CN101525233A - Piezoceramic material, piezoelectric element and non-resonance knock sensor - Google Patents
Piezoceramic material, piezoelectric element and non-resonance knock sensor Download PDFInfo
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Abstract
The invention relates to piezoceramic material, a piezoelectric element and non-resonance knock sensor. A piezoceramic material according to an embodiment of the present invention has a composition represented by Pb n [Zr 1-x-y-z Ti x Sn y (Sb 1-n Nb n ) z ]O 3 where 1.000<=m<=1.075, 0.470<=x < 0.490, 0.020<=y<=0.040, 0 < n < 1.000 and 0 < z<= 0.025 and a crystallite size of 30 to 39 nm.
Description
Technical field
The present invention relates to piezoceramic material, it is suitable in piezoelectric transducer such as pressure transmitter, acceleration transducer, detonation sensor, Yaw rate sensor, gyro sensor and vibration transducer and other piezo-electric devices, also relates to piezoelectric element that uses this piezoceramic material and the off-resonance type detonation sensor that uses this piezoelectric element.
Background technology
Various piezoelectric transducers have been widely used in electronics and dynamo-electric field.Each piezoelectric transducer comprises the piezoelectric element that is equipped with agglomerating piezoelectric ceramic body (piece) and at least one pair of element electrode, so that the piezoelectric effect by piezoelectric ceramic body will be converted into curtage to its mechanical stress that applies, and based on the curtage generation electrical signal that transforms.Because the piezoelectric property of piezoelectric ceramic body is along with the surrounding temperature of operating environment changes, the susceptibility of piezoelectric transducer (output voltage) changes.When the temperature of piezoelectric transducer changes during operation or changes along with the surrounding temperature of operating environment, because thermal expansion is different between piezoelectric ceramic body and element electrode or other adjacent sensors parts, the thermal stresses in the piezoelectric element appears.Voltage also appears in the pyroelectric effect of the piezoelectrics that change by response temperature in piezoelectric transducer.These are introduced noise in the output of piezoelectric transducer, thereby cause the susceptibility of piezoelectric transducer to change.In addition, under the weight that piezoelectric element is applied, thereby the piezoelectric property of piezoelectric ceramic body may deterioration cause that transmitter output reduces.For above-mentioned reasons, common service temperature with piezoelectric transducer is set at-40 ℃ to 170 ℃ approximately.Yet, consider the fact of under the severe condition in the motor car engine for example, using piezoelectric transducer, the not change of displays temperature characteristic in wide temperature range of expectation piezoelectric element.
In order to realize the piezoelectric element of this temperature-stable, Japanese Patent No.2789374, Japanese Patent No.2964265 and Japanese Patent No.2957002 disclose PZT (Pb-based lanthanumdoped zirconate titanates) piezoceramic material of doping Sn, Nb and Sb, to obtain the improvement of thermostability by interpolation Sn, become possible (that is, improving piezoelectric property) with making low-temperature sintering by interpolation Nb and Sb and softening with big crystal distortion.
Summary of the invention
Above-mentioned conventional piezoelectric stupalith requires further improvement piezoelectricity and temperature profile.For example, there is following demand: have piezoelectric constant d33 and be the piezoceramic material of 340pC/N above (as the index of piezoelectricity susceptibility) and have the piezoceramic material that Curie temperature is (as a stable on heating index) more than 340 ℃, so that this piezoceramic material can be applied to the piezoelectric transducer in the motor car engine suitably, described motor car engine can reach about 170 ℃ top temperature.Yet, also do not have the above piezoelectric constant d33 of 340pC/N and/or the report of the piezoceramic material of Curie temperature more than 340 ℃ about any.
Therefore the object of the present invention is to provide piezoceramic material with good piezoelectricity and temperature profile.The present invention also aims to provide piezoelectric element that uses this piezoceramic material and the off-resonance type detonation sensor that uses this piezoelectric element.
Result as broad research finds: be controlled in the specified range by composition and crystalline state with material, the Pb/Zr/Ti/Sn/Sb/Nb oxide material with high heat resistance and good piezoelectric property can be provided.The present invention is based on this discovery.
According to a first aspect of the invention, provide the piezoceramic material with the composition that is expressed from the next: Pb
m{ Zr
1-x-y-zTi
xSn
y(Sb
1-nNb
n)
zO
3, wherein 1.000≤m≤1.075,0.470≤x＜0.490,0.020≤y≤0.040,0＜n＜1.000 and 0＜z≤0.025, and crystallite dimension is 30 to 39nm.
