of figure 2).
  • the upward curve 1 (dotted line Qup of the upward arrow 3 in the figure) is shown from the generated charge amount Q (about 572 pC), and the relationship increases almost linearly.
  • FIG. 4 shows the case where the vicinity of the intermediate point of the pressure P in FIG. 4 is enlarged and displayed (expa.part expansion of figure 4).
  • the pressure P 25.6N and the generated charge amount Q (about 636 pC) from the upward curve 1 (dotted line Qup of the upward arrow 3 in the figure). ) And the relationship increases almost linearly.
  • FIG. 6 shows the hysteresis measuring device 18 at the pressure P (N) and the generated charge amount (pC).
  • the piezoelectric ceramic composition 5 is sandwiched and attached by an upper contact jig 6 and a lower contact jig 7.
  • the upper contact jig 6 is attached to a bias pressure application motor 12 via a precision pressure application actuator 8 and a connecting linear guide 11.
  • the lower contact jig 7 is attached to a load cell 10 for bias pressure measurement via a crystal force sensor 9 for precise pressure measurement.
  • the calculation processing waveform display condition input computer 13 is connected to the bias pressure application motor 12 via the power control device 14 and the cable 17. Similarly, the calculation processing waveform display condition input computer 13 is connected to the charge amplifier 15 and displays the output from the piezoelectric ceramic composition 5 via the upper contact jig 6 and the lower contact jig 7. On the other hand, the crystal pressure sensor 9 for precision pressure measurement and the load cell 10 for bias pressure measurement are connected to a computer 13 for calculation processing waveform display condition input via an amplifier signal measuring device 16.
  • a signal necessary for the calculation is obtained from the signal (pressure: N) of the crystal force sensor 9 for precision pressure measurement and the signal (generated charge amount: pQ) of the charge amplifier 15.
  • the set of the measurement sample 5 (piezoelectric ceramic composition) is sandwiched and attached by the upper contact jig 6 and the lower contact jig 7.
  • the precision pressure application actuator 8 is continuously driven at a constant frequency (standard is 10 Hz). Two seconds after the start of driving, the data (2000 points) of the pressure signal and generated charge amount signal in one cycle are taken in a PC (not shown) and processed.
  • the equivalent piezoelectric constant (d 33 ) is obtained from the generated charge amount Qmax (pC) at the maximum pressure P (N) (point b in FIG. 1).
  • a pressure value 1 ⁇ 2 of the maximum pressure (Fmax / 2, point d in FIG. 1) is determined.
  • the point d (Fmax / 2) is determined by the proportional distribution ratio between the two points.
  • the generated charge quantity Q at the point d is determined with the same proportional distribution ratio (point d in FIG. 1). This generated charge amount is Qup.
  • the piezoelectric ceramic composition produced by the present invention and the production method thereof will be described in detail.
  • the idea for reducing the influence of the electrode material of the present invention will be described in advance.
  • the hysteresis value of the ferroelectric ceramic composition is ideally zero.
  • the composition and its manufacturing method must satisfy extremely high conditions and cost measures. Therefore, the piezoelectric ceramic composition of the present invention and the method for producing the piezoelectric ceramic composition according to the present invention are studied by earnestly studying the conditions for achieving a composition that satisfies the above-mentioned countermeasures and the method for producing the composition while ensuring sufficient performance in terms of performance.
  • an electrode material and a method for applying the electrode material to the piezoelectric ceramic composition will be described.
  • the electrode material adhered to the piezoelectric ceramic composition that is, its component
  • diffusion to the piezoelectric ceramic composition must be suppressed as much as possible.
  • the reason for this is that when the electrode material is baked at a high temperature (700 ° C. to 900 ° C.), the glass frit component diffuses in the composition, although in a small amount. This diffusion may change the composition of the composition and change the properties of the piezoelectric ceramic composition.
  • the piezoelectric ceramic composition also has a problem of Curie temperature and insulation.
  • the Curie temperature is the temperature at which the ferroelectric (ferromagnetic) loses its ferroelectricity (ferromagnetism), but the bismuth layered compound used in the piezoelectric ceramic composition has a high Curie temperature and also has a coercive electric field. Since it is high, polarization treatment at a high temperature (near 200 ° C.) and a high electric field (50 kV / cm or more) is necessary. For this reason, it must have high insulation as a piezoelectric ceramic composition.
