WO2014192164A1 - Piezoelectric ceramic composition and production method therefor - Google Patents
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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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- 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
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- 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
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- 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
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3208—Calcium oxide or oxide-forming salts thereof, e.g. lime
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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
- C04B2235/3205—Alkaline earth oxides or oxide forming salts thereof, e.g. beryllium oxide
- C04B2235/3213—Strontium oxides or oxide-forming salts thereof
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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
- C04B2235/3262—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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Abstract
The present invention relates, in particular, to a piezoelectric ceramic composition having a low hysteresis in the amount of electric charge generated with respect to pressure, and a large equivalent piezoelectric constant, as well as a production method therefor. Provided is a piezoelectric ceramic composition comprising two types of components, an A component and a B component having different charge generation tendencies in response to a compression force and a decompression force, (1-y) {(Na0.5,Bi0.5)0.95Ca0.05Bi4Ti4O15 + 0. 2 Wt% Mn} being the A component, and (y) SrBi4Ti4O15 being the B component, wherein the range for y is 0.05 ≤y ≤ 0.4, said piezoelectric ceramic composition having an equivalent piezoelectric constant within a specific range and a hysteresis of ±0.1% or less.
Description
本発明は、圧電磁器組成物及びその製造方法、特に圧力に対する発生電荷量の低ヒステリシス、かつ、大きな等価圧電定数を有する圧力検知に好適な圧電磁器組成物及びその製造方法に関する。また、本発明における「特定範囲内の等価圧電定数を有する」とは、等価圧電定数d33として少なくとも20pC/N以上35pC/N以下と定義する。
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. Also, "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.
従来、圧力検知素材として水晶や強誘電特性のある圧電磁器組成物が用いられてきた。前者の水晶はヒステリシスが”0”(以下「ゼロ」という)であるが、等価圧電定数(d33)は極めて低く(約2pC/N)、圧力検知に好適な素材とは言えなかった。
後者の強誘電特性のある圧電磁器組成物では、後述する本発明のような組成物での等価圧電定数(d33)が大きく、かつ、低ヒステリシス特性に着目した特許文献1ないし4及び非特許文献1が知られている。しかしながら、これら従来技術では、本発明のような作用効果を具備した圧電磁器組成物は得られていなかった。 Conventionally, 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, andPatent 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.
後者の強誘電特性のある圧電磁器組成物では、後述する本発明のような組成物での等価圧電定数(d33)が大きく、かつ、低ヒステリシス特性に着目した特許文献1ないし4及び非特許文献1が知られている。しかしながら、これら従来技術では、本発明のような作用効果を具備した圧電磁器組成物は得られていなかった。 Conventionally, 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
特許文献1(特許文献2はその対応米国出願)によれば、圧力に対する発生電荷量について「・・ヒステリシスの発生もない。」(0011)との記載が認められる。また、図3においてヒステリシスの大きさについて、Mnの作用効果を挙げているが(0018)、そこには「Mnの量が0.02重量%より少ないと感度が急激に低下し、Mnの量が0.25重量%を超えると急激にヒステリシスが生じることが明らか」でありとの記載が認められる。さらに、同発明の構成として「マンガンがMnOとして0.02~0.25重量%含有されていることを特徴とするビスマス層状化合物」を請求項に挙げている。これは明らかに、同特許文献1に示された「高感度と低ヒステリシスを両立できること」の作用効果を発揮しているものとは認められない。したがって、「ヒステリシスを生じることなく感度を向上できる。」旨の記載はあるがこれらは、低ヒステリシスについてMnによる作用効果を挙げているだけでヒステリシスに関して課題解決を図ったものではない。
According to 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. In addition, in 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. Further, as a constitution of the invention, “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. Obviously, it cannot be recognized that the effect of “capability of achieving both high sensitivity and low hysteresis” as shown in Patent Document 1 is exhibited. Therefore, although there is a statement that “sensitivity can be improved without causing hysteresis”, these merely indicate the effect of Mn with respect to low hysteresis, but do not attempt to solve the problem with respect to hysteresis.
その理由は、Mnのみならず他の成分、(Sr1-2xNaxBi4+x)Ti4O15からなる強誘電体組成物は、本来ヒステリシスを有し、xの量によりその結晶構造が変化することでヒステリシス、感度も変化する。また、ヒステリシスや感度は、その評価のために付与される電極材料構成物質の内部拡散による影響を含んだ構成組成物の状態で決定される特性でもある。よって、これらを包含した作用効果により低ヒステリシスと高感度を達成できるものであり、本発明によってのみ課題解決が図られるものである。
The reason is that 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.
また、特許文献3によれば、ヒステリシスを定義して本発明の組成式と異なる組成式
[Bi4Ti3O12・α[(1-β)MTiO3+βBiFeO3]にて圧電特性の課題を解決している旨記載されている。
同特許文献3による課題解決策は、「Mnの量はMnO2換算で0.1質量部以下であることが好ましい。MnO2換算のMn量が0.1質量部より多いと、ヒステリシスが大きくなるおそれがある。」(0033)との記載も認められる。
しかしながら、本発明は、Mnの量はzwt%(zとしては0.2wt%に限定)(ビスマス層状化合物の主成分[(Na0.5 ,Bi0.5)1-xMxBi4Ti4O15]の100質量部に対するwt%と定義する。)である。この範囲は同特許文献には否定された範囲内で課題解決を図ったものであり、本発明によってのみ課題解決が図られるものである。主たる組成が異なることは結晶構造も異なることである。よって、本発明とMnの効果も同じになるとは言えない。 In addition, according toPatent Document 3, the problem of piezoelectric characteristics is defined by a composition formula [Bi 4 Ti 3 O 12 · α [(1-β) MTiO 3 + βBiFeO 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 thepatent 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.
However, according to the present invention, 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.
[Bi4Ti3O12・α[(1-β)MTiO3+βBiFeO3]にて圧電特性の課題を解決している旨記載されている。
同特許文献3による課題解決策は、「Mnの量はMnO2換算で0.1質量部以下であることが好ましい。MnO2換算のMn量が0.1質量部より多いと、ヒステリシスが大きくなるおそれがある。」(0033)との記載も認められる。
しかしながら、本発明は、Mnの量はzwt%(zとしては0.2wt%に限定)(ビスマス層状化合物の主成分[(Na0.5 ,Bi0.5)1-xMxBi4Ti4O15]の100質量部に対するwt%と定義する。)である。この範囲は同特許文献には否定された範囲内で課題解決を図ったものであり、本発明によってのみ課題解決が図られるものである。主たる組成が異なることは結晶構造も異なることである。よって、本発明とMnの効果も同じになるとは言えない。 In addition, according to
Problem solution according to the
However, according to the present invention, 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.
特許文献4によれば、ヒステリシスについて、本発明の組成式と異なる組成式・・
Bi4Ti3O12・α[(1-β)M1TiO3・βM2M3O3 ]
にて圧電特性の課題が解決されている。また、同特許文献4表1によれば、試料26,47では、d33は20以上、ヒステリシスは0.11となっており、これに近い7、18ではd33は16、19、ヒステリシスは0.12程との記載が認められる。 According toPatent Document 4, with respect to hysteresis, a composition formula different from the composition formula of the present invention.
Bi 4 Ti 3 O 12 · α [(1-β) M1TiO 3 · βM2M3O 3 ]
The problem of piezoelectric characteristics has been solved. According to Table 1 ofPatent 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.
Bi4Ti3O12・α[(1-β)M1TiO3・βM2M3O3 ]
にて圧電特性の課題が解決されている。また、同特許文献4表1によれば、試料26,47では、d33は20以上、ヒステリシスは0.11となっており、これに近い7、18ではd33は16、19、ヒステリシスは0.12程との記載が認められる。 According to
Bi 4 Ti 3 O 12 · α [(1-β) M1TiO 3 · βM2M3O 3 ]
The problem of piezoelectric characteristics has been solved. According to Table 1 of
また、「VをV2O5換算では0.1~1.5質量部含有する、試料番号、No.3~10、12~14、16~19、23~29、31~38、40、41、43、44および46~49は、ヒステリシスが0.98%以下と非常に小さく、また、動的圧電定数(等価圧電定数の意味)d33が15.1pC/N以上を有し、25℃の動的圧電定数d33に対する-40および150℃の動的圧電定数d33の変化も±5%以内になった。」(0049)との記載が認められる。すなわち、酸化バナジウム(V2O5)を加えることで課題解決を図っている。
Further, “Sample Nos. 3 to 10, 12 to 14, 16 to 19, 23 to 29, 31 to 38, 40, containing 0.1 to 1.5 parts by mass in terms of V 2 O 5 ,” 41, 43, 44 and 46 to 49, the hysteresis of 0.98% or less and very small and dynamic (equivalent meanings piezoelectric constant) the piezoelectric constant d 33 has a higher 15.1pC / N, 25 change in ° C. dynamic piezoelectric constant d 33 relative to -40 and 0.99 ° C. dynamic piezoelectric constant d 33 became within ± 5%. "is observed wherein the (0049). That is, the problem is solved by adding vanadium oxide (V 2 O 5 ).
しかしながら、酸化バナジウムを必須とした点、「Mnの量はMnO2換算で0.1質量部以下であることが好ましい。MnO2換算のMn量が0.1質量部より多いと、ヒステリシスが大きくなるおそれがある。」(0033)との記載も認められ、本発明の組成式と異なる組成式 酸化バナジウムを必須とした点、Mnを同特許文献より高い点でも本発明によってのみ課題解決が図られるものである。
However, that was essential vanadium oxide, 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
非特許文献1によれば、本発明の圧電磁器組成物と同様な磁器組成物が明示されている。この文献は、パイロ効果を評価した文献であり、圧電特性について結論(Conclusion)の項でマンガンを添加した(Na0.5 ,Bi0.5)1-xCaxBi4Ti4O15系組成物の特性の記載がある。
しかしながら、水晶に比べ高い圧電特性が得られたことは明記されているがヒステリシスに関する記載はない。なお、同非特許文献1に付言すれば、特にカルシウムで修飾されたビスマス層状化合物についての記載が認められる。ここでは、マンガンを添加したことで高いキュリー温度(Tc=660~680℃)で低比誘電率(~130)、高い電気機械結合係数(k33=30~40%)、高い異方性(k33/k31=13~17%)を持ち焦電センサ材料として優れて作用効果を挙げている。 According to Non-PatentDocument 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. There is a description of the properties of the composition.
However, although it is clearly stated that high piezoelectric characteristics were obtained compared to quartz, there is no description regarding hysteresis. In addition, if it adds to the saidnonpatent literature 1, the description about the bismuth layered compound modified especially with calcium is recognized. Here, by adding manganese, a low dielectric constant (˜130), a high electromechanical coupling coefficient (k 33 = 30 to 40%), a high anisotropy (Tc = 660 to 680 ° C.) k 33 / k 31 = 13 to 17%), and it has excellent effects as a pyroelectric sensor material.
