CN1255358C - Piezoelectric ceramic material - Google Patents
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- CN1255358C CN1255358C CN 01109578 CN01109578A CN1255358C CN 1255358 C CN1255358 C CN 1255358C CN 01109578 CN01109578 CN 01109578 CN 01109578 A CN01109578 A CN 01109578A CN 1255358 C CN1255358 C CN 1255358C
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Abstract
The present invention provides leadless piezoelectric ceramic materials which have high piezoelectric strain constant d33 and high heat resistance, and are suitable for vibration sensor elements. In particular, the present invention provides the leadless piezoelectric ceramic materials whose piezoelectric strain constant d33 is 100 pc/n even higher, and the absolute value of rate of ash reduction (Dd33) of the piezoelectric strain constant d33 when the leadless piezoelectric ceramic materials are carried out on a high temperature test in 150 DEG C for 72 hours is 15% even lower. The leadless piezoelectric ceramic materials comprises three ingredients: BNT (bismuth titanate sodium, (Bi0.5Na0.5)TiO3, BT (barium titanate, BaTiO3), and BKT (bismuth titanate potassium, (Bi0.5K0.5)TiO3). The piezoelectric ceramic materials are optimally composed of crystalline structures containing tetragonal perovskite types.
Description
The present invention relates to piezoceramic material.In more detail, the present invention relates to have the high piezoelectric strain constant and the lead-free piezoceramic material of high heat resistance.Piezoceramic material of the present invention can be used for producing piezo-electric device such as vibrator, controller, transmitter and wave filter etc.Special suitable for producing shock sensor element.
The piezoceramic material that uses is the leaded piezoceramic material as PT (lead titanate) and PZT (lead zirconate titanate) etc. mostly at present., these leaded piezoceramic materials evaporate in firing and contain lead composition such as plumbous oxide etc., have polluted environment.In order environment not to be exerted an influence, handle that this evaporable contains the expense of lead composition or cost just becomes big.Therefore urgent hope realizes lead-free lead-free piezoceramic material.
At present, as lead-free piezoceramic material is known (Bi arranged
0.5Na
0.5) TiO3 (bismuth-sodium titanate is hereinafter referred to as " BNT ").BNT and PZT are similar, are the piezoceramic materials of perovskite typed, have high relatively electromagnetic coupled coefficient.
BNT as basic substance, is studied various improved compositions.Japan's special permission communique discloses BaTiO for 4-60073 number
3(barium titanate is hereinafter referred to as " BT ") or (Bi
0.5K
0.5) TiO
3(bismuth potassium titanate is hereinafter referred to as " BKT ") is solid-solubilized in the piezoceramic material composition among the BNT.Day disclosure special permission communique discloses the piezoceramic material composition of solid solution BKT and transition metal oxide in BNT for 11-217262 number.Day disclosure special permission communique discloses solid solution NaNbO in BNT for 9-100156 number
3The piezoceramic material composition of (sodium columbate).Day disclosure special permission communique discloses for 11-60333 number and has contained the solid solution ceramic material of BNT as a kind of perovskite typed of composition.
Piezoceramic material can be used for producing shock sensor.Shock sensor is used to detect the vibratility of engine and regulate ignition time.The shock sensor of detection that is used for the vibrations of engine and pressure is mainly by piezoelectric element production.
The piezoelectric element that is used to produce shock sensor must satisfy, and for example, following condition: (1) in order to obtain satisfied sensitivity, piezoelectric element should have high piezoelectric strain constant; When (2) using under 150 ℃ high temperature, piezoelectric element should tolerate insignificant cause thermal damage.In order to satisfy above-mentioned condition, above-mentioned PT or PZT routine are used to produce this piezoelectric element., from above-mentioned protection environmental problem, require to produce piezo ceramic element with the lead-free piezoceramic material of above-mentioned BNT class.
, the piezoelectric strain constant d of BNT
33,, little to 70pC/N with respect to the 300pC/N of PZT.And when about 150 ℃ or higher temperature, the piezoelectric property of BNT begins deterioration owing to BNT shifts to antiferroelectric phase.Therefore, it is difficult using BNT to produce shock sensor.