According to a second aspect of the invention, provide the piezoceramic material with the composition that is expressed from the next: Pb
m{ Zr
1-x-y-zTi
xSn
y(Sb
1-nNb
n)
zO
3, wherein 1.000≤m≤1.075,0.470≤x＜0.490,0.020≤y≤0.040,0＜n＜1.000 and 0＜z≤0.025, and piezoelectric constant d33 is more than the 340pC/N.
According to a third aspect of the invention we, provide the piezoelectric element that comprises the element body that forms by above-mentioned piezoceramic material.
According to a forth aspect of the invention, provide off-resonance type detonation sensor, it comprises: piezoelectric element, and it has the element body that is formed by above-mentioned piezoceramic material and at least one pair of electrode that is arranged on the described element body; Support member, it has support section to support described piezoelectric element; The weightening finish member, it is disposed on the described piezoelectric element so that described piezoelectric element is pressed to described support section; Resin forming portion, it is from outside described piezoelectric element and the described weightening finish member of covering of described support member.
According to a fifth aspect of the invention, provide off-resonance type detonation sensor, it comprises: piezoelectric element, and it has element body that is formed by above-mentioned piezoceramic material and a pair of first and second electrodes that are arranged on the described element body; Support member, it has support section to support described piezoelectric element; The weightening finish member, it is disposed on the described piezoelectric element so that described piezoelectric element is pressed to described support section, wherein when with described piezoelectric element and described weightening finish member during along the thickness direction projection of described piezoelectric element, the part surface at least of described first electrode is towards the basal surface of described weightening finish member; This of described first electrode ratio of area and the area of the basal surface of described weightening finish member of part surface at least is more than 45%.
Also will understand the other objects and features of the invention from following description.
Description of drawings
Fig. 1 is the scanning electron microscopy sheet according to the piezoceramic material of early stage technology.
Fig. 2 is for showing the figure that concerns according between the crystallite dimension of piezoceramic material of the present invention and the piezoelectric constant d33.
Fig. 3 is according to the present invention, at the scanning electron microscopy sheet of 1250 ℃ of following agglomerating piezoceramic materials.
Fig. 4 is according to the present invention, at the scanning electron microscopy sheet of 1300 ℃ of following agglomerating piezoceramic materials.
Fig. 5 is the sectional view according to the off-resonance type detonation sensor of one embodiment of the invention.
Fig. 6 is the decomposition diagram of the off-resonance type detonation sensor of Fig. 5.
Fig. 7 be Fig. 5 and 6 off-resonance type detonation sensor piezoelectric element and the weightening finish member sectional view.
Fig. 8 is for showing according to one embodiment of the invention, and the output characteristic of off-resonance type detonation sensor is about the electrode surface area of piezoelectric element and the figure of the ratio of the bottom surface area of weightening finish member.
Embodiment
Describe the present invention in detail below with reference to accompanying drawing.
Piezoceramic material (hereinafter only being called " piezoceramic material ") according to an exemplary of the present invention is the PZT (PbTiO of doping Sn, Sb and Nb
3-PbZrO
3) pottery.
When at cubic ferroelectric material PbTiO
3Middle Zr replaces Ti when the amount of Zr in gained PZT sosoloid reaches about 53mol%, and the crystalline structure of material is changed into diamond structure.Will be at the crystalline structure of material along with this border of forming change place is called accurate homotype phase boundary (MPB).Known: the piezoelectricity of PZT material becomes maximum near accurate homotype phase boundary, but near accurate homotype phase boundary, thus the stability degradation of PZT material cause capacitor C p with respect to temperature great variety.
Therefore, piezoceramic material has the composition that is expressed from the next: Pb
m{ Zr
1-x-y-zTi
xSn
y(Sb
1-nNb
n)
zO
3Wherein 1.000≤m≤1.075,0.470≤x＜0.490,0.020≤y≤0.040,0＜n＜1.000 and 0＜z≤0.025, so that it is different with accurate homotype phase boundary on forming, benefit from replacement (doping) effect of Sn, Sb and Nb, guarantee the piezoelectric property of capacitor C p in the present embodiment and the consistency between the temperature stability thus.
Have above-mentioned specific composition, piezoceramic material reaches the above piezoelectric constant d33 of 340pC/N.Piezoelectric constant d33 is defined as at the mechanical force that applies to it, stress, pressure etc. down the amount of the electric charge that the direct piezoelectric effect by piezoceramic material produces.It is said that piezoelectric constant d33 is big more, the amount of the electric charge that produces by piezoceramic material is big more, piezoceramic material is being used under the situation of piezoelectric transducer, and the output of piezoelectric transducer (susceptibility) is high more.