しかしながら、水晶に比べ高い圧電特性が得られたことは明記されているがヒステリシスに関する記載はない。なお、同非特許文献1に付言すれば、特にカルシウムで修飾されたビスマス層状化合物についての記載が認められる。ここでは、マンガンを添加したことで高いキュリー温度(Tc=660~680℃)で低比誘電率(~130)、高い電気機械結合係数(k33=30~40%)、高い異方性(k33/k31=13~17%)を持ち焦電センサ材料として優れて作用効果を挙げている。 According to Non-Patent
However, although it is clearly stated that high piezoelectric characteristics were obtained compared to quartz, there is no description regarding hysteresis. In addition, if it adds to the said
上記各文献にはそれぞれ次の解決課題があった。前述の3事例の製造方法は、ほぼ同じである。また、電極材料種についても圧電磁器組成物への拡散によるヒステリシスに与える影響についての言及はない。言い換えるとこの電極材料種についても圧電磁器組成物への拡散が課題解決として重要であることである。本発明はこれらの拡散状態を含めて圧電磁器組成物の材料組成及び製造手段を提供するにある。
Each of the above documents had the following problem to be solved. 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 | diffusion to a piezoelectric ceramic composition also about an electrode material kind. In other words, also for this electrode material type, diffusion into the piezoelectric ceramic composition is important as a solution to the problem. The present invention provides a material composition of a piezoelectric ceramic composition including these diffusion states and means for producing the piezoelectric ceramic composition.
特に圧力に対する発生電荷量の低ヒステリシスをゼロ近傍とするためには、後述するように主に材料組成、電極材料によって決定される。特に電極材料とその付与方法は、圧電磁器組成物へ大きく影響を与える。これは、電極材料を構成する組成物は、その付与条件と材料内への拡散が磁器組成物の性状を変化させることである。この組成物はヒステリシスの変化、絶縁抵抗を変化させる。このように拡散の影響に配慮した製造方法が重要であり、本発明により提供される。
従来、電極構成物の拡散を少なくする手段としては、電極材料及びその付与方法については、メッキ、スパッタリング、蒸着などの物理的固着方法が一般的であった。
これらは、設備、治工具等を含め製造条件を制約し、製造コストが高くなる傾向にあった。 In particular, in order to make the low hysteresis of the generated charge amount with respect to the pressure close to zero, it is mainly determined by the material composition and the electrode material as described later. In particular, the electrode material and its application method greatly affect the piezoelectric ceramic composition. This is because 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. Thus, the manufacturing method in consideration of the influence of diffusion is important and is provided by the present invention.
Conventionally, as a means for reducing the diffusion of the electrode composition, a physical fixing method such as plating, sputtering, and vapor deposition has been generally used for the electrode material and the application method thereof.
These limited production conditions including equipment, jigs and tools, and tended to increase production costs.
従来、電極構成物の拡散を少なくする手段としては、電極材料及びその付与方法については、メッキ、スパッタリング、蒸着などの物理的固着方法が一般的であった。
これらは、設備、治工具等を含め製造条件を制約し、製造コストが高くなる傾向にあった。 In particular, in order to make the low hysteresis of the generated charge amount with respect to the pressure close to zero, it is mainly determined by the material composition and the electrode material as described later. In particular, the electrode material and its application method greatly affect the piezoelectric ceramic composition. This is because 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. Thus, the manufacturing method in consideration of the influence of diffusion is important and is provided by the present invention.
Conventionally, as a means for reducing the diffusion of the electrode composition, a physical fixing method such as plating, sputtering, and vapor deposition has been generally used for the electrode material and the application method thereof.
These limited production conditions including equipment, jigs and tools, and tended to increase production costs.
本発明はかかる事情に鑑みなされたものであり、圧電磁器組成物及びその製造方法、特に圧力に対する発生電荷量の低ヒステリシス、かつ、特定範囲内の等価圧電定数を有する圧力検知に好適な圧電磁器組成物及びその製造方法を提供しようとするものである。
より、詳細には、電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物に着目した。特に、2種のA成分、B成分の配合比を一定範囲内に制御することで課題解決を図ったものである。 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.
より、詳細には、電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物に着目した。特に、2種のA成分、B成分の配合比を一定範囲内に制御することで課題解決を図ったものである。 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.
本発明は、加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とし、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とし、該焼成体に分極用導電性樹脂電極を形成させた圧電体とし、該圧電体を分極し、前記樹脂電極を分極後除去してその部位に圧電出力検出用電極を付与させた特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物により提供される。 In the present invention, 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 When expressed as the B component, 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 hysteresis having an equivalent piezoelectric constant within a specific range in which a piezoelectric body is formed with a conductive resin electrode, the piezoelectric body is polarized, the resin electrode is removed after polarization, and a piezoelectric output detection electrode is applied to the portion. Provided by the piezoelectric ceramic composition within ± 0.1%.
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とし、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とし、該焼成体に分極用導電性樹脂電極を形成させた圧電体とし、該圧電体を分極し、前記樹脂電極を分極後除去してその部位に圧電出力検出用電極を付与させた特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物により提供される。 In the present invention, 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 When expressed as the B component, 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 hysteresis having an equivalent piezoelectric constant within a specific range in which a piezoelectric body is formed with a conductive resin electrode, the piezoelectric body is polarized, the resin electrode is removed after polarization, and a piezoelectric output detection electrode is applied to the portion. Provided by the piezoelectric ceramic composition within ± 0.1%.
また、加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とし、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とした後、前記焼成体の電極表面部位を粗面化させ、該表面から分極処理を行い、該表面に圧電出力検出用電極を付与させた特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物により提供される。 Moreover, the composition formula of the porcelain composition which consists of 2 types of A component and B component from which the generation | occurrence | production tendency of an electric charge differs with respect to pressurization force and pressure reduction 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 When expressed as the B component, 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, and then the electrode of the calcined body. A piezoelectric ceramic composition having a hysteresis within ± 0.1% within a specific range in which a surface portion is roughened, a polarization treatment is performed from the surface, and a piezoelectric output detection electrode is applied to the surface. Provided by the object.
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とし、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とした後、前記焼成体の電極表面部位を粗面化させ、該表面から分極処理を行い、該表面に圧電出力検出用電極を付与させた特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物により提供される。 Moreover, the composition formula of the porcelain composition which consists of 2 types of A component and B component from which the generation | occurrence | production tendency of an electric charge differs with respect to pressurization force and pressure reduction 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 When expressed as the B component, 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, and then the electrode of the calcined body. A piezoelectric ceramic composition having a hysteresis within ± 0.1% within a specific range in which a surface portion is roughened, a polarization treatment is performed from the surface, and a piezoelectric output detection electrode is applied to the surface. Provided by the object.
前記yが前記yが0.05≦y≦0.25であるである前記記載の圧電磁器組成物により効果的に提供される。
さらに、加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とする工程、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とする工程、該焼成後分極用導電性樹脂電極作製工程、この樹脂を分極後除去する工程、その上で圧電出力検出用電極を付与する工程の一連を行い特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物の製造方法により提供される。 The y is effectively provided by the piezoelectric ceramic composition as described above, wherein the y is 0.05 ≦ y ≦ 0.25.
Furthermore, 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 When expressed as the B component, 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 step of making each of the A component and the B component a calcined powder, a step of preparing the calcined powder by mixing, mixing, granulating, molding and firing the calcined powder at a blending ratio of y, after the firing ± 0.1% hysteresis with an equivalent piezoelectric constant within a specific range by conducting a series of steps of making a conductive resin electrode for polarization, removing the resin after polarization, and applying a piezoelectric output detection electrode on the resin It is provided by the method for producing a piezoelectric ceramic composition within the range.
さらに、加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とする工程、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とする工程、該焼成後分極用導電性樹脂電極作製工程、この樹脂を分極後除去する工程、その上で圧電出力検出用電極を付与する工程の一連を行い特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物の製造方法により提供される。 The y is effectively provided by the piezoelectric ceramic composition as described above, wherein the y is 0.05 ≦ y ≦ 0.25.
Furthermore, 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 When expressed as the B component, 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 step of making each of the A component and the B component a calcined powder, a step of preparing the calcined powder by mixing, mixing, granulating, molding and firing the calcined powder at a blending ratio of y, after the firing ± 0.1% hysteresis with an equivalent piezoelectric constant within a specific range by conducting a series of steps of making a conductive resin electrode for polarization, removing the resin after polarization, and applying a piezoelectric output detection electrode on the resin It is provided by the method for producing a piezoelectric ceramic composition within the range.
さらに、前記yが前記yが0.05≦y≦0.25であるである前記記載の圧電磁器組成物の製造方法により効果的に提供される。
である前記記載の圧電磁器組成物及びその製造方法により効果的に提供される。
さらにまた、前記焼成後分極において電極材料の構成物の拡散防止用導電性樹脂を用いて電極形成を行う工程からなる前記記載の圧電磁器組成物の製造方法により効果的に提供される。
また、前記拡散防止用導電性樹脂を分極後除去する工程後、電極材料として分極状態の性能劣化をさせない耐熱性のあるキュリー温度以下で焼成可能な焼成タイプの電極材料として銀粉末入りの水溶性導電性樹脂材料を用いる工程からなる前記記載の圧電磁器組成物の製造方法により効果的に提供される。 Furthermore, 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.
Furthermore, 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.
In addition, after the step of removing the conductive resin for preventing diffusion after 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.
である前記記載の圧電磁器組成物及びその製造方法により効果的に提供される。
さらにまた、前記焼成後分極において電極材料の構成物の拡散防止用導電性樹脂を用いて電極形成を行う工程からなる前記記載の圧電磁器組成物の製造方法により効果的に提供される。
また、前記拡散防止用導電性樹脂を分極後除去する工程後、電極材料として分極状態の性能劣化をさせない耐熱性のあるキュリー温度以下で焼成可能な焼成タイプの電極材料として銀粉末入りの水溶性導電性樹脂材料を用いる工程からなる前記記載の圧電磁器組成物の製造方法により効果的に提供される。 Furthermore, 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.
Furthermore, 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.
In addition, after the step of removing the conductive resin for preventing diffusion after 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.
加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とする工程、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とする工程、該焼成後、前記焼成体の電極表面部位を粗面化させる工程、該表面から分極処理を行い、その上で圧電出力検出用電極を付与する工程の一連を行い特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物の製造方法により提供される。 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 When expressed as the B component, 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 step of making each of the A component and the B component a calcined powder, a step of preparing the calcined powder by mixing, mixing, granulating, molding and firing the calcined powder at a blending ratio of y, after the firing A hysteresis process having an equivalent piezoelectric constant within a specific range by roughening the electrode surface portion of the fired body, performing a polarization process from the surface, and then applying a piezoelectric output detection electrode thereon Provided by the method for producing a piezoelectric ceramic composition within ± 0.1%.
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とする工程、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とする工程、該焼成後、前記焼成体の電極表面部位を粗面化させる工程、該表面から分極処理を行い、その上で圧電出力検出用電極を付与する工程の一連を行い特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物の製造方法により提供される。 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 When expressed as the B component, 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 step of making each of the A component and the B component a calcined powder, a step of preparing the calcined powder by mixing, mixing, granulating, molding and firing the calcined powder at a blending ratio of y, after the firing A hysteresis process having an equivalent piezoelectric constant within a specific range by roughening the electrode surface portion of the fired body, performing a polarization process from the surface, and then applying a piezoelectric output detection electrode thereon Provided by the method for producing a piezoelectric ceramic composition within ± 0.1%.
