Patent Application
20130168596
The present invention is related to a piezoelectric material, and in particular, a high performance polycrystalline piezoelectric material based on lead hafnate.
For the past 60 years, perovskite Pb(ZrxTi1-x)O3 (PZT) piezoelectric ceramics have dominated the commercial market of piezoelectric sensors, actuators and medical ultrasonic transducers due to their high dielectric, piezoelectric and electromechanical coupling factor properties. In addition, the properties of PZT piezoelectric ceramics can be further modified with different additives and/or dopants. In particular, PZT piezoelectric ceramics with compositions in the vicinity of a morphotropic phase boundary (MPB) that separates a rhombohedral phase from a tetragonal ferroelectric phase can exhibit anomalously high dielectric and piezoelectric properties. The high properties are the result of enhanced polarizability from the coupling between two equivalent energy states, i.e. between a tetragonal phase and a rhombohedral phase, which allows optimum domain reorientation during poling.
Numerous PZT formulations/compositions have been engineered for specific characteristics that enhance their use in many applications. For example, Tables I and II list the properties of commercially available soft PZT ceramics, and
1TRS Technologies;
2CTS;
3PIceramic;
4Piezo-kinetics;
5Ferroperm;
6Morgan.
1TRS Technologies;
2CTS;
3PIceramic;
4Piezo-kinetics;
5Ferroperm;
6Morgan.
It is appreciated that innovations in electronic devices have been the driving force for new developments in piezoelectric ceramics. In fact, and in order to meet the newly developed electromechanical devices, materials with Curie temperatures equivalent to heretofore developed materials but with higher dielectric and piezoelectric properties, and/or materials with similar dielectric and piezoelectric properties but higher Curie temperatures, are desired.
In addition to the above, the electromechanical coupling factor—the square of which is closely related to output power density—is known to be an important material parameter in ultrasonic transducer applications and the dielectric variation for prior art PZT based materials is relatively broad and on the order of 2000-8000 ppm/° C. Therefore, a new polycrystalline piezoelectric material with increased electromechanical coupling factor and reduced dielectric variation would also be desirable.
Ternary polycrystalline materials based on lead hafnate (PbHfO3) and having improved dielectric, piezoelectric, and/or thermal stability properties are provided. In addition, the PbHfO3 based materials can exhibit enhanced electromechanical coupling factors when compared to PZT based ceramics. The inventive materials can be used as high performance actuators, piezoelectric sensors and/or ultrasonic transducers.
In particular, the ternary polycrystalline materials provide piezoelectric ceramic materials based on lead hafnium titanate, e.g. PbHfO3—PbTiO3 (PHT), that have a perovskite crystal structure with an ABO3 formula and are characterized by a substitution of heterovalent acceptor and donor ions at Zr/Hf sites. In addition, Pb(MI3+,MII5+)O3—PHT ternary systems are provided that have: (1) equivalent Curie temperatures as prior art PZT based ceramics but exhibit higher dielectric and piezoelectric properties when compared thereto; and/or (2) comparable dielectric and piezoelectric properties as prior art PZT based ceramics but exhibit higher Curie temperatures when compared thereto.
In some instances, the ternary polycrystalline materials have a formula of Pb1-xMx [(MI,MII)O3]1-y-zHfzTiyO3, where M is Ba2+, Ca2+, Sr2+, La3+ and the like; MI is Mg2+, Zn2+, Ni3+, Yb3+, Sc3+, In3+ and the like; MII is Nb5+, Ta5+, Sb5+ and the like; x is greater than or equal to 0.0 and less than 0.2; y is greater than 0.3 and less than 0.7; and z is greater than 0.3 and less than 0.7. In other instances, the ternary piezoelectric polycrystalline material has a formula of Pb1-xMx [(MI3+,MII5+)O3]1-y-zHfzTiyO3, where Hf 4+ or Ti4+ ions are at least partially replaced with donor dopants or acceptor dopants. The donor dopants can be Nb5+, Ta5+, W5+ and the like and the acceptor dopants can be Fe2+,3+, Co2+,3+, Mn2+,3+ and the like.