If m＜1, because different with the PZT composition, the piezoelectric constant d33 of piezoceramic material reduces.If m＞1.075, owing to form PbO, the piezoelectric constant d33 of piezoceramic material reduces.If x＜0.470, the amount of Ti is very little in piezoceramic material, so that piezoceramic material can have the big rate of change of capacitance of Δ Cp＞2500ppm/K.If 0.490≤x, piezoceramic material is tending towards low on piezoelectric constant d33, and by adding the big deterioration of thermal discharge piezoelectric constant d33.If y＜0.020, because a small amount of Sn, the Curie temperature Tc of piezoceramic material may reduce.If n=0, owing to there are not Nb, the crystal stability deterioration of piezoceramic material.If n=1.000, owing to there is not Sb, the crystal stability of piezoceramic material is deterioration also.If z=0, owing to do not have Nb and Sb, the sintering temperature of piezoceramic material increases, so that the crystallite dimension of piezoceramic material can not be controlled in the aforementioned specified range.In addition, the big deterioration that shows piezoelectric constant d33 by the heating piezoceramic material.If 0.025≤z owing to exist too much Nb and Sb, piezoceramic material can have the big rate of change of capacitance of Δ Cp＞2500ppm/K, maybe can reduce Curie temperature Tc.
In addition, piezoceramic material has 30 to 39nm crystallite dimension.Crystallite is defined as the territory (crystallite) that can be considered monocrystalline, and crystallite dimension is used as the parameter of degree of crystallinity (crystalline perfection), and be defined as the size in this territory.Most of materials are formed by a plurality of crystallites.If crystallite dimension is lower than 30nm, it is little that wherein all parts have the territory of identical crystalline orientation.This feasible piezoelectric property that is difficult to improve piezoceramic material.In theory, the piezoelectric property of piezoceramic material can improve by sintering (burning till (firing)) temperature that improves piezoceramic material and the crystallite dimension that increases piezoceramic material thus.Yet in fact, the composition of piezoceramic material destroys by the evaporation of volatile element Pb, Sn and Sb, so that when the sintering temperature of piezoceramic material became too high, the piezoelectric property of piezoceramic material was with deterioration rather than improve.Be appreciated that and sintering temperature by adjusting piezoceramic material and calcination condition and raw material powder pulverize size to control crystallite dimension be suitable.
On the other hand, because grain-size does not always reflect the micro-domains size of above-mentioned piezoceramic material, so be difficult to improve the piezoelectric property of piezoceramic material by the grain-size of control piezoceramic material.Yet, if grain-size is excessive, exist the interval of the intergranule of piezoceramic material to increase, thereby reduce by applying the trend of mechanical load to the amount of the electric charge of piezoceramic material generation.Thereby, in the present embodiment, with crystallite dimension rather than the grain-size controlled variable that acts on the piezoelectric property that improves piezoceramic material.
The crystallite dimension of piezoceramic material can pass through XRD (X-ray diffraction), and more specifically, by with the measurement of getting off: the X-ray diffraction pattern of taking piezoceramic material, determine the half-width (or integral breadth) at the peak of the scattering degree of expression incident X-bundle of rays in the X-ray diffraction pattern, then, with the following Scherrer equation of peak half width (integral breadth) substitution (Scherrer equation): D=K λ/(β cos θ), wherein D is a crystallite dimension; K is the Scherrer constant; λ is the X-beam wavelength; β is the half-width at half maximum of reflection X-bundle of rays; θ is a diffraction angle.
Preferably, piezoceramic material has the Curie temperature Tc more than 340 ℃.The thermotolerance of piezoceramic material strengthens along with Curie temperature Tc, so this piezoceramic material becomes and is more suitable for being used for high-temperature use such as motor car engine.
In 20 ℃ to 150 ℃ temperature range, piezoceramic material also preferably has the following rate of change of capacitance Δ Cp of 2500ppm/K.Because rate of change of capacitance Δ Cp reduces, so capacitor C p is little with the change quantitative change of temperature.Use in piezoelectric transducer under the situation of piezoceramic material, the susceptibility that this low rate of change of capacitance Δ Cp causes reducing piezoelectric transducer changes.
Further preferred, heat-resisting test is during 10 hours down at 250 ℃ in air, and the deterioration rate of the piezoelectric constant d33 of piezoceramic material (hereinafter only being called " piezoelectric constant deterioration rate Δ d33 ") is in-10%.Piezoelectric constant deterioration rate Δ d33 provides by following formula: { (the piezoelectric constant d33 after the heat-resisting test)-(initial piezoelectric constant d33) }/(initial piezoelectric constant d33).When the absolute value of piezoelectric constant deterioration rate Δ d33 reduced, the thermotolerance of piezoceramic material strengthened.