前記粗面化させる工程を前記粗面化させる工程を研磨粗度#600から#3000の範囲で研磨し、表面粗さが0.1から0.4μmに形成させた前記記載の圧電磁器組成物の製造方法により提供される。
The piezoelectric ceramic composition according to the above, wherein the roughening step is performed by polishing the roughening step in a polishing roughness range of # 600 to # 3000 to have a surface roughness of 0.1 to 0.4 μm. Provided by the manufacturing method.
本発明によれば、導電性樹脂系材料を印刷塗布、乾燥後、素子の分極処理を行った後、これら樹脂を水、有機溶剤等で除去し、電極の耐熱性を付与させるため新たな電極材料を圧電磁器組成物のキュリー温度以下で付加することで圧電磁器組成物の電極構成物による変性を無くすことができた。他方、焼成後、電極を使用せずに前記焼成体の電極表面部位を粗面化させ、該表面から分極処理を行うことも可能で、これらにより特定範囲内の等価圧電定数を有する圧力に対する発生電荷量のヒステリシスが±0.1%以内とする磁器組成物磁器組成物のヒステリシスを最小にすることが可能となった。
According to the present invention, 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. By adding 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. On the other hand, 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%.
また、発生電荷量のヒステリシスは、圧力を増圧する場合と減圧する場合で発生電荷量の大小関係が異なる場合がある。例えば、発生電荷量が増圧するときの電荷量>減圧するときの電荷量となる圧電磁器組成物と発生電荷量が増圧するときの電荷量<減圧するときの電荷量となる圧電磁器組成物がある。加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物を、それぞれの成分で仮焼き粉体とし、前記仮焼粉体を配合比yで調合、混合、整粒及び成型させ、これを焼成後分極用導電性樹脂電極を作製し、この樹脂を分極後除去してその上で圧電出力検出用電極を付与させた特定範囲内の等価圧電定数を有するヒステリシスが±0.1%以内とする圧電磁器組成物及びその製造方法を提供できた。
Also, 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. For example, a piezoelectric ceramic composition in which the charge amount when the generated charge amount is increased> a charge amount when reducing the pressure amount and a piezoelectric ceramic composition where the charge amount when the generated charge amount is increased <the charge amount when reducing the pressure amount are is there. 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. Mixing, sizing and molding, firing this to produce a conductive resin electrode for polarization, removing this resin after polarization, and then applying an equivalent piezoelectric constant within a specific range to which a piezoelectric output detection electrode was applied A piezoelectric ceramic composition having a hysteresis of ± 0.1% or less and a method for producing the same were provided.
以下、本発明を実施するための形態をもとに図面を参照しながら説明する。各図面に示される構成、部材、処理には、同一の符号を付するものとし、適宜重複した説明は省略する。また、実施をするための形態は、発明を限定するものではなく例示であって、実施の形態に記述されるすべての特徴やその組み合わせは、必ずしも発明の本質的なものであるとは限らない。以下、本発明を図1ないし図7を用いて具体的に説明する。
Hereinafter, description will be made with reference to the drawings based on the embodiments for carrying out the present invention. The configurations, members, and processes shown in the drawings are denoted by the same reference numerals, and repeated descriptions are omitted as appropriate. Further, the modes for carrying out the embodiments are merely examples, not limiting the invention, and all features and combinations thereof described in the embodiments are not necessarily essential to the invention. . Hereinafter, the present invention will be described in detail with reference to FIGS.
図1は本発明のヒステリシス値の定義を説明するための図である。横軸を圧力(Force)P、縦軸を発生電荷量(Electric Charge Output)Qとした圧力-発生電荷量の関係図である。圧力P(N)と発生電荷量Q(pC)それらのゼロとなる原点a、圧力P(N)と発生電荷量Qの双方の最大点bが示され、図には上側曲線と下側曲線を原点aと最大点bとの間に描いている。この2つの曲線はいわゆる圧電磁器組成物、磁性体らに見られるヒステリシスの様子を表したものである。
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.
下側曲線1は原点a、圧力の中間点d及び最大点bとの間を圧力Pを増加させることで発生する発生電荷量Qとの関係が描かれている(図の上向き矢印3)。他方、上側曲線2は最大点b、圧力の中間点c及び原点aとの間で圧力Pを減少させたとき発生する発生電荷量Qとの関係が描かれている(図の下向き矢印4)。ヒステリシスはこれら圧力の中間点c、dの間(図の上下間)の大きさとして求められる。水晶のような例ではこのヒステリシスの幅はゼロとして表される。しかしながら、一般に圧電磁器は特有のヒステリシス現象が発生しこの幅は大きくなっている。
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). On the other hand, 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.
具体的には、本発明におけるヒステリシス値を以下のように定義する。前記最大点bにおける圧力P(N)をFmax、発生電荷量Q(pC)をQmaxとする。圧力P(N)の中間点における発生電荷量Q(pC)を上側の曲線2の中間点cのときQdown、下側の曲線1の中間点dのときQupとすると、ヒステリシス値HyQ(%)は次式(1)で表される。
HyQ(%)=(Qdown-Qup)/Qmax×100 (1)
ここで・・
Qmax:最大の圧力P(N)のときに発生した電荷量Q(pC)
Qup:圧力Pを増加させるときに最大の圧力(Fmax)の1/2圧力(=Fmax/2)で発生したd点における電荷量Q(pC)
Qdown:圧力Pを減少させるときに最大の圧力(Fmax)の1/2圧力(=Fmax/2)で発生したc点における電荷量Q(pC)とする。 Specifically, 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. When the generated charge amount Q (pC) at the intermediate point of the pressure P (N) is Qdown at the intermediate point c of theupper 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 (%) = (Qdown−Qup) / Qmax × 100 (1)
here··
Qmax: the amount of charge Q (pC) generated at the maximum pressure P (N)
Qup: the amount of charge Q (pC) at point d generated at 1/2 pressure (= Fmax / 2) of the maximum pressure (Fmax) when the pressure P is increased
Qdown: Charge amount Q (pC) at point c generated at 1/2 pressure (= Fmax / 2) of the maximum pressure (Fmax) when the pressure P is decreased.
HyQ(%)=(Qdown-Qup)/Qmax×100 (1)
ここで・・
Qmax:最大の圧力P(N)のときに発生した電荷量Q(pC)
Qup:圧力Pを増加させるときに最大の圧力(Fmax)の1/2圧力(=Fmax/2)で発生したd点における電荷量Q(pC)
Qdown:圧力Pを減少させるときに最大の圧力(Fmax)の1/2圧力(=Fmax/2)で発生したc点における電荷量Q(pC)とする。 Specifically, 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. When the generated charge amount Q (pC) at the intermediate point of the pressure P (N) is Qdown at the intermediate point c of the
HyQ (%) = (Qdown−Qup) / Qmax × 100 (1)
here··
Qmax: the amount of charge Q (pC) generated at the maximum pressure P (N)
Qup: the amount of charge Q (pC) at point d generated at 1/2 pressure (= Fmax / 2) of the maximum pressure (Fmax) when the pressure P is increased
Qdown: Charge amount Q (pC) at point c generated at 1/2 pressure (= Fmax / 2) of the maximum pressure (Fmax) when the pressure P is decreased.
本発明にあっては、実質的にヒステリシス値HyQ=0となる範囲としてヒステリシス値HyQを、
HyQ(%)≦|0.1%| (2)
の範囲を得るべく鋭意研究の上以下の組成及びその製造方法により課題解決を図ったものである。また、(2)式ではHyQ(%)はプラス及びマイナスの範囲として表され、
QdownからQupを引くときそれが正ならプラス、すなわち、Qdown>Qupということになる。負ならこの逆でマイナス(Qdown<Qup)ということになる。詳細は以下に述べるが、ヒステリシス値(HyQ)はこの定義に従い説明する。 In the present invention, the hysteresis value HyQ is set as a range where the hysteresis value HyQ = 0 is substantially satisfied.
HyQ (%) ≦ | 0.1% | (2)
In order to obtain the above range, the present invention has been intensively studied to solve the problem by the following composition and production method thereof. In addition, 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). Although details will be described below, the hysteresis value (HyQ) will be described according to this definition.
HyQ(%)≦|0.1%| (2)
の範囲を得るべく鋭意研究の上以下の組成及びその製造方法により課題解決を図ったものである。また、(2)式ではHyQ(%)はプラス及びマイナスの範囲として表され、
QdownからQupを引くときそれが正ならプラス、すなわち、Qdown>Qupということになる。負ならこの逆でマイナス(Qdown<Qup)ということになる。詳細は以下に述べるが、ヒステリシス値(HyQ)はこの定義に従い説明する。 In the present invention, the hysteresis value HyQ is set as a range where the hysteresis value HyQ = 0 is substantially satisfied.
HyQ (%) ≦ | 0.1% | (2)
In order to obtain the above range, the present invention has been intensively studied to solve the problem by the following composition and production method thereof. In addition, 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). Although details will be described below, the hysteresis value (HyQ) will be described according to this definition.
次に、ヒステリシス値(HyQ)のプラスマイナスが発生する様子を図3及び図5として表したものである。ここで、図2及び図4は圧力P(N)により発生する電荷量Q(pC)の様子を示した説明図である。これらの図ではヒステリシス値(HyQ)が極めて微小な場合には上側及び下側曲線は重なり、ほぼ直線状態を呈する。このうち図2では、圧力50Nで発生電荷量Q(約1130pC)となっている。
Next, FIG. 3 and FIG. 5 show how the hysteresis value (HyQ) increases or decreases. Here, FIG. 2 and FIG. 4 are explanatory views showing the state of the charge amount Q (pC) generated by the pressure P (N). In these figures, when the hysteresis value (HyQ) is extremely small, the upper and lower curves overlap and exhibit a substantially linear state. In FIG. 2, the generated charge amount Q (about 1130 pC) is obtained at a pressure of 50 N.
図3は前記図2の圧力の中間点付近を拡大表示中間点付近を拡大表示(expa.part expansion of figure 2)した場合である。図3によれば、圧力N=24.8Nで、発生電荷量Q(約572pC)から、上向曲線1(図の上向き矢印3の点線Qup)が示され、その関係はほぼ直線に増加していく。他方、圧力P=24.8Nで、発生電荷量Q(約595pC)から、圧力Pを徐々に減少させていく下向曲線2(図の下向き矢印4の実線Qdown)が示され、ほぼ直線的に減少していく。
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). According to FIG. 3, at the pressure N = 24.8N, 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. To go. On the other hand, the downward curve 2 (solid line Qdown of the downward arrow 4 in the figure) in which the pressure P is gradually decreased from the generated charge amount Q (about 595 pC) at the pressure P = 24.8N is shown, which is almost linear. It will decrease to.
