CN104326745B - A kind of have high tension performance and the piezoelectric of temperature stability and application thereof in wide warm area - Google Patents
A kind of have high tension performance and the piezoelectric of temperature stability and application thereof in wide warm area Download PDFInfo
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- CN104326745B CN104326745B CN201410534379.4A CN201410534379A CN104326745B CN 104326745 B CN104326745 B CN 104326745B CN 201410534379 A CN201410534379 A CN 201410534379A CN 104326745 B CN104326745 B CN 104326745B
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Abstract
The invention discloses and a kind of in wide warm area, there is high tension performance and the piezoelectric of temperature stability and application thereof.Described piezoelectric is the pure ABO without burnt green stone phase3Type perovskite structure, has and forms formula as follows: (1 x y) Pb (Mgl/3Nb2/3)O3‑x PbTiO3‑yXTiO3+ z M, in formula: X is at least one in Ca, Ba, Sr；M is MnO2, at least one in ZnO, MgO；0.29 < x≤0.38,0 ＜ y≤0.1,0 ＜ z≤0.1.Present invention achieves PMN PT material, in wide warm area, there is high piezoelectric constant and nearly zero-temperature coefficient simultaneously, the application requirement in driver and sensor field can be met, there is significant using value.
Description
Technical field
The present invention relates to a kind of have high tension performance and the piezoelectric of temperature stability and application thereof in wide warm area, tool
Body is said, relates to a kind of have high piezoelectric constant and the doping PMN-PT material of nearly zero-pressure electric constant temperature coefficient at wide warm area
Formula and this material, in driver and the application of sensor field, belong to technical field of function materials.
Background technology
Piezoelectric ceramics is the information functional material that a class is capable of the conversion of power electricity, at the numerous areas such as driver and sensor all
Have a wide range of applications.Now widely used piezoelectric ceramics includes lead zirconate titanate base piezoelectric ceramic Pb (ZrxTi1-x)O3(PZT)
And lead base composite perofskite piezoelectric ceramics such as (1-x) Pb (Mg1/3Nb2/3)O3-xPbTiO3(PMN-PT)、
(1-x)Pb(Zn1/3Nb2/3)O3-xPbTiO3(PZN-PT) etc..These materials have the piezoelectric property of excellence, but the opposing party at normal temperatures
Face is strongly depend on temperature due to its piezoelectric constant, such as Pb (Zr0.52Ti0.48)O3Pottery only has in the piezoelectric constant of about 100K
Under room temperature 1/3, its device application worked at low temperature or wide warm area of serious restriction.Research shows: cause piezoelectric
Can have by unstable main mechanism: polarization variation with temperature, phase transformation, the freezing of domain wall motion；Freeze with the electric charge at electricdomain
Knot etc., wherein phase transformation and domain wall motion to freeze be considered as two most important factor.In order to obtain the piezoresistive material of temperature stabilization
Material, traditional method is that material is carried out Mn-modified, makes to form disfigurement model at material internal, domain wall is carried out pinning,
To weaken or to sacrifice the domain wall motion contribution to piezoelectric.But this method has a biggest drawback, obtained material
Piezoelectric property significantly declines relative under room temperature.It addition, be made up of to regulate and control by changing material research
(LiNaK)(NbTa)O3Phase transformation, improves the temperature stability of piezoelectric constant.