The inventive material can have a Curie temperature in the range of 180° C. to 280° C. and a piezoelectric coefficient d33 greater than 600 pC/N, a Curie temperature of greater than 300° C. and a piezoelectric coefficient d33 greater than 500 pC/N, a Curie temperature in the range of 260-300° C. and a piezoelectric coefficient d33 in the range of 450-680 pC/N, and/or a Curie temperature greater than 120° C. and a piezoelectric coefficient d33 greater than 800 pC/N. In addition, the material can have electromechanical coupling k33 greater than or equal to 78-80%.
a is a graphical plot illustrating piezoelectric coefficient d33 as a function of PMN content;
b is a graphical plot illustrating planar electrochemical coupling kp as a function of PMN content;
Inventive lead hafnium titanate-lead magnesium niobate (PHT-PMN) ternary ceramics with compositions of (1-x)Pb(Hf1-yTiy)O3-xPb(Mg1/3Nb2/3)O3 ((1-x)Pb(Hf1-yTiy)O3-xPMN, x=0˜0.5, y=0.515˜0.7) are provided. For example and for illustrative purposes only, an example of how typical PHT-PMN ternary ceramics according to one or more embodiments of the present invention were produced and associated properties are described below.
The inventive materials were prepared using a two-step precursor method. Raw materials of MgCO3 (99.9%, Alfa Aesar, Ward Hill, Mass.), Nb2O5 (99.9%, Alfa Aesar), HfO2 (99.9%, Alfa Aesar) and TiO2 (99.9%, Ishihara, San Francisco, Calif.) were used to synthesize columbite precursors of MgNb2O6 and Hf0.45Ti0.55O2 at 1000° C. and 1200° C., respectively. Thereafter, Pb3O4 (99%, Alfa Aesar) and the MgNb2O6 and Hf0.45Ti0.55O2 percursor powders were batched stoichiometrically by wet-milling in alcohol for 24 hours (h). Dried mixed powders of the Pb3O4, MgNb2O6 and Hf0.45Ti0.55O2 were then calcined at 800° C. for 4 h to produce synthesized powders which were subsequently vibratory milled in alcohol for 12 h. The synthesized powders were then granulated and pressed into pellets having a 12 mm diameter, followed by a binder burnout at 550° C. and sintering in a sealed crucible at 1250° C. In order to minimize PbO evaporation during sintering, PbZrO3 was used as a lead (Pb) source in the sealed crucible.
Sintered pellets were tested for temperature dependence of dielectric permittivity with
Based on the above results, an isothermal map of Currie temperature (TC) for (1-x)Pb(Hf1 -yTiy)O3-xPMN was developed and is shown in
The dielectric, piezoelectric and electromechanical properties of all studied (1-x)Pb(Hf1-yTiy)O3-xPMN compositions are summarized in Table III. In addition, the piezoelectric coefficient d33 and planar electromechanical coupling kp as a function of PMN are shown in
The main properties of other systems, such as (1-x)Pb(Hf1-yTiy)O3-xPb(Ni1/3Nb2/3)O3 (PHT-PNN), (1-x)Pb(Hf1-yTiy)O3-xPb(Sc0.5Nb0.5)O3 (PHT-PSN) and (1-x)Pb(Hf1-yTiy)O3-xPb(Zn1/3Nb2/3)O3 (PHT-PZN), are given in Tables IV and V below, respectively.
In order to provide a clearer view of the enhanced properties exhibited by the inventive materials,
The invention is not restricted to the illustrative examples and embodiments described above. The examples are not intended as limitations on the scope of the invention. Methods, apparatus, compositions, and the like described herein are exemplary and not intended as limitations on the scope of the invention. Changes therein and others will occur to those skilled in the art and, as such, the specification and the appendices should be interpreted broadly.
This application claims priority of U.S. Provisional Application 61/581,365, filed Dec. 29, 2011, the contents of which are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| 61581365 | Dec 2011 | US |
