Patent Application
20130161556
The present disclosure generally relates to piezoelectric ceramic materials, and more particularly to lead-free piezoelectric ceramic materials based on ternary compositions containing bismuth zinc titanate-bismuth potassium titanate-bismuth sodium titanate.
Piezoelectric ceramic materials (also referred to as piezoelectric ceramics or piezoceramics) have been widely used in applications such as actuators, transducers, resonators, sensors, and random access memories. Among those piezoelectric ceramics, lead zirconate titanate (PZT), and its related solid solutions are the most widely used due to their excellent piezoelectric properties and the ease with which modifications by doping can be made during manufacturing. However, there are drawbacks to using PZT which limit its desirability in many applications. One concern is its possible environmental effects due to the toxicity of highly volatile PbO which can evolve from PZT during fabrication. Another drawback of PZT piezoceramics is the strong fatigue behavior associated with PZT. Fatigue is a phenomenon in which a piezoelectric material loses its switchable polarization and electromechanical strain during electrical cyclic loading.
For a detailed description of exemplary embodiments of the invention, reference will now be made to the accompanying drawings in which:
Certain terms are used throughout the following description and claims. In the following description and in the claims, the terms “including” and “comprising” are used in an open-ended fashion, and thus should be interpreted to mean “including, but not limited to . . . .”
The term “Curie temperature” refers to the temperature above which a piezoelectric material loses its spontaneous polarization and piezoelectric characteristics.
The term “polarization hysteresis” refers to lead-free piezoelectric ceramic materials that display non-linear polarization characteristics indicative of a polar state.
The term “electromechanical strain” refers to an electric field induced strain and is commonly expressed in terms of one or more piezoelectric coefficients (d33 and d31, for example), where dij (units pm/V) is the tensor property that relates the strain to the applied electric field (V/m). The d33 coefficient can be measured in many different ways, such a piezoelectric resonance, the direct piezoelectric effect, the indirect piezoelectric effect, and others. In the context of this disclosure, the d33 coefficient is calculated as the ratio between the maximum electromechanical strain and the applied electric field (d33=Smax/Emax). Sometimes this is described as the effective piezoelectric coefficient or the normalized strain or d33*. An example of its use is given in Y. Hiruma et al., J. Appl. Phys. 103:084121 (2008).
In the context of piezoelectric ceramic materials, the term “fatigue” refers to the observed loss of polarization and electromechanical strain after the application of a cyclic electric field.
The relative amounts or proportions of the components in a lead-free piezoelectric material are expressed in terms of either mole fraction or mole percent (mol %), as for example, 0.01≦x≦0.1, 0.3≦y≦0.5, and 0.4≦z≦0.6, or 10BZT-30BKT-60BNT.
The term “about” when referring to a numerical value or range is intended to include larger or smaller values resulting from experimental error that can occur when taking measurements. Such measurement deviations are usually within plus or minus 10 percent of the stated numerical value.
Temperature, ratios, concentrations, amounts, and other numerical data may be presented herein in a range format. It is to be understood that such range format is used merely for convenience and brevity and should be interpreted flexibly to include not only the numerical values explicitly recited as the limits of the range, but also to include all the individual numerical values or sub-ranges encompassed within that range, as if each numerical value and sub-range is explicitly recited. For example, a temperature range of about 100° C. to about 500° C. should be interpreted to include not only the explicitly recited limits of 100° C. and 500° C., but also to include every intervening temperature such as 250° C., 300° C., 350° C. and 400° C., and all sub-ranges such as 300° C. to 400° C., and so forth.
The following discussion is directed to various embodiments of the invention. The embodiments disclosed should not be interpreted, or otherwise used, as limiting the scope of the disclosure, including the claims. In addition, one skilled in the art will understand that the following description has broad application, and the discussion of any embodiment is meant only to be exemplary of that embodiment, and not intended to intimate that the scope of the disclosure, including the claims, is limited to that embodiment.
Lead-Free Piezoelectric Ceramics
Referring to
The compositions identified as C-I and K in Table 1, which are representative of the compositions enclosed by a black ellipse in
The Curie temperature (Tc) of most BZT-BKT-BNT compositions is in the range of about 100° C. and about 500° C. In some cases the Tc of a composition is between about 300° C. and about 400° C. The relative proportions of BZT, BKT and BNT may be varied during production of the ternary composition so that the product will have a specified Curie temperature range. Depending upon the desired end use of the composition, the operating temperature of the ceramic product may differ from the Tc of the BZT-BKT-BNT composition. For example, in some situations the operating temperature will be about 100° C.-150° C. lower than the Tc. As a practical matter, maximum operating temperature of a BZT-BKT-BNT ceramic product is its depolarization temperature.