Lead magnesio-niobate lead titanates PMN-PT is to have the ferroelectric material of high tension performance at quasi-homotype phase boundary (PMN-PT is mono-
Brilliant d33> 1500pC/N, k33> 95%).Theoretical Calculation shows, its intrinsic piezoelectric property is relatively big for PZT material,
After material i.e. carries out Mn-modified, its piezoelectric property is more excellent than PZT, and therefore it is considered as that the most potential wide warm area makes
Use piezoelectric.But there are some researches show, PMN-PT material, due to the B bit architecture of its complexity, is difficult to obtain as PZT
Mn-modified；On the other hand, there is ferroelectricity-ferroelectric phase transition, piezoelectricity near transformation temperature in PMN-PT material near 80 DEG C
Constant with temperature acutely changes, and also has research to obtain the PIN-PMN-PT material of high-curie temperature by doping In, and will
Ferroelectricity-ferroelectric phase height moves to more than 100 DEG C, reduces material temperature dependency more than room temperature to a certain extent, but
It is that its piezoelectric property is the most unstable at low temperatures.Recently, also studies have found that relaxor ferroelectric monocrystal is in tripartite and orthogonal phase boundary
Place's shear piezoelectric constant d24Temperature stability is good, but longitudinal piezoelectric strain constant d33With horizontal piezoelectric strain constant d31Temperature is steady
Qualitative poor.
Summary of the invention
The problems referred to above existed for prior art, it is an object of the invention to provide one and have high tension performance in wide warm area
With piezoelectric and the application thereof of temperature stability, to meet piezoelectric application requirement in the range of wide warm area.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of piezoelectric in wide warm area with high tension performance and temperature stability, its composition formula is (1-x-y) Pb
(Mg1/3Nb2/3)O3-x PbTiO3-yXTiO3+ z M, for the pure ABO without burnt green stone phase3Type perovskite structure, wherein:
X is at least one in Ca, Ba, Sr；M is MnO2, at least one in ZnO, MgO；0.29<x≤0.38、0
＜ y≤0.1,0 ＜ z≤0.1.
Preferably, in the composition formula of described piezoelectric, 0.30≤x≤0.37,0.005≤y≤0.08,0.01≤z
≤0.085。
The preparation of piezoelectric of the present invention can first use traditional solid-phase synthesis or first synthesize MgNb2O6Resynthesis
The two-step synthesis method of PMN-PT prepares the PMN-PT ceramic powder of doping, is then shaped and sinters.
Experiment shows: by the x, y, z in regulation composition formula, available Curie temperature changes in 160～180 DEG C not
Pure ABO containing burnt green stone phase3The doping PMN-PT material of type perovskite structure, this material piezoelectric constant when 25 DEG C becomes
Moving in 400～700pC/N, in-75～100 DEG C of temperature ranges, piezoelectric constant does not varies with temperature (d33The highest stablize
At 580pC/N, d31Maximum can be stablized at 200pC/N), and in this temperature range, material is applied the electric field of varying strength,
The strain that material occurs does not varies with temperature.Illustrate that doping PMN-PT material provided by the present invention is a kind of at wide warm area
Inside there is the piezoelectric of high tension performance and temperature stability, can be applicable to driver or sensor field.
Due to much more shallow than PT of the free energy potential barrier of XT, therefore the present invention is by replacing PT with XT, it is achieved that to phase boundary two
Phase coexisting temperature range carries out accurate control, thus reaches the change of this component physical property and vary with temperature controlled purpose.Separately
Outward, the present invention is in combination with compound M (MnO2, one or more in ZnO, MgO) system carried out suitable lacking
Falling into regulation and control, by controlling the size that piezoelectric property is contributed by domain wall motion, thus to have high-tension electricity in obtaining wide warm area normal simultaneously
Number and the doping PMN-PT material of nearly zero-temperature coefficient.
Compared with prior art, present invention achieves PMN-PT material and there is in wide warm area high piezoelectric constant and nearly zero simultaneously
Temperature coefficient, can be used for preparing piezoelectric actuator, piezo-electric motor, pressure transducer, piezoelectric accelerometer, piezoelectric gyroscope,
The devices such as micro-mass sensor, ultrasonic transducer, energy storage, especially can meet the application requirement in driver and sensor field,
There is significant using value.