  • the electrode material a precious metal material and glass frit are used as a commonly used high-temperature firing (700 ° C. or higher) type.
  • the glass frit fixes the noble metal material.
  • the glass frit may diffuse into the piezoelectric ceramic composition and change the physical properties of the composition. As a result, it has a great influence on the insulation, and this also has a big influence on the hysteresis. For this reason, the electrode material used for a piezoelectric ceramic composition had the subject which must consider these compatibility.
  • a conductive resin is used as a solution to this problem.
  • the conductive resin an attempt was made to perform a polarization treatment method in which an electrode was formed so as to prevent diffusion of constituents of the electrode material.
  • the present invention has a background in which the necessity of a piezoelectric ceramic composition particularly requiring heat resistance is required. Therefore, it is also a fact that heat resistance cannot be obtained with a general conductive resin.
  • the electrode material of the present invention has been developed by solving the problem by developing a fired type that does not deteriorate the performance of the polarization state and has heat resistance and can be fired at a Curie temperature or lower. That is, the electrode material for polarization was solved by using a water-soluble conductive resin material containing silver powder.
  • the heat resistance of the electrode on the device could be obtained.
  • the electrode is applied onto the element with a screen printing tool, a hand-painting tool (brush, brush, etc.), and an electrode paste is formed.
  • the coated surface is dried with a hot air dryer, an oven, or the like, and baked at about 500 ° C. in an oven, a baking furnace, or the like.
  • the development of the electrode material and its application method finds a guideline that can provide a piezoelectric ceramic composition that meets the problems of the present invention and does not impair the deterioration of the piezoelectric characteristics (d 33 ) and the hysteresis, and a manufacturing method thereof. Became possible.
  • the composition of the present invention to be described later is particularly expensive even if it is a known piezoelectric ceramic composition. Manufacture is possible without using expensive electrode materials.
  • the composition within the above-mentioned range of the hysteresis value has a tendency to generate the generated charge amount Q with respect to the applied pressure that increases the pressure P (N) applied to the piezoelectric ceramic composition and the decompression force that decreases the pressure from the maximum pressure.
  • two types of piezoelectric ceramic compositions [porcelain composition (A) and porcelain composition (B)] are respectively calcined powders, which are prepared, mixed, sized and molded at a blending ratio y and fired. After forming the body, a polarizing conductive resin electrode is formed on the upper and lower parts of the fired body.
  • the piezoelectric ceramic composition was a combination of the later-described porcelain composition (A) and porcelain composition (B).
  • the selection conditions are parameters for the equivalent piezoelectric constant (d 33 ) and the hysteresis value (HyQ).
  • the composition of the porcelain composition (A) and the porcelain composition (B) was determined by observing the characteristics of the porcelain composition (A) and the porcelain composition (B).
  • the porcelain composition (A) and the porcelain composition (B) were studied under composition selection and other conditions. First, many candidates were considered for the A component and B component having different charge generation tendencies with respect to the applied pressure and the decompression force, but when the hysteresis value of the generated charge amount Q is within ⁇ 0.1%, the composition of the porcelain composition Has its limits.
  • the inventors decided on the following porcelain composition. (1-y) ⁇ (Na 0.5 , Bi 0.5 ) 0.95 Ca 0.05 Bi 4 Ti 4 O 15 +0.2 Wt% Mn ⁇ as component A, (y) SrBi 4 Ti 4 O 15 When expressed as B component, the range of y defining the blending ratio of A component and B component was combined so that 0.05 ⁇ y ⁇ 0.4.
  • the equivalent piezoelectric constant (d 33 ) and hysteresis value (HyQ) were confirmed. As shown in Table 1, a significant difference was observed in the hysteresis value (HyQ). That is, in the porcelain composition (A), the equivalent piezoelectric constant (d 33 ) is 23.1 pC / N, the hysteresis value (HyQ) is a positive value of 0.18 to 1.76%, and in the porcelain composition (B) The piezoelectric constant (d 33 ) was 10.9 pC / N, and the hysteresis value (HyQ) was a negative value of 21 to 44%. The measurement was performed with the d 33 -hysteresis evaluation apparatus shown in FIG. 6, and the frequency range was 0.5 to 50 Hz.