The present invention in light of this situation, its purpose is to provide has high piezoelectric strain constant d
33, and have high stable on heating, be suitable for as the lead-free piezoceramic material of producing the shock sensor element material.According to the present invention, can obtain having piezoelectric strain constant d
33Be 100pC/N or higher, and at 150 ℃ of piezoelectric strain constant d that place 72 hours high temperature test
33Reduced rate (D
D33) absolute value be 15% or lower lead-free piezoceramic material.
Present inventors have carried out studying extensively and profoundly, found that, by add the combination of the three component system of BT and BKT in BNT, can make piezoelectric strain constant d
33Reach thermotolerance and improve simultaneously, finish the present invention thus.Explain the present invention below.
The main points of first invention are to contain BNT, BT and the ternary piezoceramic material of BKT.BNT, BT and BKT are ferroelectric materials, but are different from BT and BKT, and BNT has the brilliant perovskite structure of rhombohedron, and BT and BKT then have the tetragonal perovskite structure.Piezoceramic material of the present invention is with the sosoloid of this three composition as necessary composition, and has the MPB identical with PZT (metacrystal phase border).
One of the present invention is characterised in that not only tetragonal perovskite structure compound and the brilliant perovskite structure compound of rhombohedron (BNT) is made up simply, and will be used for becoming 2 kinds (BT and BKT) with the kind of the tetragonal perovskite structure compound of BNT combination is specific, obtain having high piezoelectric strain constant d
33With good stable on heating piezoceramic material.At 150 ℃ of piezoelectric strain constant d that place 72 hours high temperature test
33Reduced rate (D
D33) absolute value be 15% or lower, shown good thermotolerance.In addition, D
D33Can calculate from following formula 1.Piezoceramic material of the present invention is applicable to the production of shock sensor element.
D
D33(%)=100 * (d after the test
33D before the value-test
33Value)/(d before the test
33Value)
When the proportion of composing of BNT hour (that is, when the perovskite structure compound proportion of composing of tetragonal is higher), the thermotolerance of piezoceramic material of the present invention sharply increases.Improving this stable on heating effect is, will with the specific 2 kinds of special effects that obtain of kind of the tetragonal perovskite structure compound of BNT combination for BT and BKT.The reason that why improves the thermotolerance effect is: when this specific tetragonal perovskite structure compound and BNT are used in combination, improved temperature that the piezoceramic material antiferroelectric phase shifts or the transfer that do not cause antiferroelectric phase.
The main points of second invention provide the BNT-BT-BKT series piezoelectric ceramic material of the crystalline texture that contains the tetragonal perovskite typed.When the BNT of the crystalline texture that will have the brilliant perovskite typed of rhombohedron and BT-BKT combination with tetragonal perovskite typed crystalline texture when forming the sosoloid of the crystalline texture that mainly has the tetragonal perovskite typed, can obtain having high piezoelectric strain constant d
33Piezoceramic material with good thermotolerance (at high temperature not taking place to shift) to antiferroelectric phase.At 150 ℃ of piezoelectric strain constant d that place 72 hours high temperature test
33Reduced rate (D
D33) absolute value be 15% or when lower, shown good thermotolerance.Therefore, the piezoceramic material of the present invention production that is used for the shock sensor element preferably.
In the present invention, can add characteristic according to the purposes of piezoceramic material and regulate auxiliary agent, thereby regulate material behavior.Regulate auxiliary agent as characteristic, preferred, for example, transistion metal compound.Preferred transistion metal compound is a transition metal oxide.The example of preferred transition metal oxide comprises Mn
2O
3, MnO
2, Co
2O
3, Fe
2O
3, NiO and Cr
2O
3Particularly preferably be Mn
2O
3Or MnO
2
Piezoceramic material of the present invention needn't have the crystalline texture of single tetragonal perovskite typed.Except the crystalline texture of tetragonal perovskite typed, as long as for piezoelectric strain constant d
33Do not have negative impact with good thermotolerance, can contain other crystalline texture yet because of adding that above-mentioned characteristic regulates that auxiliary agent has.