Accompanying drawing explanation
The XRD figure of the piezoelectric that Fig. 1 is obtained by embodiment 1；
The SEM figure of the piezoelectric that Fig. 2 is obtained by embodiment 1；
The change curve of the dielectric constant with temperature of the piezoelectric that Fig. 3 is obtained by embodiment 1；
The piezoelectric that Fig. 4 is obtained by embodiment 1 strains variation with temperature curve under the electric field；
The piezoelectric d of the piezoelectric that Fig. 5 is obtained by embodiment 231With d33Variation with temperature curve；
The piezoelectric that Fig. 6 is obtained by embodiment 2 plastic strain amplitude variation with temperature curve under 2kV/cm electric field.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is expanded on further.The purity of raw material used in the present invention be AR level or
CP level；D under room temperature33By acoustics institute of Chinese Academy of Sciences d33Tester records, d31And d33Vary with temperature is to utilize resonance-the most humorous
The method of shaking records.
Embodiment 1
According to 0.63Pb (Mg1/3Nb2/3)O3-0.35PbTiO3-0.02BaTiO3+0.005MnO2The chemistry of+0.005MgO
Metering ratio is by PbO, MgCO3、TiO2、Nb2O5、BaCO3、MnO2Carry out dispensing, with deionized water as medium, warp
Planetary ball mill mixing 5 hours, powder body is through synthesizing 4 hours in 850 DEG C the most after drying, and planetary ball mill 6 hours is the most again
The PMN-PT ceramic powder that must adulterate；Add binding agent polyvinyl butyral resin, sinter at 1150 DEG C after dry-pressing formed,
Obtain described piezoelectric.
Fig. 1 is the XRD spectra of the piezoelectric that the present embodiment obtains, as seen from Figure 1: this piezoelectric is pure phase ABO3
Structure, without burnt green stone phase.
Fig. 2 is the SEM photograph of the piezoelectric that the present embodiment obtains, as seen from Figure 2: this piezoelectric has high cause
Density.
Fig. 3 is the change curve of the dielectric constant with temperature of the piezoelectric that the present embodiment obtains, as seen from Figure 3: this piezoelectricity
The Curie temperature of material is about 160 DEG C.
Fig. 4 is the piezoelectric that obtains of the present embodiment at 2kV/cm unidirectional electrical strain variation with temperature curve after the match, by
Fig. 4 is visible: this piezoelectric maximum strain amount in the range of-25～105 DEG C is almost unchanged.
It addition, after testing, the piezoelectric that the present embodiment obtains piezoelectric d at normal temperatures33For 580pC/N；At-75～85 DEG C
In temperature range, d31Stable at about 200pC/N；Under 2kV/cm electric field, this piezoelectric is at applied direction of an electric field
Strain reaches 0.11%.
Embodiment 2
According to 0.62Pb (Mg1/3Nb2/3)O3-0.35PbTiO3-0.03BaTiO3+0.005MnO2+0.002MgO+0.003ZnO
Stoichiometric proportion by PbO, MgCO3、ZnO、TiO2、Nb2O5、BaCO3、MnO2Carry out dispensing, with deionization
Water is medium, mixes 5 hours through planetary ball mill, and powder body is through the most after drying in 850 DEG C of synthesis 4 hours, planet the most again
Ball milling 6 hours, obtains the PMN-PT ceramic powder of doping；Add binding agent polyvinyl butyral resin, after dry-pressing formed
Sinter at 1300 DEG C, obtain described piezoelectric.
After testing, the Curie temperature of the piezoelectric that the present embodiment obtains is 162 DEG C, piezoelectric d at normal temperatures33For 510pC/N；
In-75～85 DEG C of temperature ranges, d31Stable at about 175pC/N.
The piezoelectric d of the piezoelectric that Fig. 5 is obtained by the present embodiment31With d33Variation with temperature curve, as seen from Figure 5:
Under 2kV/cm electric field, this piezoelectric reaches 0.095% in the strain of applied direction of an electric field.
The piezoelectric that Fig. 6 is obtained by the present embodiment plastic strain amplitude variation with temperature curve under 2kV/cm electric field, by
Fig. 6 is visible: the dependent variable in-50～140 DEG C of temperature ranges does not varies with temperature.