By at least one pair of anodal and negative pole element electrode is set on piezoceramic material, piezoceramic material advantageously can be applied on the piezoelectric element.Because piezoceramic material has satisfactory stability, thermotolerance and weather resistance as mentioned above, so the piezoelectric element that obtains is suitable for piezoelectric transducer such as combustion pressure sensor, detonation sensor, gyro sensor, piezo-resonator, piezoelectric vibrator, piezoelectric actuator, ultrasonic motor, fingerprint identification device or pressure-responsive device.
Piezoceramic material and piezoelectric element can be by following steps productions.
At first, oxide compound, carbonate or supercarbonate raw material powder are weighed up, and blend together, to obtain above-mentioned specific piezoceramic material composition.Powdered mixture is added in dispersion medium such as ethanol or the water, by wet blend such as ball mill and pulverizing.With the gained slurry drying to produce the raw materials mixed powdered material.
The raw material powder material was for example calcined 10 to 300 minutes down at 600 to 1100 ℃ in air.Incinerating powder stock and organic binder bond such as polyvinyl alcohol or polyvinyl butyral acetal, water-soluble binder and dispersion medium are mixed as alcohol, ether or water, and broken by wet-millings such as ball mills.With the powdered material of gained slurry drying with the generation pulverizing.
The powdered material of pulverizing is compacted into the shape of expectation.Shape about compacts has no particular limits.This compacts can be any suitable shape such as annular or dish type.For example, be desirably in about 30MPa and pass through the single shaft moulding down, then isostatic cool pressing (CIP) under about 150Mpa the powdered material compacting.For example under 900 to 1250 ℃ with this compacts sintering 1 to 10 hour.
Forming at least one pair of element electrode on the opposite side of sintered compact body by for example following steps: be under the situation of dish type when the sintered compact body, the relative panel surface of plane lapping sintered compact body, apply the apparent surface of conductive resin via silk screen printing to the grinding of sintered compact body, and roasting conductive resin suitably.Usually prepare conductive resin from conductive component, glass powder and organic medium.The example of conductive component is the powder of precious metal as silver, gold, palladium and platinum and alloy and its any mixture.As conductive component, also can use the powder of other metals such as copper and mickel and alloy thereof and its any mixture.The example of glass powder is for comprising SiO
2, Al
2O
3, ZnO and TiO
2Those.The example of organic medium is to be generally used for those of this kind conductive resin, as pure and mild ether.
At last, by in room temperature to about 200 ℃ temperature range, in transformer oil such as silicone oil, between electrode, applied about volts DS of 3 to 20kV/mm about 10 to 100 minutes, with the sintered compact body polarization.Polarization is optionally by applying high pressure to the sintered compact body, makes that the sintered compact body is overheated to carry out simultaneously in air.Can choose wantonly and remove electrode.The thus obtained sintered compact body and function that has or do not have element electrode can be made piezoceramic material.
A purposes of piezoelectric element is as shown in Figure 5, as the piezoelectric element 15 of off-resonance type detonation sensor 10.In the present embodiment, detonation sensor 10 is designed for so-called " center pass " off-resonance type detonation sensor of oil engine, described oil engine for short cylinder shape, has the transmitter pilot hole 12f that is formed centrally therein, on the cylinder body that is installed on engine as a whole.
More specifically, as illustrated in Figures 5 and 6, detonation sensor 10 comprises resin forming portion 11 and sensor unit 20 and weightening finish member 17, in described sensor unit 20, piezoelectric element 15 is made up with support member (metal casing) 12.
As shown in Figure 7, piezoelectric element 15 has ring-type element body 15c that is formed by piezoceramic material and a pair of element electrode 15a and the 15b that forms on the upper and lower side of this element body 15c.Support member 12 has cylindrical portion 12a that forms with outer lines 12x and the 12b of flange support section that forms on the lower end of this cylindrical portion 12a, to support piezoelectric element 15 thereon.Weightening finish member 17 has annular shape, installs around cylindrical portion 12a, and is configured on the piezoelectric element 15 so that piezoelectric element 15 is pressed to the 12b of support section.
Resin forming portion 11 has housing department 11a and the 11b of junctor portion, this housing department 11a is configured to cover piezoelectric element 15 and weightening finish member 17 etc. from the outside of support member 12 around sensor unit 20, and the 11b of this junctor portion is radial outwards outstanding from the outer surface of housing department 11a.