The main points of the 3rd invention provide the BNT-BT-BKT series piezoelectric ceramic material that crystalline texture is the tetragonal perovskite typed.When the BNT of the crystalline texture with the brilliant perovskite typed of rhombohedron is the sosoloid of tetragonal perovskite typed with the BT-BKT combination with tetragonal perovskite typed crystalline texture to form crystalline texture, can obtain having higher piezoelectric strain constant d
33Better stable on heating piezoceramic material.
Piezoceramic material of the present invention has the crystalline texture of single tetragonal perovskite typed, therefore, can further improve thermotolerance.At 150 ℃ of piezoelectric strain constant d that place 72 hours high temperature test
33Reduced rate (D
D33) absolute value be 15% or when lower, shown good thermotolerance.Therefore, piezoceramic material of the present invention is specially adapted to the production of shock sensor element.
The main points of the 4th invention are to have stipulated the preferred ratio of components of BNT, BT, BKT.The typical test of estimating in the thermotolerance that is used for the shock sensor element when sample is placed when carrying out high temperature test in 72 hours in 150 ℃, requires the piezoelectric strain constant d of piezoceramic material
33Reduced rate D
D33Absolute value be necessary for 15% or lower, more preferably 10% or lower.Each that drops on BNT-BT-BKT three component system composition diagram when the proportion of composing of BNT, BT and BKT formed some A, E, F, B, C, I, J and D and connected the zone that surrounds and (wherein do not comprise line segment between an A, E, F and the B and the line segment between some C, I, J and the D, do not comprise described point yet) in, piezoelectric strain constant d can be obtained
33Be 100pC/N or higher, and at 150 ℃ of piezoelectric strain constant d that place 72 hours high temperature test
33Reduced rate D
D33Absolute value be 15% or lower piezoceramic material.
The piezoceramic material of the present invention of the 4th above-mentioned invention main points is applicable to the production of shock sensor element.On the contrary, beyond the proportion of composing of BNT, BT and BKT drops on aforementioned region, because the piezoelectric strain constant d of piezoceramic material
33Or the thermotolerance reduction, so this piezoceramic material can not be actually used in the production of shock sensor element.
In Fig. 1, (in the high zone of BNT ratio) has above-mentioned MPB near line segment between composition point B and the C.Because the piezoelectric property of piezoceramic material is much improved near MPB, so can obtain high piezoelectric strain constant d
33For near composition point B and the C this MPB, can obtain showing piezoelectric strain constant d
33The piezoceramic material that surpasses 150pC/N.
The proportion of composing of BNT be higher than line segment between a B and the C near the zone of BNT proportion of composing in, piezoceramic material has the brilliant perovskite structure of rhombohedron.On the contrary, the proportion of composing of BNT be lower than line segment between a B and the C near the zone of BNT proportion of composing in, piezoceramic material has the tetragonal perovskite structure.According to the 4th main points of the present invention, can obtain to have the piezoceramic material of excellent heat resistance and suitable for producing shock sensor element, this piezoceramic material mainly has the tetragonal perovskite structure.This piezoceramic material has high piezoelectric strain constant d
33, and at 150 ℃ of piezoelectric strain constant d that place 72 hours high temperature test
33Reduced rate D
D33Absolute value be 15% or lower.
The 5th invention main points of the present invention are to have stipulated BNT, BT and the preferred ratio of components of BKT.The typical test of estimating in the thermotolerance that is used for the shock sensor element when sample is placed when carrying out high temperature test in 72 hours in 150 ℃, requires the piezoelectric strain constant d of piezoceramic material
33Reduced rate D
D33Absolute value be necessary for 15% or lower, be preferably 10% or lower.When the proportion of composing of BNT, BT and BKT drops in this compositing area, can obtain the utmost point and be suitable for the piezoceramic material that the shock sensor element is produced, the piezoelectric strain constant d of this piezoceramic material
33Be 100pC/N or higher, and 150 ℃ of piezoelectric strain constant d that place 72 hours high temperature test
33Reduced rate D
D33Absolute value be 10% or lower.