Embodiment 3
According to 0.62Pb (Mg1/3Nb2/3)O3-0.3PbTiO3-0.08BaTiO3+0.005MnO2+0.05MgO+0.03ZnO
Stoichiometric proportion by PbO, MgCO3、ZnO、TiO2、Nb2O5、BaCO3、MnO2Carry out dispensing, with deionization
Water is medium, mixes 5 hours through ball milling, and powder body is through the most after drying in 850 DEG C of synthesis 4 hours, ball milling 6 the most again
Hour, obtain the PMN-PT ceramic powder of doping；Add binding agent polyvinyl butyral resin, at 1200 DEG C after dry-pressing formed
Lower sintering, obtains described piezoelectric.
After testing, the Curie temperature of the piezoelectric that the present embodiment obtains is 140 DEG C, piezoelectric d at normal temperatures33For 400C/N；
In-75～85 DEG C of temperature ranges, d31Stable at about 125pC/N.
Embodiment 4
According to 0.625Pb (Mg1/3Nb2/3)O3-0.37PbTiO3-0.003BaTiO3-0.001SrTiO3-0.001
CaTiO3The stoichiometric proportion of+0.05MgO is by PbO, MgCO3、ZnO、TiO2、Nb2O5、BaCO3、SrCO3、
CaCO3Carrying out dispensing, with deionized water as medium, mix 5 hours through ball milling, powder body is through abundant dried in 850 DEG C of synthesis
4 hours, ball milling 6 hours the most again, obtain the PMN-PT ceramic powder of doping；Add binding agent polyvinyl alcohol contracting fourth
Aldehyde, sinters at 1250 DEG C after dry-pressing formed, obtains described piezoelectric.
After testing, the Curie temperature of the piezoelectric that the present embodiment obtains is about 175 DEG C, piezoelectric d at normal temperatures33For
420pC/N；In-75～85 DEG C of temperature ranges, d31Stable at about 130pC/N.
Finally it is necessary described herein: above example is served only for saying technical scheme in further detail
Bright, it is impossible to be interpreted as limiting the scope of the invention, those skilled in the art makes according to the foregoing of the present invention
Some nonessential improvement and adjustment belong to protection scope of the present invention.
Claims (4)
1. a piezoelectric in wide warm area with high tension performance and temperature stability, it is characterised in that for without Jiao
The pure ABO of green stone phase3Type perovskite structure, has and forms formula as follows: (1-x-y) Pb (Mgl/3Nb2/3)O3-x PbTiO3-
yXTiO3+ z M, in formula: X is at least one in Ca, Ba, Sr；M is MnO2, in ZnO, MgO extremely
Few one；0.29 < x≤0.38,0 ＜ y≤0.1,0 ＜ z≤0.1.
2. piezoelectric as claimed in claim 1, it is characterised in that: in the composition formula of described piezoelectric, 0.30≤x
≤0.37、0.005≤y≤0.08、0.01≤z≤0.085。
3. piezoelectric as claimed in claim 1 or 2, it is characterised in that: described piezoelectric is by first using biography
System solid-phase synthesis or first synthesize MgNb2O6The two-step synthesis method of resynthesis PMN-PT prepares the PMN-PT pottery of doping
Powder body, is then shaped preparing with sintering process.
4. the piezoelectric described in claim 1 or 2 is in driver and the application of sensor field.
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| CN107915486A (en) * | 2017-11-17 | 2018-04-17 | 南京大学 | A kind of method of raising PMN PT Curie temperature, piezoelectricity and heat endurance |
| CN111423231A (en) * | 2020-03-31 | 2020-07-17 | 上海师范大学 | Ternary system relaxor ferroelectric film material and preparation method and application thereof |
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| CN101194376A (en) * | 2005-06-10 | 2008-06-04 | 压电公司 | Piezo-electric composite sensor |
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| CN101194376A (en) * | 2005-06-10 | 2008-06-04 | 压电公司 | Piezo-electric composite sensor |
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| Synthesis of nanocomposities of PMN-PT-BT with metal oxides via surface modification;, Kyoung R. Han et al.;《J.Electroceram》;20061231;第17卷;第965-970页 * |
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