As illustrated in Figures 5 and 6, sensor unit 20 further comprises insulating component such as cylinder insulating sleeve 13s and annular insulcrete 13p and 13t, upper and lower annular lead electrode 16 and 14, and retaining member such as saucerspring 18 and nut 19.
Insulcrete 13p is inserted between 12b of support section and the following lead electrode 14, and with between lead electrode 16 in the insulcrete 13t insertion and the weightening finish member 17.Insulating sleeve 13s is installed around cylindrical portion 12a.By these insulating components 13p, 13t and 13s, piezoelectric element 15 and lead electrode 16 and 14 keep the electrical isolation with support member 12 and weightening finish member 17.
Saucerspring 18 is installed around cylindrical portion 12a, and be positioned on the weightening finish member 17.Nut 19 is formed with internal thread 19y, and be screwed on the outside screw 12x, to keep insulcrete 13p, following lead electrode 14, piezoelectric element 15, to go up lead electrode 16, insulcrete 13t, weightening finish member 17 and the saucerspring 18 between 12b of support section and nut 19 (with the order of mentioning), allow weightening finish member 17 thus.When these retaining members 18 and 19 make weightening finish member 17 that piezoelectric element 15 is pressed to the 12b of support section, in the assembled state of detonation sensor 10, place piezoelectric element 15 down at mechanical load (predetermined load).Randomly, can under mechanical load, piezoelectric element 15 be remained on the position by adhesive member or mould.
When in this sensor states mechanical force, stress, pressure etc. being applied to piezoelectric element 15, piezoelectric element 15 produces curtage by its direct piezoelectric effect.The curtage that produces is taken out from piezoelectric element 15 by lead electrode 14 and 16.
Though do not show in the accompanying drawings, detonation sensor 10 further comprises circuit taking out curtage from piezoelectric element 15, and curtage is converted into electrical signal (voltage signal).Circuit can be incorporated into or separately be arranged on the detonation sensor 10.
As shown in Figure 7, when with piezoelectric element 15 and weightening finish member 17 during along the thickness direction projection of piezoelectric element 15, element electrode 15a to lower surface (basal surface) SA of small part upper surface (top surface) SB towards weightening finish member 17.In the present embodiment, whole element electrode 15a passes through insulcrete 13t vertical surface to weightening finish member 17.Consider the cost performance and the susceptibility of detonation sensor 10, the ratio to the area S2 of small part upper surface SB and the area S1 of the lower surface SA of weightening finish member 17 of preferred element electrode 15a is more than 45%.As the top surface area S2 of element electrode 15a during less than the following table area S1 of weightening finish member 17, can reduce the amount of the electrode materials that uses among the amount of the electrode materials that uses among the element electrode 15a and the counter electrode 15b, reduce the cost of detonation sensor 10 thus.Can also guarantee to change the higher DE of surface area ratio S2/S1, and suitably adjust the capacitor C p of piezoelectric element 15.Yet, if the top surface area S2 of element electrode 15a excessively less than the following table area S1 of weightening finish member 17 because the transmitter that descends output, the susceptibility of detonation sensor 10 becomes deterioration.
As shown in Figure 7, under cutting sth. askew the inside and outside edge of lower end of weightening finish member 17 with the situation that forms beveled areas 17f, these beveled areas 17f is not included among the basal surface SA of weightening finish member 17.With vertical surface to any flat surfaces territory except that beveled areas of the weightening finish member 17 of element electrode 15a the basal surface SA as weightening finish member 17.Similarly, as shown in Figure 7, when being cut sth. askew to form beveled areas 15f in the inside and outside edge of the upper end of the element body 15c of piezoelectric element 15, element electrode 15a is formed under the situation on the top surface of element body 15c of the piezoelectric element 15 except that beveled areas 15f, and these beveled areas 15f is not included among the top surface SB of element electrode 15a.With vertical surface to any surperficial territory except that beveled areas 15f of the element electrode 15a of weightening finish member 17 as the top surface SB of element electrode 15a.
To the present invention be described in more detail with reference to following examples.Yet, it should be noted that following examples just schematically, are not intended to limit the invention to this.