The BNT proportion of composing (that is, when the ratio of BT and BKT is higher) of near the proportion of composing of BNT is lower than MPB shown in Figure 1 some B or some C, the piezoelectric strain constant d of piezoceramic material
33Slowly reduce.But the proportion of composing of working as BNT, BT and BKT drops on usefulness shown in Figure 2 each composition point E, F, G, H, I and J is connected in the zone (comprise the zone of line segment between F, G, H and I point and put G and H) that surrounds the piezoelectric strain constant d of piezoceramic material
33Be 100pC/N or higher, therefore, this piezoceramic material can be actually used in the production of shock sensor element.In addition, the piezoceramic material corresponding to some A among Fig. 1 and some D has the piezoelectric strain constant d that is approximately equal to above-mentioned value
33
As mentioned above, material is relevant to the transfer of antiferroelectric phase under the thermotolerance of piezoceramic material and the high temperature.Near MPB, the tansition temperature of piezoceramic material temporarily reduces, therefore, its thermotolerance also reduces, on the contrary, and near the zone of the BNT proportion of composing the proportion of composing of BNT is lower than described MPB, wherein piezoceramic material has the tetragonal structure, and the thermotolerance of piezoceramic material sharply raises.This can think because the tansition temperature of the antiferroelectric phase of piezoceramic material raises or do not cause the cause that antiferroelectric phase shifts.
The piezoelectric strain constant d of piezoceramic material corresponding near some B the MPB shown in Figure 1 and some C
33Reduced rate D
D33Be about-50%.On the contrary, corresponding to the piezoelectric strain constant d of composition point F, G, H and I piezoceramic material in the described scope of the present invention's the 5th invention main points
33Reduced rate D
D33Be-10～-5%, promptly reduced rate reduces sharp.Show good thermotolerance corresponding to the piezoceramic material of forming some A and D, i.e. the piezoelectric strain constant d of this piezoceramic material
33Reduced rate D
D33Be-15～0%.
Embodiment
Below explain the present invention in the mode of embodiment.
As initial feed, use BaCO
3Powder, Bi
2O
3Powder, K
2CO
3Powder, Na
2CO
3Powder and TiO
2Powder carries out weighing with the proportion of composing shown in the acquisition table 1 (or as three component system composition diagram shown in Figure 3).These powder and ethanol packed into carried out wet mixing 15 hours in the ball milling.
The mixture that obtains is dry in hot water bath, 800 ℃ of following roastings 2 hours.Then product, organic binder bond and the ethanol of this roasting are packed into and carried out case of wet attrition 15 hours in the ball milling.The crushed material that obtains is dry in hot water bath, form particle, with the single shaft pressurization of particle, make diameter 20mm, the forming composition of thickness 3mm then by 1Gpa.The forming composition that obtains is carried out cold equipressure and is handled (CIP) under the pressure of 15GPa.
Forming composition after CIP handled obtains sinter 1050～1250 ℃ of following sintering 2 hours.The upper and lower surface of the sinter that obtains is carried out polished finish, and the garden that makes is tabular.Coating silver paste and sintering obtain the garden fuel plate on the upper and lower surface of this garden plate.Then, the direct current of in 10～200 ℃ transformer oil, the garden panel element the being used 3～7kV/mm processing that polarized in 30 minutes.After polarization is handled, this garden fuel plate is cut into inch strips, obtain measuring the flat column sample that piezoelectric property is used.
Before following test, for the flat column sample that obtains, use impedance analysis device (name of an article: HP4194A, Hallite Seals Pa Ka society system), measure piezoelectric strain constant d by resonance anti-resonance method
33Then, sample is carried out high temperature test in 72 hours in 150 ℃ of placements, obtain the piezoelectric strain constant d of test front and back
33Between difference rate D
D33The results are shown in the table 1.