  • the hysteresis value (HyQ) becomes positive by selecting the porcelain composition (A).
  • the porcelain composition (B) is negative.
  • the hysteresis value (HyQ) can be offset by plus / minus and reduced by selecting a combination ratio by combining these.
  • the search for the electrode forming method and manufacturing conditions centered on the mixing ratio, but some solutions were obtained.
  • Ca is selected as the A component.
  • Ca is contained in alkaline earth metals, and in addition, Sr, Ba, Ra and the like are also contained. Among these, it was confirmed that Ca can raise the Curie point (Curie temperature) most in the piezoelectric ceramic composition of the present invention. Conversely, the inclusion of Sr, Ba, K + Bi, etc. also confirmed the adverse effect of lowering the Curie point.
  • the Curie point of the piezoelectric ceramic composition is a transition temperature at which the ferroelectric material changes to the paraelectric material when the temperature exceeds the Curie point. A high Curie point is a very important option because the piezoelectric ceramic can be used up to high temperatures.
  • the hysteresis value (HyQ) was also confirmed.
  • the combination of the A component and the B component was sought in order to achieve a hysteresis value (HyQ) within ⁇ 0.1%.
  • Ca is the most suitable alkaline earth metal that can be used. This is because other Ba and Sr have narrow tolerances for achieving within ⁇ 0.1%, and manufacturing difficulties have been recognized.
  • the piezoelectric ceramic composition of the present invention and the production method thereof will be specifically described in detail.
  • the porcelain composition was produced as described above for the compositions (A) and (B).
  • the raw materials used were bismuth oxide, titanium oxide, manganese oxide, strontium carbonate, calcium carbonate, sodium carbonate and the like having a purity of 3N.
  • the porcelain composition (A) and the porcelain composition (B) were separately weighed and prepared according to the respective composition formulas. Furthermore, each was separately mixed at room temperature with a dry mixer for 1 hour. Preliminary firing of each mixture was performed by keeping at 800 ° C. for 2 hours. A calcined powder of the porcelain composition (A) and the porcelain composition (B) was produced. The calcining temperatures of the porcelain composition (A) and the porcelain composition (B) may be different.
  • each calcined powder obtained was prepared at the following blending ratio and mixed with a ball mill, a dry powder mixer or the like.
  • the calcined powders of the porcelain composition (A) and the porcelain composition (B) were fractionated and mixed at each blending ratio (% by weight) shown in Table 2. These are represented by production example numbers.
  • the results are shown in Table 2 as Production Examples 1 to 6 (ex. 1 to 6).
  • the powder was formed by adding an organic binder such as polyvinyl alcohol and sizing with a spray dryer.
  • the sample was molded to an outer shape of about 4 mm and a thickness of about 1 mm. Thereafter, firing is performed. The firing temperature is kept at 1100-1150 ° C. for 2 hours.
  • the temperature increase / decrease rate was about 100 ° C./hour.
  • the ceramic composition (A) was set at a firing temperature at which the hysteresis value (HyQ) was positive.
  • the firing temperature condition for obtaining a plus is about 1120 to 1160 ° C, preferably about 1140 ° C.
  • the firing temperature at which the hysteresis value (HyQ) is negative was set for the porcelain composition (B).
  • the firing temperature condition is about 1120 to 1160 ° C, preferably about 1140 ° C.
  • the surface condition of the sample changes the hysteresis value. In order to keep it constant, it is desirable to polish or mirror-finish with an abrasive of # 2000 or more.
  • the thickness of the sample was 0.5 mm, there is no limitation as long as the thickness can maintain the fired state.
  • the obtained porcelain composition was screen-printed with a water-soluble conductive resin on the surface of the sample for polarization.
  • a water-soluble conductive resin material containing silver powder manufactured by NAMICS, product number: H9184
  • the film was dried at a thickness of 20 ⁇ m and a drying temperature of 100 ° C.
  • Polarization was performed in silicon oil at 160 ° C. and 6 kV / mm for 5 minutes.