そして、圧力P=24.2Nで、発生電荷量Q(約580pC)となり、Qdown>Qupの状態を呈しヒステリシス値(HyQ)はプラスの値として計算される。この直線変化をより詳細に確認すると、図2では認められなかった、圧力P(N)の最大値の半分部分では、図3のような拡大図(expa)で見られるヒステリシスの様子を観察することができる。
Then, at the pressure P = 24.2N, the generated charge amount Q (about 580 pC) is obtained, the state of Qdown> Qup is exhibited, and the hysteresis value (HyQ) is calculated as a positive value. When this linear change is confirmed in more detail, the state of hysteresis seen in the enlarged view (expa) as shown in FIG. 3 is observed at a half portion of the maximum value of the pressure P (N), which was not recognized in FIG. be able to.
次に、図4も図2のようにヒステリシス値(HyQ)が極めて微小な場合には上側及び下側曲線は重なり、ほぼ直線状態を呈している。この例では、圧力P=50Nで発生電荷量Q(約1250pC)となっている。
図5は図4の前記圧力Pの中間点付近を拡大表示(expa.part expansion of figure 4)した場合である。図5によれば、図4の拡大表示(expa部分)の例では、圧力P=25.6Nで、発生電荷量Q(約636pC)から、上向曲線1(図の上向き矢印3の点線Qup)が示され、その関係はほぼ直線に増加していく。 Next, in FIG. 4 as well, when the hysteresis value (HyQ) is extremely small as shown in FIG. 2, the upper and lower curves are overlapped and almost linear. In this example, the generated charge amount Q (about 1250 pC) is obtained at a pressure P = 50N.
FIG. 5 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). According to FIG. 5, in the example of the enlarged display (expa portion) in FIG. 4, the pressure P = 25.6N and the generated charge amount Q (about 636 pC) from the upward curve 1 (dotted line Qup of theupward arrow 3 in the figure). ) And the relationship increases almost linearly.
図5は図4の前記圧力Pの中間点付近を拡大表示(expa.part expansion of figure 4)した場合である。図5によれば、図4の拡大表示(expa部分)の例では、圧力P=25.6Nで、発生電荷量Q(約636pC)から、上向曲線1(図の上向き矢印3の点線Qup)が示され、その関係はほぼ直線に増加していく。 Next, in FIG. 4 as well, when the hysteresis value (HyQ) is extremely small as shown in FIG. 2, the upper and lower curves are overlapped and almost linear. In this example, the generated charge amount Q (about 1250 pC) is obtained at a pressure P = 50N.
FIG. 5 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). According to FIG. 5, in the example of the enlarged display (expa portion) in FIG. 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
他方、圧力P=26.2N、発生電荷量Q(約646pC)から圧力Pを徐々に減少させていくと(図の下向き矢印4の実線Qdown)、発生電荷量Qは上側の曲線1と同様曲線2のカーブのように直線的に減少していく。そして、圧力P=25.6Nで、発生電荷量Q(約632pC)となる。この様子は図3と同様な様子として示されている。
また、図5は図3に比べ、Qup>Qdownの状態を呈しヒステリシス値(HyQ)はマイナスの値として計算される。 On the other hand, when the pressure P is gradually decreased from the pressure P = 26.2N and the generated charge amount Q (about 646 pC) (solid line Qdown of thedownward arrow 4 in the figure), the generated charge amount Q is the same as the upper curve 1. It decreases linearly like curve 2 curve. At a pressure P = 25.6 N, the generated charge amount Q (about 632 pC) is obtained. This state is shown as a state similar to FIG.
Further, FIG. 5 shows a state of Qup> Qdown as compared with FIG. 3, and the hysteresis value (HyQ) is calculated as a negative value.
また、図5は図3に比べ、Qup>Qdownの状態を呈しヒステリシス値(HyQ)はマイナスの値として計算される。 On the other hand, when the pressure P is gradually decreased from the pressure P = 26.2N and the generated charge amount Q (about 646 pC) (solid line Qdown of the
Further, FIG. 5 shows a state of Qup> Qdown as compared with FIG. 3, and the hysteresis value (HyQ) is calculated as a negative value.
図6は圧力P(N)と発生電荷量(pC)におけるヒステリシス計測装置18を示したものである。圧電磁器組成物5は上部コンタクト治具6と下部コンタクト治具7によりサンドイッチされ取り付けられている。上部コンタクト治具6は、精密圧力印加用アクチュエータ8、接続リニアガイド11を介してバイアス圧力印加用モータ12に取り付けられている。下部コンタクト治具7は、精密圧力計測用水晶フォースセンサ9を介してバイアス圧力計測用ロードセル10に取り付けられている。
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.
演算処理波形表示条件入力用コンピュータ13は電源制御装置14、ケーブル17を介してバイアス圧力印加用モータ12に接続されている。同様に、演算処理波形表示条件入力用コンピュータ13はチャージアンプ15に接続され上部コンタクト治具6と下部コンタクト治具7を介して圧電磁器組成物5からの出力を表示させる。他方、精密圧力計測用水晶フォースセンサ9及びバイアス圧力計測用ロードセル10はアンプ信号計測器16を介して演算処理波形表示条件入力用コンピュータ13に接続されている。
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.
つぎに、ヒステリシス計測装置を用いた圧力P(N)と発生電荷量Q(pC)の測定及び計算処理について説明する。
計算に必要な信号は、精密圧力計測用水晶フォースセンサ9の信号(圧力:N)とチャージアンプ15の信号(発生電荷量:pQ)から求められる。
測定試料5(圧電磁器組成物)のセットは上部コンタクト治具6と下部コンタクト治具7によりサンドイッチされ取り付ける。
セット後、精密圧力印加用アクチュエータ8は連続的に一定の周波数(標準は10Hz)で駆動させる。駆動開始から2秒後に一周期の圧力信号と発生電荷量信号のデータ(2000ポイント)は図示しないPCに取りこまれ演算処理される。 Next, measurement and calculation processing of the pressure P (N) and the generated charge amount Q (pC) using the hysteresis measuring device will be described.
A signal necessary for the calculation is obtained from the signal (pressure: N) of thecrystal 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 theupper contact jig 6 and the lower contact jig 7.
After the setting, the precisionpressure 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.
計算に必要な信号は、精密圧力計測用水晶フォースセンサ9の信号(圧力:N)とチャージアンプ15の信号(発生電荷量:pQ)から求められる。
測定試料5(圧電磁器組成物)のセットは上部コンタクト治具6と下部コンタクト治具7によりサンドイッチされ取り付ける。
セット後、精密圧力印加用アクチュエータ8は連続的に一定の周波数(標準は10Hz)で駆動させる。駆動開始から2秒後に一周期の圧力信号と発生電荷量信号のデータ(2000ポイント)は図示しないPCに取りこまれ演算処理される。 Next, measurement and calculation processing of the pressure P (N) and the generated charge amount Q (pC) using the hysteresis measuring device will be described.
A signal necessary for the calculation is obtained from the signal (pressure: N) of the
The set of the measurement sample 5 (piezoelectric ceramic composition) is sandwiched and attached by the
After the setting, the precision
以下図1を参照して演算処理につき説明する。最大の圧力P(N)のとき(図1のb点)の発生電荷量Qmax(pC)から等価圧電定数(d33)を求める。
次に最大圧力の1/2の圧力値(Fmax/2、図1のd点)を決める。
圧力を増す場合の例(図1の矢印3)では、1/2の圧力値(Fmax/2)に最も近い上と下の圧力値の2ポイントを決める。点d(Fmax/2)を2ポイント間の比例配分比で決める。同じ比例配分比で(図1のd点)、すなわち、点dにおける発生電荷量Qを決める。この発生電荷量がQupとなる。 Hereinafter, the arithmetic processing will be described with reference to FIG. 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).
Next, a pressure value ½ of the maximum pressure (Fmax / 2, point d in FIG. 1) is determined.
In the example of increasing the pressure (arrow 3 in FIG. 1), two points of the upper and lower pressure values closest to the 1/2 pressure value (Fmax / 2) are 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.
次に最大圧力の1/2の圧力値(Fmax/2、図1のd点)を決める。
圧力を増す場合の例(図1の矢印3)では、1/2の圧力値(Fmax/2)に最も近い上と下の圧力値の2ポイントを決める。点d(Fmax/2)を2ポイント間の比例配分比で決める。同じ比例配分比で(図1のd点)、すなわち、点dにおける発生電荷量Qを決める。この発生電荷量がQupとなる。 Hereinafter, the arithmetic processing will be described with reference to FIG. 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).
Next, a pressure value ½ of the maximum pressure (Fmax / 2, point d in FIG. 1) is determined.
In the example of increasing the pressure (
同様に圧力を減じる場合の例(図1の矢印4)では最大圧力の1/2の圧力値(図1のc点)の発生電荷量Qdownを決める。これらよりヒステリシスHyQが(1)式により計算される。
以上より1回目(n=1)のd33とHyQが得られる。
演算終了後、再度、同様に一周期のサンプリングを行い演算処理をする。これを50回(n=50)まで繰り返す。
得られた50回のデータを算術平均して被測定物のd33とHyQを決定する。有効数字としては、得られたd33(pC/N)は小数点以下2桁、HyQ(%)は3桁を採用した。 Similarly, in the case of reducing the pressure (arrow 4 in FIG. 1), the generated charge amount Qdown of the pressure value ½ of the maximum pressure (point c in FIG. 1) is determined. From these, the hysteresis HyQ is calculated by the equation (1).
From the above, d 33 and HyQ for the first time (n = 1) are obtained.
After the calculation is completed, the calculation process is performed again by sampling for one cycle. This is repeated up to 50 times (n = 50).
The resulting 50 times data by the arithmetic mean determining d 33 and HyQ of the object to be measured. As significant figures, d 33 (pC / N) obtained was 2 digits after the decimal point, and HyQ (%) was 3 digits.
以上より1回目(n=1)のd33とHyQが得られる。
演算終了後、再度、同様に一周期のサンプリングを行い演算処理をする。これを50回(n=50)まで繰り返す。
得られた50回のデータを算術平均して被測定物のd33とHyQを決定する。有効数字としては、得られたd33(pC/N)は小数点以下2桁、HyQ(%)は3桁を採用した。 Similarly, in the case of reducing the pressure (
From the above, d 33 and HyQ for the first time (n = 1) are obtained.
After the calculation is completed, the calculation process is performed again by sampling for one cycle. This is repeated up to 50 times (n = 50).
The resulting 50 times data by the arithmetic mean determining d 33 and HyQ of the object to be measured. As significant figures, d 33 (pC / N) obtained was 2 digits after the decimal point, and HyQ (%) was 3 digits.
本発明により作製される圧電磁器組成物及びその製造方法について詳細に述べる。
本発明の電極材料の影響を少なくするための工夫につき予め説明しておきたい。
強誘電体磁器組成物は理想的にはヒステリシス値がゼロが望ましい。しかしながら、組成物、その製法は極めて高度な条件、さらにコスト面対策をクリアしなければならない。そこで、性能的に充分な性能確保を図り、かつ、前記の対策にも合致した組成物及びその製造方法を達成するための条件を鋭意研究することにより本発明の圧電磁器組成物及びその製造方法を得ることができた。 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. However, 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. Could get.