Table 1
| The sample sequence number | Form point | d 33 (pC/N) | D d33 (％) | |||
| (Fig. 3) | x | y | z | |||
| 1 | A | 0.5 | 0 | 0.5 | 96 | -15 |
| 2 | B | 0.8 | 0 | 0.2 | 158 | -55 |
| 3 | C | 0.9 | 0.1 | 0 | 151 | -53 |
| 4 | D | 0.5 | 0.5 | 0 | 93 | -15 |
| 5 | E | 0.6 | 0 | 0.4 | 102 | -10 |
| 6 | F | 0.7 | 0 | 0.3 | 113 | -10 |
| 7 | G | 0.8 | 0.05 | 0.15 | 127 | -8 |
| 8 | H | 0.85 | 0.1 | 0.05 | 134 | -6 |
| 9 | I | 0.8 | 0.2 | 0 | 121 | -5 |
| 10 | J | 0.6 | 0.4 | 0 | 104 | -9 |
| 11 | K | 0.6 | 0.2 | 0.2 | 105 | -9 |
| 12 | L | 0.8 | 0.15 | 0.05 | 120 | -5 |
| 13 | M | 0.7 | 0.25 | 0.05 | 104 | -7 |
| 14 | N | 0.55 | 0.1 | 0.35 | 101 | -12 |
| 15 | O | 0.85 | 0.125 | 0.025 | 129 | -15 |
| 16 | P | 0.55 | 0.35 | 0.1 | 103 | -12 |
Obviously find out from table 1, in the sample that has with according to the corresponding composition of the composition point E～P of the 4th invention main points of the present invention, piezoelectric strain constant d
33Be 101～134pC/N, reduced rate D
D33Being-5～-15%, is preferred.In addition, this result is presented in the sample that has with according to the corresponding composition of the composition point E～M of the 5th invention main points of the present invention, piezoelectric strain constant d
33Be 102～134pC/N, reduced rate D
D33Being-5～-10%, is preferred.
The crystallization phases of each sample is accredited as the crystalline texture of tetragonal perovskite typed with X-ray diffraction.For example, Fig. 4 and Fig. 5 have shown the X ray diffracting data that has respectively corresponding to the sample of forming some I and some F composition.There is the peak of (002) and (200) in this data presentation near 2 θ=45 degree, illustrate that these samples have the crystalline texture of tetragonal perovskite typed.
Have with the sample that falls into scope of the present invention but will put the corresponding composition of composition point A, B, C and D outside 4 and 5 the scope in invention of the present invention be the crystalline texture of tetragonal perovskite typed, but the piezoelectric strain constant d of these samples
33Be lower than 100pC/N, reduced rate D
D33Absolute value greater than 15% (promptly being lower than-15%), so these samples can not be actually used in production, shock sensor element particularly.
In addition, piezoceramic material of the present invention is not restricted to the described embodiments, as long as without prejudice to spirit of the present invention, can make up arbitrarily in the scope of main points of the present invention.And then as required, piezoceramic material of the present invention also can contain trace assistant such as manganese oxide.In addition, for the crystallization phases of piezoceramic material of the present invention, there is no need must be the single-phase of tetragonal perovskite typed, also can have other crystallization phasess in the scope that piezoelectric property is not exerted an influence.
According to the present invention, can obtain unleaded, have a high piezoelectric strain constant (d
33Be 100pC/N or higher) and high heat resistance (promptly at 150 ℃ of d that place in 72 hours the high temperature test
33The absolute value of reduced rate be 15% or lower, or 10% or lower) piezoceramic material.Piezoceramic material of the present invention can be used for producing piezo-electric device such as vibrator, controller, transmitter and wave filter.Piezoceramic material of the present invention is specially adapted to produce the shock sensor element.
Fig. 1 is the three component system composition diagram, and expression will be put 4 described zones according to invention of the present invention.
Fig. 2 is the three component system composition diagram, and expression will be put 5 described zones according to invention of the present invention.
Fig. 3 is the enlarged view of three component system composition diagram, the composition point of describing in the expression respective embodiments.
Fig. 4 represents the X ray diffracting data corresponding to the sample of forming some I.
Fig. 5 represents the X ray diffracting data corresponding to the sample of forming some F.