  • the conductive resin was removed with a suitable solvent such as water, ethanol, isopropyl alcohol and dried.
  • a new silver paste (manufactured by Fuji Chemical Laboratory Co., Ltd., model: low-temperature sintered silver paste) was screen-printed, dried and baked at 450 ° C. for 10 minutes.
  • the electrodes of the piezoelectric ceramic composition were baked below the Curie temperature.
  • the obtained sample was measured for the equivalent piezoelectric constant (d 33 ) and hysteresis value (HyQ) with the apparatus shown in FIG.
  • an alternating pressure of a bias compression pressure of 250 N, a maximum pressure of 300 N, and a change pressure range (Fp-p) of 50 N was applied.
  • the drive frequency (Fd) was 0.5, 1, 5, 10, 15, 25, and 50 Hz.
  • Equivalent piezoelectric constant d 33 was measured with 10 Hz.
  • the hysteresis value HyQ was measured at each frequency.
  • Table 3 The measurement results are shown in Table 3, and the graph is expressed as FIG.
  • the vertical axis represents the hysteresis value Magnitude of Hysteresis (HyQ), and the horizontal axis represents the drive frequency (Fd).
  • the hysteresis value HyQ was fluctuated due to the difference in the blending ratio of the porcelain composition (A) and the porcelain composition (B) obtained in the present invention. According to this, within the range of 0.05 ⁇ y ⁇ 0.4 (Production Examples 1 to 6), the hysteresis value (HyQ) is in the range of ⁇ 0.1% ⁇ (HyQ) ⁇ 0.1%. A place was obtained. That is, 0.08% in Production Example 1, 0.02% to 0.08% in Production Example 2, -0.01% to + 0.04% in Production Example 4, and -0.01% in Production Example 6 The measurement result was confirmed.
  • the equivalent piezoelectric constant d 33 of 20.6 to 22.8 pC / N was obtained in Production Examples 1 to 6, and it was confirmed that it was 10 times that of quartz.
  • the (HyQ) value could be kept low with a wide bandwidth with a driving frequency of 5 to 50 Hz.
  • HyQ could be kept low in a high driving frequency band such as a driving frequency of 25 to 50 Hz.
  • FIG. 7 is created from Table 3. 6 shows the relationship between the hysteresis value (HyQ) and the drive frequency (Fd) for Production Examples 1 to 6.
  • the vertical axis represents the hysteresis value (HyQ), and the horizontal axis represents the drive frequency (Fd).
  • Production Example 3 has a wide driving frequency (Fd) range in which the hysteresis value is within ⁇ 0.1%. It will be recognized that production examples 1, 2, 4 and 5 follow this as well.
  • These can be understood as information depending on the blending ratio of the porcelain composition (A) and the porcelain composition (B). That is, an effect that the hysteresis value can be further reduced in the range of y, 0.05 ⁇ y ⁇ 0.4, preferably 0.05 ⁇ y ⁇ 0.25 is recognized.
  • the porcelain composition (A) and the porcelain composition (B) respective samples were prepared under the following conditions and procedures.
  • the molding was performed in a disk shape having an outer diameter of 4 mm, a thickness of 2.5 mm, and a density of 4.9 g / cm 3. Firing was performed using alumina sheath at 1130 ° C. for 2 hours. Further, it was polished to a thickness of 2 mm with an abrasive # 3000.
  • the piezoelectric ceramic composition is produced by forming a fired body from the ceramic composition (A) and the ceramic composition (B). A rough surface is created on the surface of the electrode portion of the fired body. A rough surface (surface roughness) is formed on the surface of the fired body with the abrasive.
  • a piezoelectric element needs to be provided with a polarization electrode.
  • the electrode for polarization is not required by polishing the electrode portion of the element with an abrasive.
  • Such a rough surface portion can be polarized by directly contacting a polarization power supply terminal to obtain a piezoelectric element.
  • the electrode portion of the piezoelectric ceramic composition is required to be roughened with an abrasive.
  • the present inventors have found the conditions and obtained the prospect of practical use. Table 4 shows the types of polishing agents and the polishing results.