本発明の電極材料の影響を少なくするための工夫につき予め説明しておきたい。
強誘電体磁器組成物は理想的にはヒステリシス値がゼロが望ましい。しかしながら、組成物、その製法は極めて高度な条件、さらにコスト面対策をクリアしなければならない。そこで、性能的に充分な性能確保を図り、かつ、前記の対策にも合致した組成物及びその製造方法を達成するための条件を鋭意研究することにより本発明の圧電磁器組成物及びその製造方法を得ることができた。 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. However, 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. Could get.
まず、ヒステリシス値としては、使用可能な範囲として、HyQ≦|0.1%|とするためにこれに影響を与える因子は(1)磁器組成物への電極材料及びその付与方法、(2)磁器組成物自体の開発とその製造条件の開発、さらに、(3)磁器組成物への電極材料を付与しない方法、すなわち、磁器組成物の表面処理についても検討を加えた。
First, as a hysteresis value, in order to satisfy HyQ ≦ | 0.1% | as a usable range, factors that affect this are (1) an electrode material and a method for applying the same to a porcelain composition, (2) We also studied the development of the porcelain composition itself and the production conditions thereof, and (3) the method of not applying the electrode material to the porcelain composition, that is, the surface treatment of the porcelain composition.
そこで、まず、(1)圧電磁器組成物への電極材料及びその付与方法につき述べる。
圧電磁器組成物に貼着される電極材料、すなわちその構成物については圧電磁器組成物への拡散を出来る限り抑制しなければならない。その理由は、電極材料は高温(700℃~900℃)で焼き付けるとき、特にガラスフリット成分が組成物内に微量ではあるが拡散する。この拡散により組成物の組成が変化し圧電磁器組成物の性状を変化させることがある。 First, (1) an electrode material and a method for applying the electrode material to the piezoelectric ceramic composition will be described.
With respect to 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.
圧電磁器組成物に貼着される電極材料、すなわちその構成物については圧電磁器組成物への拡散を出来る限り抑制しなければならない。その理由は、電極材料は高温(700℃~900℃)で焼き付けるとき、特にガラスフリット成分が組成物内に微量ではあるが拡散する。この拡散により組成物の組成が変化し圧電磁器組成物の性状を変化させることがある。 First, (1) an electrode material and a method for applying the electrode material to the piezoelectric ceramic composition will be described.
With respect to 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.
また、圧電磁器組成物はキュリー温度と絶縁性も課題となる。キュリー温度は強誘電体(強磁性体)が強誘電性(強磁性性)を失う(転移)温度を指すが、圧電磁器組成物に用いるビスマス層状化合物はキュリー温度が高く、なおかつ、抗電界も高いため高温度(200℃近傍)、高電界(50kV/cm以上)での分極処理が必要である。このため圧電磁器組成物として高い絶縁性を有しなければならない。
Also, 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.
また、電極材料は一般的に使用される高温焼成(700℃以上)タイプとして、貴金属材料とガラスフリットが用いられる。ガラスフリットは貴金属材料を固着させる。また、ガラスフリットは、圧電磁器組成物内部に拡散し組成物の物性を変化させることがある。その結果、絶縁性に大きな影響を与え、これによりヒステリシスにも大きな影響も生ずる。このため圧電磁器組成物に用いられる電極材料はこれらの適合性を考慮しなければならない課題があった。
Also, as 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. Further, 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.
本発明ではこの解決策として導電性樹脂を用いた。導電性樹脂は電極材料の構成物の拡散防止を図った電極形成を行う分極処理方法を試みた。また、本発明は特に耐熱性が必要な圧電磁器組成物とする必要性が求められる背景があった。したがって、一般的な導電性樹脂では耐熱性が得られないことも事実であった。
In the present invention, a conductive resin is used as a solution to this problem. For 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. In addition, 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.
そこで、導電性樹脂を用い、かつ、それを除去したのち、これに代わる電極材料を用いる方法を試みた。このため、本発明の電極材料は、分極状態の性能劣化をさせない、耐熱性がありキュリー温度以下で焼成可能な焼成タイプのものを開発しこの課題を解決した。すなわち、分極用電極材料は銀粉末入りの水溶性導電性樹脂材料を用いることで解決した。
Therefore, after using a conductive resin and removing it, an attempt was made to use an alternative electrode material. For this reason, 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.
この電極材料を使うことで素子上の電極の耐熱性を得ることができた。電極はスクリーン印刷用具、手塗り用具(刷毛、筆等)等で素子上に塗布し電極ペーストを形成させる。塗布面は熱風ドライヤー、オーブン等で乾燥させ、500℃程度でオーブン、焼き付け炉等で焼成する。このように、電極材料及びその付与方法の開発で圧電特性(d33)の低下とヒステリシスを損ねることがない本発明の課題に合致した圧電磁器組成物及びその製造方法を提供できる目安を見いだすことが可能となった。
By using this electrode material, 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. As described above, 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.
このように、焼成可能な焼成タイプの電極材料及び電極形成方法を用いることにより、後述する本発明の組成物には特に、さらに、既知の圧電磁器組成物であっても高価な電極形成設備や高価な電極材料を利用しなくても製造が可能となる。
As described above, by using a firing type electrode material and an electrode forming method that can be fired, 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.
さらに、(2)の圧電磁器組成物自体の開発とその製造条件については、次の実施例で詳細に説明する。
Further, the development of the piezoelectric ceramic composition itself (2) and the production conditions thereof will be described in detail in the following examples.
ヒステリシス値の前記範囲での組成物としては、圧電磁器組成物に与える圧力P(N)を増加させる加圧力と、圧力最大から圧力を減少させる減圧力に対し、発生電荷量Qの発生傾向が異なる2種の圧電磁器組成物の組み合わせに着目した。すなわち、圧電磁器組成物の2種[磁器組成物(A)及び磁器組成物(B)]をそれぞれ仮焼き粉体とし、それを配合比yで調合、混合、整粒及び成型をして焼成体とした後、その焼成体の上下部位に分極用導電性樹脂電極を形成させる。この樹脂は分極後除去され、その上で圧電出力検出用電極を付与させ圧電磁器組成物を得た。その結果、特定範囲内の等価圧電定数(d33)を有するとともに、圧力P(N)に対する発生電荷量Qのヒステリシス値が±0.1%以内となる圧電磁器組成物が得られる。
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. We paid attention to the combination of two different piezoelectric ceramic compositions. That is, 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. This resin was removed after polarization, and a piezoelectric output detecting electrode was applied thereon to obtain a piezoelectric ceramic composition. As a result, a piezoelectric ceramic composition having an equivalent piezoelectric constant (d 33 ) within a specific range and a hysteresis value of the generated charge amount Q with respect to the pressure P (N) is within ± 0.1% is obtained.
磁器組成物(A)及び磁器組成物(B)の選択
圧電磁器組成物は後述する磁器組成物(A)及び磁器組成物(B)の組み合わせとした。選択条件は等価圧電定数(d33)とヒステリシス値(HyQ)についてのパラメータである。それには、磁器組成物(A)及び磁器組成物(B)それぞれの特性を見ることで、磁器組成物(A)及び磁器組成物(B)の組成を決定した。確認手段として磁器組成物へ圧力Pを印加し、その出力を見ることと、ヒステリシス値に対しては、サイン波波形を印加して確認した。より、具体的には、圧力P=50Nを周波数0.5~50Hzの範囲で変化させた。 Selection of Porcelain Composition (A) and Porcelain Composition (B) 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). For that purpose, 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). As a confirmation means, the pressure P was applied to the porcelain composition, the output was observed, and the hysteresis value was confirmed by applying a sine wave waveform. More specifically, the pressure P = 50 N was changed in the frequency range of 0.5 to 50 Hz.
圧電磁器組成物は後述する磁器組成物(A)及び磁器組成物(B)の組み合わせとした。選択条件は等価圧電定数(d33)とヒステリシス値(HyQ)についてのパラメータである。それには、磁器組成物(A)及び磁器組成物(B)それぞれの特性を見ることで、磁器組成物(A)及び磁器組成物(B)の組成を決定した。確認手段として磁器組成物へ圧力Pを印加し、その出力を見ることと、ヒステリシス値に対しては、サイン波波形を印加して確認した。より、具体的には、圧力P=50Nを周波数0.5~50Hzの範囲で変化させた。 Selection of Porcelain Composition (A) and Porcelain Composition (B) 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). For that purpose, 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). As a confirmation means, the pressure P was applied to the porcelain composition, the output was observed, and the hysteresis value was confirmed by applying a sine wave waveform. More specifically, the pressure P = 50 N was changed in the frequency range of 0.5 to 50 Hz.
磁器組成物(A)及び磁器組成物(B)は、組成の選択、その他の諸条件で検討した。
まず、加圧力と減圧力に対し電荷の発生傾向が異なるA成分、B成分は多くの候補が考えられたが発生電荷量Qのヒステリシス値が±0.1%以内となると磁器組成物の組成には限界がある。本発明者らは以下の磁器組成物に決定した。
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲は、0.05≦y≦0.4となるよう組み合わせた。その理由は前記等価圧電定数(d33)が高いこと、同時にヒステリシス値(HyQ)を±0.1%以内とするためには、以下の磁器組成物組成に限定されることが見いだされたからである。以下選択手順と結果を明らかにする。 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 reason is that the equivalent piezoelectric constant (d 33 ) is high, and at the same time, in order to keep the hysteresis value (HyQ) within ± 0.1%, it is found that the composition is limited to the following porcelain composition. is there. The selection procedure and results are clarified below.
まず、加圧力と減圧力に対し電荷の発生傾向が異なるA成分、B成分は多くの候補が考えられたが発生電荷量Qのヒステリシス値が±0.1%以内となると磁器組成物の組成には限界がある。本発明者らは以下の磁器組成物に決定した。
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲は、0.05≦y≦0.4となるよう組み合わせた。その理由は前記等価圧電定数(d33)が高いこと、同時にヒステリシス値(HyQ)を±0.1%以内とするためには、以下の磁器組成物組成に限定されることが見いだされたからである。以下選択手順と結果を明らかにする。 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 reason is that the equivalent piezoelectric constant (d 33 ) is high, and at the same time, in order to keep the hysteresis value (HyQ) within ± 0.1%, it is found that the composition is limited to the following porcelain composition. is there. The selection procedure and results are clarified below.
(1)ヒステリシス値HyQがプラスである磁器組成物(A)の選択
すなわち、図3のようなQdown>Qupの性質を有する組成物(A)として、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}を用いた。
(2)ヒステリシス値HyQがマイナスである磁器組成物(B)の選択
すなわち、図5のような、Qdown<Qupの性質を有する(B)として、
(y)SrBi4Ti4O15を用いた。 (1) Selection of a porcelain composition (A) having a positive hysteresis value HyQ That is, as a composition (A) having a property of Qdown> Qup as shown in FIG.
(1-y) {(Na 0.5 , Bi 0.5 ) 0.95 Ca 0.05 Bi 4 Ti 4 O 15 +0.2 Wt% Mn} was used.
(2) Selection of porcelain composition (B) having a negative hysteresis value HyQ That is, as (B) having a property of Qdown <Qup as shown in FIG.
(Y) SrBi 4 Ti 4 O 15 was used.