Claims (4)
1. piezoceramic material is characterized in that containing three kinds of compositions of BNT, BT and BKT,
Wherein BNT is (Bi
0.5Na
0.5) TiO
3, BT is BaTiO
3, BKT is (Bi
0.5K
0.5) TiO
3,
Piezoceramic material contains the crystalline texture of tetragonal perovskite typed,
The composition of stupalith is represented with general formula xBNT-yBT-zBKT, and x, y and z are comprised in each the composition point A with the three component system composition diagram of BNT-BT-BKT, E, F, B, C, I, J and D connect in the zone that surrounds, this zone does not comprise an A, E, line segment and some C between F and the B, I, line segment between J and the D, do not comprise described point yet, wherein A is (0.5,0,0.5), E is (0.6,0,0.4), F is (0.7,0,0.3), B is (0.8,0,0.2), C is (0.9,0.1,0), I is (0.8,0.2,0), J is (0.6,0.4,0), D is (0.5,0.5,0).
2. piezoceramic material as claimed in claim 1, the crystalline texture that it is characterized in that stupalith is the tetragonal perovskite typed.
3. claim 1 or 2 described piezoceramic materials, the composition that it is characterized in that stupalith is represented with general formula xBNT-yBT-zBKT, and x, y and z are comprised in and form some E, F, G, H, I and J with each of the three component system composition diagram of BNT-BT-BKT and be connected in the zone that surrounds, this zone comprises line segment and some G and the H between these points of F, G, H and I, wherein E is (0.6,0,0.4), F is (0.7,0,0.3), G is (0.8,0.05,0.15), H is (0.85,0.1,0.05), I is (0.8,0.2,0), and J is (0.6,0.4,0).
4. piezoceramic material is in the purposes of preparation in the shock sensor, and described piezoceramic material contains three kinds of compositions of BNT, BT and BKT,
Wherein BNT is (Bi
0.5Na
0.5) TiO
3, BT is BaTiO
3, BKT is (Bi
0.5K
0.5) TiO
3,
Piezoceramic material contains the crystalline texture of tetragonal perovskite typed,
The composition of stupalith is represented with general formula xBNT-yBT-zBKT, and x, y and z are comprised in each the composition point A with the three component system composition diagram of BNT-BT-BKT, E, F, B, C, I, J and D connect in the zone that surrounds, this zone does not comprise an A, E, line segment and some C between F and the B, I, line segment between J and the D, do not comprise described point yet, wherein A is (0.5,0,0.5), E is (0.6,0,0.4), F is (0.7,0,0.3), B is (0.8,0,0.2), C is (0.9,0.1,0), I is (0.8,0.2,0), J is (0.6,0.4,0), D is (0.5,0.5,0).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01109578 CN1255358C (en) | 2001-04-18 | 2001-04-18 | Piezoelectric ceramic material |
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|---|---|---|---|
| CN 01109578 CN1255358C (en) | 2001-04-18 | 2001-04-18 | Piezoelectric ceramic material |
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|---|---|
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| CN1255358C true CN1255358C (en) | 2006-05-10 |
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ID=4658005
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1298670C (en) * | 2004-11-02 | 2007-02-07 | 清华大学 | Sodium bismuth phthalate-barium zirconium phthalate leadless piezoelectric ceramic and its preparation method |
| CN100361932C (en) * | 2006-05-16 | 2008-01-16 | 华中科技大学 | Bismuth-sodium titanate base lead-free piezoelectric ceramic |
| US8501031B2 (en) * | 2008-09-26 | 2013-08-06 | The Penn State Research Foundation | NBT based lead-free piezoelectric materials for high power applications |
| CN101913860B (en) * | 2010-08-19 | 2012-11-21 | 西北工业大学 | Bismuth titanate based piezoelectric ceramic with high curie temperature and preparation method thereof |
| CN103102154B (en) * | 2013-02-03 | 2014-07-02 | 北京工业大学 | Bi0.5Na0.5TiO3-BaTiO3-BiMg0.5Ti0.5O3 lead-free piezoelectric ceramic material |
| CN106365632B (en) * | 2016-08-31 | 2019-03-12 | 淄博高新技术产业开发区先进陶瓷研究院 | Lead-free piezoceramic material of ternary system and preparation method thereof |
| GB2559387B (en) * | 2017-02-03 | 2020-05-06 | Xaar Technology Ltd | Ceramic material comprising a pseudo-cubic phase, a process for preparing and uses of the same |
| CN110282967A (en) * | 2019-07-18 | 2019-09-27 | 覃向阳 | A kind of novel lead-free piezoceramic material |
-
2001
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