Polarization hysteresis data for representative compositions indicate ferroelectric behavior, and a plot of the electric field induced strain appears as butterfly loops, consistent with other ferroelectric materials. Many of these compositions have properties similar to or exceeding those of the BKT-BNT and BKT-BZT binary systems. Table 2 shows piezoelectric data for some BNT-BKT and BKT-BZT binary compositions.
In some embodiments, a lead-free piezoelectric ceramic material has the general chemical formula xBi(Zn0.5Ti0.5)O3-y(Bi0.5K0.5)TiO3-z(Bi0.5Na0.5)TiO3, wherein x+y+z=1 and x, y, z≠0. In many embodiments, this ceramic material is a solid solution having a stable perovskite structure at standard atmospheric conditions. For example, in some embodiments the solid solution has the proportions 0.01≦x≦0.2, 0.01≦y≦0.99 and 0.01≦z≦0.75.
In some embodiments, a disclosed lead-free piezoelectric ceramic material has the proportions 0.01≦x≦0.1, 0.3≦y≦0.5, and 0.4≦z≦0.6.
Properties of the BZT-BKT-BNT materials may be evaluated by piezoelectric resonance measurements following the customary IEEE standard, poling studies to measure the low-field electromechanical strain coefficient d33, fatigue measurements, and studies of the temperature dependence of these piezoelectric properties. Polarization hysteresis data for representative compositions indicate ferroelectric behavior and the electric field induced strain appears as the expected butterfly loops. Excellent fatigue resistance exists for many of the BZT-BKT-BNT piezoelectric ceramics, with losses of ≦1 percent of the maximum polarization after 1 million cycles in many cases. This compares quite favorably to the fatigue behavior of conventional PZT materials. The piezoelectric strain coefficients (d33 and d31) of BZT-BKT-BNT compositions are generally below those of PZT. By way of comparison, conventional PZT piezoelectric ceramics typically demonstrate the following properties of piezoelectric resonance, low-field d33, fatigue and temperature dependence of piezoelectric properties: εr about 1000-3400; d33 about 200 pm/V-600 pm/V; k33 about 0.64-0.75; and Tc about 195° C.-365° C.
In some embodiments, a disclosed BZT-BKT-BNT piezoelectric ceramic material demonstrates a piezoelectric strain coefficient (d33) equal to or exceeding that of a lead zirconate titanate perovskite. In some embodiments, the ceramic material has a maximum electromechanical strain value in the range of about 0.20 percent to about 0.35 percent elongation under electric field.
In some embodiments, a disclosed lead-free piezoelectric ceramic material demonstrates fatigue resistance exceeding that of a lead zirconate titanate perovskite. In some embodiments, a BZT-BKT-BNT piezoelectric ceramic material demonstrates a maximum high-field piezoelectric d33 value in the range of about 200 pm/V to about 700 pm/V, and in some cases is in the range of about 400 pm/V to about 650 pm/V.
For many applications in which fatigue resistance of the piezoelectric ceramic is more important than the piezoelectric maximum strain performance, a disclosed BZT-BKT-BNT ceramic material may be advantageous. Many of the BZT-BKT-BNT compositions will meet or exceed the piezoelectric properties of doped PZT materials, and will provide a constant strain with minimal or no degradation over the life of a device employing such material. Many BZT-BKT-BNT ceramic materials with improved piezoelectric properties are substantially equivalent or superior to conventional PZT-based piezoelectric ceramics and have similar potential uses, including but not limited to actuators, transducers, resonators, sensors, and random access memories. Some of these applications will further benefit from the absence of lead in the piezoelectric ceramics.