すなわち、図3のようなQdown>Qupの性質を有する組成物(A)として、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}を用いた。
(2)ヒステリシス値HyQがマイナスである磁器組成物(B)の選択
すなわち、図5のような、Qdown<Qupの性質を有する(B)として、
(y)SrBi4Ti4O15を用いた。 (1) Selection of a porcelain composition (A) having a positive hysteresis value HyQ That is, as a composition (A) having a property of Qdown> Qup as shown in FIG.
(1-y) {(Na 0.5 , Bi 0.5 ) 0.95 Ca 0.05 Bi 4 Ti 4 O 15 +0.2 Wt% Mn} was used.
(2) Selection of porcelain composition (B) having a negative hysteresis value HyQ That is, as (B) having a property of Qdown <Qup as shown in FIG.
(Y) SrBi 4 Ti 4 O 15 was used.
前記で選択した磁器組成物(A)、磁器組成物(B)について、等価圧電定数(d33)とヒステリシス値(HyQ)を確認してみた。その結果を表1に示すようにヒステリシス値(HyQ)において顕著な差異が認められた。すなわち、磁器組成物(A)では、等価圧電定数(d33)は23.1pC/N、ヒステリシス値(HyQ)は0.18~1.76%のプラス値、磁器組成物(B)では等価圧電定数(d33)は10.9pC/N、ヒステリシス値(HyQ)は21~44%のマイナス値となった。
測定は図6に示すd33-ヒステリシス評価装置で行い、周波数範囲は0.5~50Hzで行った。 For the porcelain composition (A) and porcelain composition (B) selected above, 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.
測定は図6に示すd33-ヒステリシス評価装置で行い、周波数範囲は0.5~50Hzで行った。 For the porcelain composition (A) and porcelain composition (B) selected above, 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.
この結果からも明らかなようにヒステリシス値(HyQ)は前記磁器組成物(A)を選択することでプラスとなる。これに対して、前記磁器組成物(B)ではマイナスとなることが見い出された。さらに、これらを組み合わせ配合比を選べばヒステリシス値(HyQ)はプラスマイナスで相殺され小さくできる可能性も見い出された。他方、電極形成方法や製造条件の探索は配合比を中心としつつも、いくつか解決策が得られた。
As is clear from this result, the hysteresis value (HyQ) becomes positive by selecting the porcelain composition (A). On the other hand, it was found that the porcelain composition (B) is negative. Furthermore, it was found that the hysteresis value (HyQ) can be offset by plus / minus and reduced by selecting a combination ratio by combining these. On the other hand, the search for the electrode forming method and manufacturing conditions centered on the mixing ratio, but some solutions were obtained.
A成分としてCaを選択した理由について説明する。Caはアルカリ土類金属に含まれ、他に、Sr、Ba、Ra等も同様含まれる。これらのなかで、本発明における圧電磁器組成物ではCaが最もキュリー点(キュリー温度)を高くできることが確認された。
逆に、Sr、Ba、K+Bi等を含むことはキュリー点を下げてしまう悪影響も確認できた。圧電磁器組成物のキュリー点とは、これを超えると強誘電体から常誘電体に変化する転移温度である。キュリー点が高いとは、圧電磁器が高温度まで使用できることとなるから、極めて重要な選択肢となる。
つぎに、ヒステリシス値(HyQ)についても確認した。本発明はヒステリシス値(HyQ)±0.1%以内を達成させるためにA成分とB成分の組み合わせを模索した。その結果、使用可能なアルカリ土類金属ではCaが最も適していることが確認された。
他のBa、Srは±0.1%以内を達成させるための許容幅が狭く製造上の難しさが認められたからである。
これらを検討した上で具体的に本発明の圧電磁器組成物及びその製造方法につき詳細に述べる。 The reason why Ca is selected as the A component will be described. 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.
Next, the hysteresis value (HyQ) was also confirmed. In the present invention, the combination of the A component and the B component was sought in order to achieve a hysteresis value (HyQ) within ± 0.1%. As a result, it was confirmed that 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.
After examining these, the piezoelectric ceramic composition of the present invention and the production method thereof will be specifically described in detail.
逆に、Sr、Ba、K+Bi等を含むことはキュリー点を下げてしまう悪影響も確認できた。圧電磁器組成物のキュリー点とは、これを超えると強誘電体から常誘電体に変化する転移温度である。キュリー点が高いとは、圧電磁器が高温度まで使用できることとなるから、極めて重要な選択肢となる。
つぎに、ヒステリシス値(HyQ)についても確認した。本発明はヒステリシス値(HyQ)±0.1%以内を達成させるためにA成分とB成分の組み合わせを模索した。その結果、使用可能なアルカリ土類金属ではCaが最も適していることが確認された。
他のBa、Srは±0.1%以内を達成させるための許容幅が狭く製造上の難しさが認められたからである。
これらを検討した上で具体的に本発明の圧電磁器組成物及びその製造方法につき詳細に述べる。 The reason why Ca is selected as the A component will be described. 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.
Next, the hysteresis value (HyQ) was also confirmed. In the present invention, the combination of the A component and the B component was sought in order to achieve a hysteresis value (HyQ) within ± 0.1%. As a result, it was confirmed that 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.
After examining these, the piezoelectric ceramic composition of the present invention and the production method thereof will be specifically described in detail.
まず、磁器組成物は前記組成物(A)、(B)は以下の通り製造した。
使用原料は、純度3Nの酸化ビスマス、酸化チタン、酸化マンガン、炭酸ストロンチウム、炭酸カルシウム、炭酸ナトリウム等を使用した。
磁器組成物(A)、磁器組成物(B)は個々の組成式に従い、原料を別々に秤量し、調合した。さらに、それぞれを別々に室温にて乾式混合機にて1時間混合した。各混合品の仮焼成は、800℃ 2時間キープで行った。磁器組成物(A)、磁器組成物(B)の仮焼き粉体を作製した。磁器組成物(A)と磁器組成物(B)の仮焼き温度は、異なっていても良い。 First, 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.
使用原料は、純度3Nの酸化ビスマス、酸化チタン、酸化マンガン、炭酸ストロンチウム、炭酸カルシウム、炭酸ナトリウム等を使用した。
磁器組成物(A)、磁器組成物(B)は個々の組成式に従い、原料を別々に秤量し、調合した。さらに、それぞれを別々に室温にて乾式混合機にて1時間混合した。各混合品の仮焼成は、800℃ 2時間キープで行った。磁器組成物(A)、磁器組成物(B)の仮焼き粉体を作製した。磁器組成物(A)と磁器組成物(B)の仮焼き温度は、異なっていても良い。 First, 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.
次に得られた各仮焼き粉体は以下の配合比で調合し、ボールミル、乾式粉体混合機等で混合した。磁器組成物(A)、磁器組成物(B)の仮焼成粉体は表2に示す各配合比(重量%)で分取し、混合した。これらは製造例番号(Productin example number)で表す。製造例1から製造例6(ex.1から6)として表2に示した。
混合した粉体はボールミル等により粒度D50=0.5ミクロンメーター程度に粒度調整を行った。
粉体の成型はポリビニルアルコール等の有機バインダーを加えスプレードライヤーにて整粒した。試料作製は外形4mm程度、厚さ1mm程度に成型した。この後、焼成する。焼成温度は、1100~1150℃で2時間キープする。昇降温度速度は100℃/時間程度とした。 Next, 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 mixed powder was adjusted to a particle size D50 = 0.5 micrometer by a ball mill or the like.
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.
混合した粉体はボールミル等により粒度D50=0.5ミクロンメーター程度に粒度調整を行った。
粉体の成型はポリビニルアルコール等の有機バインダーを加えスプレードライヤーにて整粒した。試料作製は外形4mm程度、厚さ1mm程度に成型した。この後、焼成する。焼成温度は、1100~1150℃で2時間キープする。昇降温度速度は100℃/時間程度とした。 Next, 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 mixed powder was adjusted to a particle size D50 = 0.5 micrometer by a ball mill or the like.
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.
なお、磁器組成物(A)はヒステリシス値(HyQ)がプラスとなる焼成温度とした。プラスが得られる焼成温度条件としては、約1120~1160℃、好ましくは1140℃程度が適当である。同様に、磁器組成物(B)はヒステリシス値(HyQ)がマイナスとなる焼成温度とした。焼成温度条件としては、約1120~1160℃、好ましくは1140℃程度が適当である。
試料の表面状態はヒステリシス値を変化させる。一定に保つには、#2000以上の研磨剤で研磨又は鏡面とすることが望ましい。試料の厚さは0.5mmとしたが、要は焼成状態が維持できる厚さであれば制限はない。 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. Similarly, 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. Although the thickness of the sample was 0.5 mm, there is no limitation as long as the thickness can maintain the fired state.
試料の表面状態はヒステリシス値を変化させる。一定に保つには、#2000以上の研磨剤で研磨又は鏡面とすることが望ましい。試料の厚さは0.5mmとしたが、要は焼成状態が維持できる厚さであれば制限はない。 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. Similarly, 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. Although the thickness of the sample was 0.5 mm, there is no limitation as long as the thickness can maintain the fired state.
次に、得られた磁器組成物は分極のため試料の表面に水溶性導電性樹脂をスクリーン印刷した。分極用電極材料は、銀粉末入りの水溶性導電性樹脂材料(ナミックス社製、品番:H9184)を使用した。その条件としては、厚み20μm、乾燥可能な温度100℃で乾燥させた。
分極は、シリコンオイル中160℃、6kV/mmで5分間行った。
分極後導電性樹脂を水、エタノール、イソプロピルアルコールなどの適当な溶剤で除去し、乾燥させた。その上で、新たな銀ペースト(フジ化学研究所社製、型式:低温焼結銀ペースト)をスクリーン印刷し、乾燥後、450℃10分キープで焼成した。圧電磁器組成物の電極はキュリー温度以下で焼き付けた。 Next, the obtained porcelain composition was screen-printed with a water-soluble conductive resin on the surface of the sample for polarization. As the electrode material for polarization, a water-soluble conductive resin material containing silver powder (manufactured by NAMICS, product number: H9184) was used. As the conditions, the film was dried at a thickness of 20 μm and a drying temperature of 100 ° C.
Polarization was performed in silicon oil at 160 ° C. and 6 kV / mm for 5 minutes.
After the polarization, the conductive resin was removed with a suitable solvent such as water, ethanol, isopropyl alcohol and dried. Then, 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.
分極は、シリコンオイル中160℃、6kV/mmで5分間行った。
分極後導電性樹脂を水、エタノール、イソプロピルアルコールなどの適当な溶剤で除去し、乾燥させた。その上で、新たな銀ペースト(フジ化学研究所社製、型式:低温焼結銀ペースト)をスクリーン印刷し、乾燥後、450℃10分キープで焼成した。圧電磁器組成物の電極はキュリー温度以下で焼き付けた。 Next, the obtained porcelain composition was screen-printed with a water-soluble conductive resin on the surface of the sample for polarization. As the electrode material for polarization, a water-soluble conductive resin material containing silver powder (manufactured by NAMICS, product number: H9184) was used. As the conditions, the film was dried at a thickness of 20 μm and a drying temperature of 100 ° C.
Polarization was performed in silicon oil at 160 ° C. and 6 kV / mm for 5 minutes.
After the polarization, the conductive resin was removed with a suitable solvent such as water, ethanol, isopropyl alcohol and dried. Then, 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.