  • the equivalent piezoelectric constant d 33 and hysteresis value (HyQ) are shown in Table 4. Viewed in comparison with those using a so-called silver electrodes, d 33 is has about 80% lower without the variation about a and usage issues between elements. HyQ was found to be in the range of ⁇ 0.1% ⁇ (HyQ) ⁇ 0.1% as compared with # 1000 and # 3000, and slightly exceeded at # 600. It can be understood that there is no problem if the abrasive is roughened by using a slightly finer material.
  • the y parameter is effective within the range of 0.05 ⁇ y ⁇ 0.4. Desirably, y was more effective when 0.05 ⁇ y ⁇ 0.25. On the other hand, if y is less than 0.05 or more than 0.4, the equivalent piezoelectric constant tends to be small and cannot be used.
  • the material of the present invention has industrial applicability as a pressure sensor sensing element.
  • a pressure sensor sensing element since it is a material having a high Curie temperature, it is effective as a detection element of a pressure sensor for detecting engine combustion pressure of an automobile having a pressure fluctuation corresponding to the engine speed of 10 Hz or more (600 rpm or more). It is expected as an element with high sensitivity, high accuracy, and high temperature resistance.
  • a sensing element in a low frequency region (10 Hz or less) it can be expected as a general-purpose high-sensitivity and high-precision differential pressure sensor.
  • the production method of the present invention is effective as a production method that is not limited to electrode forming equipment or expensive electrode materials even with known porcelain compositions. In addition, it can be manufactured in large to small quantities and can be expected as a pressure sensing element used in a wide range of fields.

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  • Ceramic Engineering (AREA)
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  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
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Abstract

La présente invention concerne, en particulier, une composition de céramique piézoélectrique présentant une faible hystérèse en termes de quantité de charge électrique générée par rapport à la pression, et une constante piézoélectrique équivalente élevée, ainsi que son procédé de production. L'invention concerne une composition de céramique piézoélectrique comprenant deux types de constituants, un constituant A et un constituant B présentant des tendances différentes en termes de génération de charge en réponse à une force de compression et une force de décompression, (1-y) {(Na0,5,Bi0,5)0,95Ca0,05Bi4Ti4O15 + 0,2 % en pds de Mn} étant le constituant A, et (y) SrBi4Ti4O15 étant le constituant B, la plage pour y étant de 0,05 ≤ y ≤ 0,4, ladite composition de céramique piézoélectrique présentant une constante piézoélectrique équivalente dans une plage spécifique et une hystérèse de ± 0,1 % ou moins.
PCT/JP2013/065922 2013-05-29 2013-06-10 Composition de céramique piézoélectrique et son procédé de production WO2014192164A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0648825A (ja) * 1992-07-31 1994-02-22 Toyota Motor Corp ビスマス層状化合物
JPH1129356A (ja) * 1997-07-09 1999-02-02 Murata Mfg Co Ltd 圧電磁器組成物
JP2001158663A (ja) * 1999-11-30 2001-06-12 Kyocera Corp 圧電磁器組成物
WO2009122916A1 (fr) * 2008-03-18 2009-10-08 京セラ株式会社 Céramique piézoélectrique et élément piézoélectrique utilisant celle-ci
JP2010013295A (ja) * 2008-07-01 2010-01-21 Kyocera Corp 圧電磁器およびそれを用いた圧電素子
JP2010030832A (ja) * 2008-07-29 2010-02-12 Kyocera Corp 圧電磁器およびそれを用いた圧電素子

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0648825A (ja) * 1992-07-31 1994-02-22 Toyota Motor Corp ビスマス層状化合物
JPH1129356A (ja) * 1997-07-09 1999-02-02 Murata Mfg Co Ltd 圧電磁器組成物
JP2001158663A (ja) * 1999-11-30 2001-06-12 Kyocera Corp 圧電磁器組成物
WO2009122916A1 (fr) * 2008-03-18 2009-10-08 京セラ株式会社 Céramique piézoélectrique et élément piézoélectrique utilisant celle-ci
JP2010013295A (ja) * 2008-07-01 2010-01-21 Kyocera Corp 圧電磁器およびそれを用いた圧電素子
JP2010030832A (ja) * 2008-07-29 2010-02-12 Kyocera Corp 圧電磁器およびそれを用いた圧電素子

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