Production of Lead-Free Piezoelectric Ceramics
A. Ceramic Discs
All lead-free BZT-BKT-BNT compositions described herein may be produced by any suitable solid-state synthesis method, using Bi2O3, NaCO3, KCO3, ZnO, and TiO2 starting powders of at least 99% purity. The Curie temperature (Tc) of the resulting product is generally between about 100° C. and about 500° C. The Tc of a piezoelectric ceramic may be increased or decreased by varying the relative amounts of the starting powders. The relative amounts of BZT, BKT and BNT may be adjusted so that the product will have a Tc in a specified range. In accordance with conventional solid state synthesis methods for making ceramic materials, the powders are milled, shaped and calcined to produce the desired ceramic product. Milling can be either wet or dry type milling, as is known in the art. High energy vibratory milling may be used, for instance, to mix starting powders and for post-calcination grinding. The powders are mixed with a suitable liquid (e.g., ethanol or water, or a combination of liquids) and wet milled with a suitable high density milling media (e.g., yttria stabilized zirconia (YSZ) beads). The milled powders are calcined, then mixed with a binder, formed into the desired shape (e.g., pellets) and sintered to produce a ceramic product with high sintered density. For testing purposes, prior to electrical measurements the ceramic disc may be polished to a suitable thickness (e.g., 0.9 mm), and a silver paste (e.g., Heraeus C1000) is applied to both sides of the discs. Depending upon the intended end use, a high-density BZT-BKT-BNT ceramic disc or pellet may be polished to a thickness in the range of about 0.5 μm to about 1 μm, suitable for use as a piezoelectric actuator, for example.
B. Ceramic Thin Film
When the intended use of the BZT-BKT-BNT ceramic material requires a thin film product, the production method may be modified to include chemical solution deposition using chemical precursors such bismuth nitrate, titanium isopropoxide, etc., or sputtering using solid state sintered or hot-pressed ceramic targets. Any suitable sputtering or chemical deposition method may be used for this purpose. The resulting thin film ceramic may have a thickness in the range of about 50 nm to about 10 μm, in some cases.
C. Piezoelectric Composites
For end uses such as sensors or transducers, which require the use piezoelectric composites, the above-described sintered BZT-BKT-BNT ceramic material can be modified for this purpose. The ceramic powder is ground or milled to the desired particle size and loaded into polymer matrix to create a 0-3 piezoelectric composite. The ceramic powder can be formed into sintered rods or fibers using injection molding or similar technique and loaded into a polymer matrix to create a 1-3 piezoelectric composite. The polymer may be piezoelectric, such as PVDF, or non-piezoelectric such as epoxy depending on the final application.
Lead-free ternary compositions were produced via solid-state synthesis methods, using Bi2O3, NaCO3, KCO3, ZnO, and TiO2 starting powders of at least 99% purity. Appropriate amounts of those powders were combined to yield BZT-BKT-BNT compositions having the following relative proportions (mole percent): 10-30-60, 10-35-55, 10-40-50, 10-45-45, 5-35-60, 5-40-55, and 5-45-50. Six hours of high energy vibratory milling was used for mixing starting powders and for post-calcination grinding. Ethanol mixtures containing 15 vol. % powder were milled with high density YSZ beads approximately ⅜ inch in diameter. After removal of YSZ, calcination was performed on the milled powder in covered crucibles at 900° C. for 6 hours. The calcined powders were mixed with a 3 wt. % solution of Polyvinyl Butyral (PVB) binder, and the powders were uniaxially cold pressed into 12.7 mm pellets at a pressure of 150 MPa. Following a 400° C. binder burnout, the pellets were sintered in covered crucibles at 1100° C. for 2 hours (5% BZT) or 1050° C. for 5 hours (10% BZT). Prior to electrical measurements, the ceramics discs were polished to thickness of 0.9 mm with smooth and parallel surfaces. Silver paste (Heraeus C1000) was fired on both sides in air at 650° C. for 30 minutes.
The BZT-BKT-BNT compositions of Example 1 were subjected to X-ray diffraction testing, and the resulting XRD patterns are shown in
A 0.1 Bi(Zn0.5Ti0.5)O3-0.4 (Bi0.5K0.5)TiO3-0.5 (Bi0.5Na0.5)TiO3 ceramic (composition “F” in Table 1 and
The above discussion is meant to be illustrative of the principles and various embodiments of the present invention. Numerous variations and modifications will become apparent to those skilled in the art once the above disclosure is fully appreciated. It is intended that the following claims be interpreted to embrace all such variations and modifications.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/US10/50947 | 9/30/2010 | WO | 00 | 2/28/2013 |