得られた試料は、図6に示す装置で等価圧電定数(d33)、ヒステリシス値(HyQ)を測定した。測定条件は、バイアス圧縮圧力250N、最大圧力300N、変化圧力範囲(Fp-p)50Nの交番圧力を加えた。駆動周波数(Fd)は、0.5、1、5、10、15、25、50Hzとした。等価圧電定数d33は、10Hzで計測した。ヒステリシス値HyQは、各周波数で計測した。
測定結果は表3に示し、グラフ化は図7として表現した。縦軸はヒステリシス値
Magnitude of Hysteresys (HyQ)、横軸は駆動周波数(Fd)である。 The obtained sample was measured for the equivalent piezoelectric constant (d 33 ) and hysteresis value (HyQ) with the apparatus shown in FIG. As measurement conditions, 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.
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).
測定結果は表3に示し、グラフ化は図7として表現した。縦軸はヒステリシス値
Magnitude of Hysteresys (HyQ)、横軸は駆動周波数(Fd)である。 The obtained sample was measured for the equivalent piezoelectric constant (d 33 ) and hysteresis value (HyQ) with the apparatus shown in FIG. As measurement conditions, 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.
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).
表3の結果に示すように、本発明で得られた、磁器組成物(A)及び磁器組成物(B)の配合比の違いによりヒステリシス値HyQが変動している様子が認められた。それによれば、0.05≦y≦0.4の範囲内(製造例1~6)において、ヒステリシス値(HyQ)は、-0.1%≦(HyQ)≦0.1%の範囲となる箇所が得られた。すなわち、製造例1で0.08%、製造例2で0.02%~0.08%,製造例4で-0.01%~+0.04%及び製造例6で-0.01%といった測定結果が確認された。
また、等価圧電定数d33も前記製造例1ないし6で20.6~22.8pC/Nが得られ、水晶の10倍となることが確認された。
他方、製造例3では、前記各製造例より、より顕著な作用効果が認められた。すなわち、製造例3では、駆動周波数5ないし50Hzの広いバンド幅で(HyQ)値を低く抑えることができた。製造例5では駆動周波数25ないし50Hzといった高い駆動周波数バンドでHyQを低く抑えることができた。 As shown in the results of Table 3, it was observed that 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.
Further, 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.
On the other hand, in Production Example 3, a more remarkable effect was observed than in each Production Example. That is, in Production Example 3, the (HyQ) value could be kept low with a wide bandwidth with a driving frequency of 5 to 50 Hz. In Production Example 5, HyQ could be kept low in a high driving frequency band such as a driving frequency of 25 to 50 Hz.
また、等価圧電定数d33も前記製造例1ないし6で20.6~22.8pC/Nが得られ、水晶の10倍となることが確認された。
他方、製造例3では、前記各製造例より、より顕著な作用効果が認められた。すなわち、製造例3では、駆動周波数5ないし50Hzの広いバンド幅で(HyQ)値を低く抑えることができた。製造例5では駆動周波数25ないし50Hzといった高い駆動周波数バンドでHyQを低く抑えることができた。 As shown in the results of Table 3, it was observed that 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.
Further, 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.
On the other hand, in Production Example 3, a more remarkable effect was observed than in each Production Example. That is, in Production Example 3, the (HyQ) value could be kept low with a wide bandwidth with a driving frequency of 5 to 50 Hz. In Production Example 5, HyQ could be kept low in a high driving frequency band such as a driving frequency of 25 to 50 Hz.
図7は表3から作成したものである。製造例1~6についてヒステリシス値(HyQ)と駆動周波数(Fd)の関係を示したものである。縦軸はヒステリシス値(HyQ)、横軸は駆動周波数(Fd)である。
特に、前記したように、製造例3はヒステリシス値が±0.1%以内となる駆動周波数(Fd)範囲が広い特長が認められた。同様に製造例1,2、4及び5がこれに続いていることが認められよう。これらは磁器組成物(A)と磁器組成物(B)の配合比に依存した情報と理解できる。すなわち、yの範囲、0.05≦y≦0.4、望ましくは、0.05≦y≦0.25でヒステリシス値をより低減できる作用効果が認められる。 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).
In particular, as described above, 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.
特に、前記したように、製造例3はヒステリシス値が±0.1%以内となる駆動周波数(Fd)範囲が広い特長が認められた。同様に製造例1,2、4及び5がこれに続いていることが認められよう。これらは磁器組成物(A)と磁器組成物(B)の配合比に依存した情報と理解できる。すなわち、yの範囲、0.05≦y≦0.4、望ましくは、0.05≦y≦0.25でヒステリシス値をより低減できる作用効果が認められる。 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).
In particular, as described above, 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.
磁器組成物(A)と磁器組成物(B)は、以下の条件、手順にてそれぞれの試料を作製した。混合組成物は、ジルコニア玉石、イオン交換水、界面活性剤をボールミルに入れ粗粉砕を1時間し、スラリーとした。
さらに、スラリーはメディア式粉砕機にて粒度をD50=0.5ミクロンメーターに調整した。ポリビニルアルコール(PVA)を1wt%添加し、スプレードライヤーにて整粒した。
成型は、外形4mm、厚さ2.5mm、密度4.9g/cm3のディスク形状にした。
焼成は、1130℃、2時間キープでアルミナサヤを使用して行った。
さらに、研磨剤#3000にて2mmの厚さに研磨した。 For the porcelain composition (A) and the porcelain composition (B), respective samples were prepared under the following conditions and procedures. The mixed composition was made into a slurry by putting zirconia boulders, ion-exchanged water, and a surfactant in a ball mill and roughly pulverizing them for 1 hour.
Furthermore, the particle size of the slurry was adjusted to D50 = 0.5 micrometer using a media type pulverizer. 1 wt% of polyvinyl alcohol (PVA) was added, and the particles were sized with a spray dryer.
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.
さらに、スラリーはメディア式粉砕機にて粒度をD50=0.5ミクロンメーターに調整した。ポリビニルアルコール(PVA)を1wt%添加し、スプレードライヤーにて整粒した。
成型は、外形4mm、厚さ2.5mm、密度4.9g/cm3のディスク形状にした。
焼成は、1130℃、2時間キープでアルミナサヤを使用して行った。
さらに、研磨剤#3000にて2mmの厚さに研磨した。 For the porcelain composition (A) and the porcelain composition (B), respective samples were prepared under the following conditions and procedures. The mixed composition was made into a slurry by putting zirconia boulders, ion-exchanged water, and a surfactant in a ball mill and roughly pulverizing them for 1 hour.
Furthermore, the particle size of the slurry was adjusted to D50 = 0.5 micrometer using a media type pulverizer. 1 wt% of polyvinyl alcohol (PVA) was added, and the particles were sized with a spray dryer.
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 /
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.
電極を使用せず表面部位を粗面化させ、表面粗さを制御することで、ヒステリシス値を低減化させることを見いだした。以下製造方法について述べる。
実施例1の処方に従い、圧電磁器組成物の製造は、磁器組成物(A)と磁器組成物(B)から焼成体を形成させる。この焼成体の電極部位表面に粗面を作成させる。研磨剤で焼成体表面に粗面(表面粗さ)を形成させることになる。一般に圧電素子は分極用電極を形成しておくことが必要である。しかしながら、本発明では素子の電極部位を研磨剤で研磨することで分極用電極を必要としない。かかる粗面部位は直接分極用電源端子を接触させることで分極させ圧電素子とすることができる。
圧電磁器組成物の電極部位は研磨剤で表面を粗面化することが求められる。本発明者等はその条件を見いだし実用化の見通しが得られた。研磨剤の種類、研磨結果は表4に示す。 It has been found that the hysteresis value is reduced by roughening the surface portion without using an electrode and controlling the surface roughness. The manufacturing method will be described below.
According to the prescription in Example 1, 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. In general, a piezoelectric element needs to be provided with a polarization electrode. However, in the present invention, 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.
実施例1の処方に従い、圧電磁器組成物の製造は、磁器組成物(A)と磁器組成物(B)から焼成体を形成させる。この焼成体の電極部位表面に粗面を作成させる。研磨剤で焼成体表面に粗面(表面粗さ)を形成させることになる。一般に圧電素子は分極用電極を形成しておくことが必要である。しかしながら、本発明では素子の電極部位を研磨剤で研磨することで分極用電極を必要としない。かかる粗面部位は直接分極用電源端子を接触させることで分極させ圧電素子とすることができる。
圧電磁器組成物の電極部位は研磨剤で表面を粗面化することが求められる。本発明者等はその条件を見いだし実用化の見通しが得られた。研磨剤の種類、研磨結果は表4に示す。 It has been found that the hysteresis value is reduced by roughening the surface portion without using an electrode and controlling the surface roughness. The manufacturing method will be described below.
According to the prescription in Example 1, 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. In general, a piezoelectric element needs to be provided with a polarization electrode. However, in the present invention, 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.
表4に示す研磨粗度#600、#1000及び#3000等の表示で「#」は研磨砥粒の大きさをメッシュで表したものである。
これら研磨剤は、型番WAで、製造元は株式会社フジミインコーポレイテッドから入手したものを用いた。研磨は平面研磨機を使用し、試料表面を研磨した。平均表面粗さ(Ra)は、JIS B0601:1994に基づいて定義される表面粗さkパラメータを用いた。表面粗さRaは、#3000で Ra=0.1μm、#1000で Ra=0.3μm、#600で Ra=0.4μmとなるよう加工した。
実施例1で得られた焼成体を使用し研磨剤で電極とされる表面を粗面化した。等価圧電定数d33とヒステリシス値(HyQ)は表4に示した。いわゆる銀電極を用いたものと対比して見ると、d33は約80%程度低くなっているが素子間のバラツキ程度であり使用上の問題はない。HyQは、#1000及び#3000と対比では-0.1%≦(HyQ)≦0.1%の範囲内であり、#600でやや超えているように認められた。研磨剤をやや細かい素材の利用で粗面化すれば問題は無いと理解できる。 In the indications of polishingroughness # 600, # 1000, # 3000, etc. shown in Table 4, “#” represents the size of the abrasive grains in mesh.
These abrasives were model number WA, and the manufacturer used those obtained from Fujimi Incorporated. The surface of the sample was polished using a flat polishing machine. As the average surface roughness (Ra), a surface roughness k parameter defined based on JIS B0601: 1994 was used. The surface roughness Ra was processed so that Ra = 0.1 μm for # 3000, Ra = 0.3 μm for # 1000, and Ra = 0.4 μm for # 600.
The fired body obtained in Example 1 was used to roughen the surface to be an electrode with an abrasive. 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.