The piezoceramic material of following production example 1 to 9 and comparative example 1 to 6.In each of embodiment 1 to 9 and comparative example 1 to 6, the raw material powder of zirconium white, titanium oxide, stannic oxide, weisspiessglanz and niobium oxides is weighed up, and blend together, to form the composition of table 1 when the sintering.The gained powder blend is added into ethanol, by the ball mill blend/pulverizing and dry of wetting, to produce the raw materials mixed powdered material.This raw material powder material was calcined 2 to 3 hours down at 800 ℃ in air.The pulverizing of incinerating powdered material is of a size of about 0.6 to 1 μ m.Incinerating powdered material and organic binder bond, water-soluble binder and alcohol are mixed, and it is broken and dry to carry out wet-milling by ball mill, to produce the powdered material of pulverizing.By single shaft moulding under about 30MPa and under about 150MPa isostatic cool pressing (CIP), the powdered material of pulverizing is compacted into the dish type with 19mm diameter and 1.4mm thickness.With compacts in air 1100 ℃ or 1300 ℃ of following sintering 2 to 4 hours.By the opposite face of grinding and sintering compacts, apply silver-colored paste to the opposite face of the grinding of sintered compact body, and roasting should the silver paste, forms pair of electrodes on this sintered compact body.Then, by under 100 to 150 ℃ in silicone oil, between electrode, apply 3 to 5kV/mm volts DS polarization sintered compact body and finish piezoceramic material.
Test rate of change of capacitance Δ Cp, Curie temperature Tc, piezoelectric constant d33 and the piezoelectric constant deterioration rate Δ d33 of each piezoceramic material under the following conditions.Evaluation test the results are shown in table 1.In addition, the picture of piezoceramic material is taken by scanning electronic microscope is optional.The electron microscopic picture of comparative example 5 is shown among Fig. 1.
[1] rate of change of capacitance Δ Cp
Use electric impedance analyzer (" HP4194 type " is available from Hewlett-Packard Company) to measure at the capacitor C p (20) of the piezoceramic material under 20 ℃ and the capacitor C p (150) of the piezoceramic material under 150 ℃.Rate of change of capacitance Δ Cp determines by following equation: Δ Cp={ (Cp (150)-Cp (20))/Cp (20) }/(150-20) * 1000000.We can say, when Δ Cp＜2500ppm/K, in actual use with no problem.
[2] Curie temperature Tc
The Curie temperature Tc of piezoceramic material uses electric impedance analyzer (" HP4194 type " is available from Hewlett-Packard Company) and electric furnace to measure.
[3] piezoelectric constant d33
By resonance/anti-resonance method according to EMAS-6100, be used in combination d33 meter (available from " Chinese Academy of Sciences "), measure the piezoelectric constant d33 of piezoceramic material.
[4] piezoelectric constant deterioration rate Δ d33
Measure the initial piezoelectric constant d33 of piezoceramic material in the same manner as described above.Make this piezoceramic material in air, under 250 ℃, carry out heat-resisting test 10 hours then.After the heat-resisting test, measure the piezoelectric constant d33 of piezoceramic material in the same manner as described above.Piezoelectric constant deterioration rate Δ d33 determines by following equation: Δ d33={ (the piezoelectric constant d33 after the heat-resisting test)-(initial piezoelectric constant d33) }/(initial piezoelectric constant d33).
Table 1
Table 1 (continuing)
As from table 1 finding, the piezoceramic material of embodiment 1 to 9 (wherein 1.000≤m≤1.075,0.470≤x＜0.490,0.020≤y≤0.040,0＜n＜1.000 and 0＜z≤0.025) has the rate of change of capacitance Δ Cp below the 2500ppm/K, Curie temperature Tc more than 340 ℃, the piezoelectric constant d33 that 340pC/N is above and-10% or better piezoelectric constant deterioration rate Δ d33, thereby show good piezoelectricity and temperature profile.On the contrary, the piezoceramic material of comparative example 1 (when 0.490＜x) has the piezoelectric constant d33 that is lower than 340pC/N, surpasses-10% piezoelectric constant deterioration rate Δ d33, and shows relatively poor piezoelectric property.The piezoceramic material of comparative example 2 (when z=0) has and surpasses-10% piezoelectric constant deterioration rate Δ d33 and 1300 ℃ high sintering temperature.As will be discussed in detail, do not expect to set more than the sintering temperature to 1300 ℃, this is because the crystallite of piezoceramic material is grown to coarse grain suddenly, and causes the reduction of piezoelectric constant d33.Because in Nb and the arbitrary crystal stability deterioration that has the lower piezoelectric stupalith of Sb, the piezoceramic material of comparative example 3 (wherein n=0) and comparative example 4 (wherein n=1) has the rate of change of capacitance Δ Cp above 2500ppm/K.The piezoceramic material of comparative example 5 (wherein m＞1.075) has the piezoelectric constant d33 that is lower than 340pC/N, and show with as among Fig. 1 with the white demonstration in the relatively poor piezoelectric property with the PbO of strip form appearance in the piezoceramic material.The piezoceramic material of comparative example 6 (wherein m＜1) has the piezoelectric constant d33 that is lower than 340pC/N equally, and shows relatively poor piezoelectric property.Show the composition of the piezoceramic material that is expressed from the next by control: Pb
m{ Zr
1-x-y-zTi
xSn
y(Sb
1-nNb
n)
zO
3, wherein 1.000≤m≤1.075,0.470≤x＜0.490,0.020≤y≤0.040,0＜n＜1.000 and 0＜z≤0.025, piezoceramic material obtains good piezoelectricity and temperature profile.