これら研磨剤は、型番WAで、製造元は株式会社フジミインコーポレイテッドから入手したものを用いた。研磨は平面研磨機を使用し、試料表面を研磨した。平均表面粗さ(Ra)は、JIS B0601:1994に基づいて定義される表面粗さkパラメータを用いた。表面粗さRaは、#3000で Ra=0.1μm、#1000で Ra=0.3μm、#600で Ra=0.4μmとなるよう加工した。
実施例1で得られた焼成体を使用し研磨剤で電極とされる表面を粗面化した。等価圧電定数d33とヒステリシス値(HyQ)は表4に示した。いわゆる銀電極を用いたものと対比して見ると、d33は約80%程度低くなっているが素子間のバラツキ程度であり使用上の問題はない。HyQは、#1000及び#3000と対比では-0.1%≦(HyQ)≦0.1%の範囲内であり、#600でやや超えているように認められた。研磨剤をやや細かい素材の利用で粗面化すれば問題は無いと理解できる。 In the indications of polishing
These abrasives were model number WA, and the manufacturer used those obtained from Fujimi Incorporated. The surface of the sample was polished using a flat polishing machine. As the average surface roughness (Ra), a surface roughness k parameter defined based on JIS B0601: 1994 was used. The surface roughness Ra was processed so that Ra = 0.1 μm for # 3000, Ra = 0.3 μm for # 1000, and Ra = 0.4 μm for # 600.
The fired body obtained in Example 1 was used to roughen the surface to be an electrode with an abrasive. 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.
なお、磁器組成物(A)が20%及び磁器組成物(B)が80%の配合比でも同様確認した。結果は、ヒステリシス値が-1.1~-4.9%で極めて大、等価圧電定数d33は4.5pC/Nで極めて小であり、本発明には使用は不可であった。
この結果yパラメータは0.05≦y≦0.4の範囲内が効果的であることが理解されよう。望ましくは、yが0.05≦y≦0.25がより効果的であった。また、yが0.05より下、また、0.4超では等価圧電定数が小さくなる傾向となり使用に耐えない。 The same confirmation was made even at a blending ratio of 20% for the porcelain composition (A) and 80% for the porcelain composition (B). As a result, the hysteresis value was extremely large at −1.1 to −4.9%, and the equivalent piezoelectric constant d 33 was very small at 4.5 pC / N, which could not be used in the present invention.
As a result, it is understood that 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.
この結果yパラメータは0.05≦y≦0.4の範囲内が効果的であることが理解されよう。望ましくは、yが0.05≦y≦0.25がより効果的であった。また、yが0.05より下、また、0.4超では等価圧電定数が小さくなる傾向となり使用に耐えない。 The same confirmation was made even at a blending ratio of 20% for the porcelain composition (A) and 80% for the porcelain composition (B). As a result, the hysteresis value was extremely large at −1.1 to −4.9%, and the equivalent piezoelectric constant d 33 was very small at 4.5 pC / N, which could not be used in the present invention.
As a result, it is understood that 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.
本発明の材料は、圧力センサ検知素子としてとして産業上の利用可能性がある。その特徴としては、キュリー温度が高い材料であることからエンジンの回転数に対応する圧力変動が周波数10Hz以上(600rpm以上)の自動車のエンジン燃焼圧検知用圧力センサの検知素子として効果的である。高感度、高精度、高温耐性を持った素子として期待される。低周波数領域(10Hz以下)の検知素子としでは、汎用の高感度、高精度の微分型圧力センサとして期待できる。
圧電セラミックス製造にあっては、本発明の製造方法は既知の磁器組成物であっても電極形成設備や高価な電極材料に制限されない製造手法として効果的である。また、多量から少量の製造も可能で幅広い分野で利用される圧力検知の素子としても期待できる。 The material of the present invention has industrial applicability as a pressure sensor sensing element. As a feature thereof, 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. As 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.
In the production of piezoelectric ceramics, 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.
圧電セラミックス製造にあっては、本発明の製造方法は既知の磁器組成物であっても電極形成設備や高価な電極材料に制限されない製造手法として効果的である。また、多量から少量の製造も可能で幅広い分野で利用される圧力検知の素子としても期待できる。 The material of the present invention has industrial applicability as a pressure sensor sensing element. As a feature thereof, 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. As 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.
In the production of piezoelectric ceramics, 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.
1 圧力(N)を増加させるときの圧力-電荷曲線
2 圧力(N)を減少させるときの圧力-電荷曲線
3 圧力(N)を増加させるときの上向き矢印
4 圧力(N)を減少させるときの下向き矢印
5 圧電磁器組成物
6 上部コンタクト治具
7 下部コンタクト治具
8 精密圧力印加用アクチュエータ
9 精密圧力計測用水晶フォースセンサ
10 バイアス圧力計測用ロードセル
11 接続リニアガイド
12 バイアス圧力印加用モータ
13 演算処理波形表示条件入力用コンピュータ
14 電源制御装置
15 チャージアンプ
16 アンプ信号計測器
17 ケーブル
18 ヒステリシス計測装置 1 Pressure-charge curve when increasing pressure (N) 2 Pressure-charge curve when decreasing pressure (N) 3 Up arrow when increasing pressure (N) 4 When decreasing pressure (N) Downarrow 5 Piezoelectric ceramic composition 6 Upper contact jig 7 Lower contact jig 8 Precision pressure application actuator 9 Precision pressure measurement crystal force sensor 10 Bias pressure measurement load cell 11 Connection linear guide 12 Bias pressure application motor 13 Arithmetic processing Waveform display condition input computer 14 Power supply control device 15 Charge amplifier 16 Amplifier signal measuring device 17 Cable 18 Hysteresis measuring device
2 圧力(N)を減少させるときの圧力-電荷曲線
3 圧力(N)を増加させるときの上向き矢印
4 圧力(N)を減少させるときの下向き矢印
5 圧電磁器組成物
6 上部コンタクト治具
7 下部コンタクト治具
8 精密圧力印加用アクチュエータ
9 精密圧力計測用水晶フォースセンサ
10 バイアス圧力計測用ロードセル
11 接続リニアガイド
12 バイアス圧力印加用モータ
13 演算処理波形表示条件入力用コンピュータ
14 電源制御装置
15 チャージアンプ
16 アンプ信号計測器
17 ケーブル
18 ヒステリシス計測装置 1 Pressure-charge curve when increasing pressure (N) 2 Pressure-charge curve when decreasing pressure (N) 3 Up arrow when increasing pressure (N) 4 When decreasing pressure (N) Down
Claims (9)
- 加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とし、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とし、該焼成体に分極用導電性樹脂電極を形成させた圧電体とし、該圧電体を分極し、前記樹脂電極を分極後除去してその部位に圧電出力検出用電極を付与させた特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物。 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 When expressed as the B component, 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 hysteresis having an equivalent piezoelectric constant within a specific range in which a piezoelectric body is formed with a conductive resin electrode, the piezoelectric body is polarized, the resin electrode is removed after polarization, and a piezoelectric output detection electrode is applied to the portion. Piezoelectric ceramic composition within ± 0.1%. - 旧
加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とし、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とした後、前記焼成体の電極表面部位を粗面化させ、該表面から分極処理を行い、該表面に圧電出力検出用電極を付与させた特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物。 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 previous applied pressure and 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 When expressed as the B component, 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, and then the electrode of the calcined body. A piezoelectric ceramic composition having a hysteresis within ± 0.1% within a specific range in which a surface portion is roughened, a polarization treatment is performed from the surface, and a piezoelectric output detection electrode is applied to the surface. object. - 前記yが0.05≦y≦0.25である請求項1又は請求項2記載の圧電磁器組成物。 3. The piezoelectric ceramic composition according to claim 1, wherein y is 0.05 ≦ y ≦ 0.25.
- 加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とする工程、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とする工程、該焼成後分極用導電性樹脂電極作製工程、この樹脂を分極後除去する工程、その上で圧電出力検出用電極を付与する工程の一連を行い特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物の製造方法。 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 A component, (y) SrBi 4 Ti 4 O 15 When expressed as the B component, 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 step of making each of the A component and the B component calcined powder, a step of preparing the calcined powder by mixing, mixing, granulating, molding and firing the calcined powder at a blending ratio of y, after the firing ± 0.1% hysteresis with an equivalent piezoelectric constant within a specific range by conducting a series of steps of making a conductive resin electrode for polarization, removing the resin after polarization, and applying a piezoelectric output detection electrode on the resin A method for producing a piezoelectric ceramic composition within the range. - 前記yが0.05≦y≦0.25である請求項4記載の圧電磁器組成物の製造方法。 The method for producing a piezoelectric ceramic composition according to claim 4, wherein the y is 0.05 ≦ y ≦ 0.25.
- 前記焼成後分極において電極材料の構成物の拡散防止用導電性樹脂を用いて電極形成を行う工程からなる請求項4又は請求項5記載の圧電磁器組成物の製造方法。 The method for producing a piezoelectric ceramic composition according to claim 4 or 5, comprising a step of forming an electrode using a conductive resin for preventing diffusion of a constituent of an electrode material in the post-firing polarization.
- 前記拡散防止用導電性樹脂を分極後除去する工程後、電極材料として分極状態の性能劣化をさせない耐熱性のあるキュリー温度以下で焼成可能な焼成タイプの電極材料として銀粉末入りの水溶性導電性樹脂材料を用いる工程からなる請求項4又は請求項5記載の圧電磁器組成物の製造方法。 After the step of removing the conductive resin for preventing diffusion after polarization, the electrode material is water-soluble conductive material containing silver powder as a baked type electrode material that can be baked at a heat-resistant Curie temperature or less that does not cause deterioration of the performance of the polarized state The method for producing a piezoelectric ceramic composition according to claim 4 or 5, comprising a step of using a resin material.
- 加圧力と減圧力に対し電荷の発生傾向が異なる2種のA成分、B成分からなる磁器組成物の組成式を、
(1-y){(Na0.5 ,Bi0.5)0.95Ca0.05Bi4Ti4O15+0.2Wt%Mn}をA成分、(y)SrBi4Ti4O15をB成分
と表したとき、A成分、B成分の配合比を定めるyの範囲が、0.05≦y≦0.4である。
これを、A成分、B成分それぞれを仮焼き粉体とする工程、前記仮焼粉体をyの配合比で調合、混合、整粒、成型及び焼成させた焼成体とする工程、該焼成後、前記焼成体の電極表面部位を粗面化させる工程、該表面から分極処理を行い、その上で圧電出力検出用電極を付与する工程の一連を行い特定範囲内の等価圧電定数を有するヒステリシスを±0.1%以内とする圧電磁器組成物の製造方法。 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 A component, (y) SrBi 4 Ti 4 O 15 When expressed as the B component, 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 step of making each of the A component and the B component calcined powder, a step of preparing the calcined powder by mixing, mixing, granulating, molding and firing the calcined powder at a blending ratio of y, after the firing A hysteresis process having an equivalent piezoelectric constant within a specific range by roughening the electrode surface portion of the fired body, performing a polarization process from the surface, and then applying a piezoelectric output detection electrode thereon A method for producing a piezoelectric ceramic composition within ± 0.1%. - 前記粗面化させる工程を研磨粗度#600から#3000の範囲で研磨し、表面粗さが0.1から0.4μmに形成させた請求項8記載の圧電磁器組成物の製造方法。
9. The method of manufacturing a piezoelectric ceramic composition according to claim 8, wherein the roughening step is performed in a polishing roughness range of # 600 to # 3000 to form a surface roughness of 0.1 to 0.4 [mu] m.
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JP2001158663A (en) * | 1999-11-30 | 2001-06-12 | Kyocera Corp | Piezoelectric ceramic composition |
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