Experiment 2
Except changing the sintering temperature of piezoceramic material, produce piezoceramic material in the mode identical with the embodiment 1 of experiment 1.To test the piezoelectric constant d33 of every kind of piezoceramic material with experiment 1 identical mode.After removing electrode from the surface of piezoceramic material, observe the surface of piezoceramic material by XRD, to determine the crystallite dimension of piezoceramic material according to the Scherrer equation.Evaluation test the results are shown among table 2 and Fig. 2.In addition, take by scanning electronic microscope at 1250 ℃ and 1300 ℃ of pictures of locating the agglomerating piezoceramic material.The electron microscopic picture is shown in respectively in Fig. 3 and 4.
Table 2
| Sintering temperature (℃) | 1000 | 1050 | 1100 | 1150 | 1200 | 1250 | 1300 |
| d33(pC/N) | 320 | 365 | 384 | 381 | 358 | 347 | 312 |
| Grain-size (μ m) | 0.6 | 0.8 | 1.2 | 1.6 | 2.0 | 3.0 | 3.5 |
| Crystallite dimension (nm) | 26.2 | 30.0 | 32.1 | 34.3 | 38.4 | 39.0 | 41.4 |
As from table 2 and Fig. 2 finding, when sintering temperature was in 1050 to 1250 ℃ of scopes, piezoceramic material had above piezoelectric constant d33 of 340pC/N and 30 to 39nm crystallite dimension.When sintering temperature is lower than 1050 ℃ or when being higher than 1250 ℃, piezoceramic material has the piezoelectric constant d33 that is lower than 340pC/N and is lower than 30nm or surpasses the crystallite dimension of 39nm.As from Fig. 3 and 4 findings, when sintering temperature reached 1300 ℃, the crystallite of piezoceramic material was grown to coarse grain suddenly.Thereby shown, preferably the crystallite dimension by adjusting control piezoceramic materials such as sintering temperature 30 to 39nm, to improve the piezoelectric property of piezoceramic material.
Experiment 3
By using the piezoceramic material identical, as shown in Figs. 5 to 7, produce non-detonation sensor 10 sample of (hereinafter only being called " sample sensor ") as piezoelectric element 15 with testing 1 embodiment 1.Herein, element electrode 15a is by following formation: the upper limb of the sintered compact body of the piezoceramic material of cutting sth. askew, printed silver paste are to the top surface except that the territory, edge of chamfering of the sintered compact body of piezoceramic material, and roasting silver paste.Resin forming portion 11 is made by polyamide resin.Lead electrode 14 and 16 is made by brass.Insulcrete 13p and 13t, and insulating sleeve 13s is made by PET (polyethylene terephthalate).Weightening finish member 17 is made by iron type materials for sample No.5, is made by brass to 9 for sample Nos.1 to 4 and 6.In each of sample Nos.1 to 9, be 10.0g with the weight control of weightening finish member 17.In addition, when piezoelectric element 15 and weightening finish member 17 during along the thickness direction projection of piezoelectric element 15, the whole top surface SB of element electrode 15a is towards the basal surface SB of weightening finish member 17.The area S1 of basal surface SA of weightening finish member 17 is controlled to be 225.5mm
2On the other hand, changing the area S2 of the top surface SB of element electrode 15a, is different values to adjust surface area ratio S2/S1.With with experiment 1 identical mode at 20 ℃ of capacitor C p (20) of each sample sensor of test down.In addition, the output of the sample sensor of crossing over end 14a and 16a is measured in the vibrations that apply 3G by vibrator.Evaluation test the results are shown among table 3 and Fig. 8.
Table 3
| No. | S1(mm 2) | S2(mm 2) | (S2/S1)×100(％) | Cp(20)(pF) | Output (mV) |
| 1 | 222.5 | 74.0 | 32.8 | 810 | 48.0 |
| 2 | 222.5 | 98.5 | 43.7 | 1030 | 71.0 |
| 3 | 222.5 | 101.5 | 45.0 | 1040 | 75.0 |
| 4 | 222.5 | 111.5 | 49.4 | 1040 | 88.0 |
| 5 | 222.5 | 130.0 | 57.6 | 1050 | 90.2 |
| 6 | 222.5 | 149.7 | 66.4 | 1050 | 96.5 |
| 7 | 222.5 | 190.0 | 84.3 | 1040 | 98.4 |
| 8 | 222.5 | 223.1 | 98.9 | 1020 | 108.6 |
| 9 | 222.5 | 240.0 | 106.4 | 1040 | 110.6 |
As table 3 and shown in Figure 8, when surface area ratio S2/S1 was greater than or equal to 45%, sample sensor had the output above 75mV, and showed actual favourable susceptibility.Thereby shown that expectation control table area is than more than the S2/S1 to 45%, to guarantee the balance of high sensitivity and cost performance.
The full content of introducing Japanese patent application 2008-054433 (submission on March 5th, 2008), 2008-185029 (submission on July 16th, 2008) and 2008-317858 (submission on December 15th, 2008) herein is with for referencial use.
Though describe the present invention with reference to above-mentioned particular, the invention is not restricted to these schematic embodiments.According to above-mentioned instruction, the various corrections and the change of above-mentioned embodiment will take place for those skilled in the art.Scope of the present invention limits with reference to following claim.
Claims (6)
1. piezoceramic material, it has the composition that is expressed from the next: Pb
m{ Zr
1-x-y-zTi
xSn
y(Sb
1-nNb
n)
zO
3, wherein 1.000≤m≤1.075,0.470≤x＜0.490,0.020≤y≤0.040,0＜n＜1.000 and 0＜z≤0.025, and crystallite dimension is 30 to 39nm.
2. piezoceramic material according to claim 1, wherein said piezoceramic material have the above piezoelectric constant d33 of 340pC/N.
3. piezoceramic material, it has the composition that is expressed from the next: Pb
m{ Zr
1-x-y-zTi
xSn
y(Sb
1-nNb
n)
zO
3, wherein 1.000≤m≤1.075,0.470≤x＜0.490,0.020≤y≤0.040,0＜n＜1.000 and 0＜z≤0.025, and piezoelectric constant d33 is more than the 340pC/N.
4. piezoelectric element, it comprises the element body that forms by according to each described piezoceramic material of claim 1 to 3.
5. piezoelectric transducer, it comprises:
Piezoelectric element, it has by the element body that forms according to each described piezoceramic material of claim 1 to 3 and at least one pair of electrode that is arranged on the described element body;
Support member, it has support section to support described piezoelectric element;
The weightening finish member, it is disposed on the described piezoelectric element so that described piezoelectric element is pressed to described support section; And
Resin forming portion, it is from outside described piezoelectric element and the described weightening finish member of covering of described support member.
6. piezoelectric transducer, it comprises:
Piezoelectric element, it has by element body that forms according to each described piezoceramic material of claim 1 to 3 and a pair of first and second electrodes that are arranged on the described element body;
Support member, it has support section to support described piezoelectric element; And
The weightening finish member, it is disposed on the described piezoelectric element so that described piezoelectric element is pressed to described support section,
Wherein, when with described piezoelectric element and described weightening finish member during along the thickness direction projection of described piezoelectric element, the part surface at least of described first electrode is towards the basal surface of described weightening finish member; This of described first electrode ratio of area and the area of the basal surface of described weightening finish member of part surface at least is more than 45%.
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| JP2008-185029 | 2008-07-16 | ||
| JP2008185029A JP5062759B2 (en) | 2008-07-16 | 2008-07-16 | Non-resonant knock sensor |
| JP2008185029 | 2008-07-16 | ||
| JP2008317858A JP5222120B2 (en) | 2008-03-05 | 2008-12-15 | Piezoelectric ceramic composition, piezoelectric element using the same, and non-resonant knock sensor |
| JP2008-317858 | 2008-12-15 | ||
| JP2008317858 | 2008-12-15 |
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| CN102539066A (en) * | 2010-12-10 | 2012-07-04 | 比亚迪股份有限公司 | Preparation method for knock sensor |
| CN103204679A (en) * | 2013-04-24 | 2013-07-17 | 淄博宇海电子陶瓷有限公司 | Low-temperature sintering and low-aging rate PZT (lead zirconate titanate) piezoelectric ceramic material and preparation method thereof |
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| CN101525233B (en) | 2013-08-14 |
| JP2009234904A (en) | 2009-10-15 |
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