GB2237928A - Piezoelectric composite material - Google Patents
Piezoelectric composite material Download PDFInfo
- Publication number
- GB2237928A GB2237928A GB8924987A GB8924987A GB2237928A GB 2237928 A GB2237928 A GB 2237928A GB 8924987 A GB8924987 A GB 8924987A GB 8924987 A GB8924987 A GB 8924987A GB 2237928 A GB2237928 A GB 2237928A
- Authority
- GB
- United Kingdom
- Prior art keywords
- composite material
- powder
- composite
- oxide
- matrix
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 230000007704 transition Effects 0.000 claims abstract description 9
- 239000003822 epoxy resin Substances 0.000 claims abstract description 6
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 6
- 239000012772 electrical insulation material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 6
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 238000010671 solid-state reaction Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 1
- 239000000919 ceramic Substances 0.000 abstract description 12
- 239000000463 material Substances 0.000 description 19
- 230000005684 electric field Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000470 constituent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- HFGPZNIAWCZYJU-UHFFFAOYSA-N lead zirconate titanate Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4].[Pb+2] HFGPZNIAWCZYJU-UHFFFAOYSA-N 0.000 description 4
- 238000006073 displacement reaction Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000030808 detection of mechanical stimulus involved in sensory perception of sound Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- BUKHSQBUKZIMLB-UHFFFAOYSA-L potassium;sodium;dichloride Chemical compound [Na+].[Cl-].[Cl-].[K+] BUKHSQBUKZIMLB-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/852—Composite materials, e.g. having 1-3 or 2-2 type connectivity
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A piezoelectric composite body 1 comprises a powder of a composition which exhibits a field-enforced ferroelectric phase transition, the said powder being supported as a dispersion in matrix of an electrical insulation material eg. epoxy resin. The powder may comprise a PLZT ceramic. <IMAGE>
Description
PIEZOELECTRIC COMPOSITE MATERIAL
This invention relates to a piezoelectric composite material. In particular. it relates to the use as a piezoelectric of a material which consists of a dispersion of a powder which exhibits an electric field enforced ferroelectric phase transition effect in a non-ferroelectric insulating matrix, usually a polymer.
Piezoelectric materials are materials which, when subjected to stress, will generate electric charge. Conversely, such materials will, when subjected to an electric field, undergo a strain which is proportional to the applied field. Such materials have been applied to a wide range of devices, including "passive" devices for the detection of sound and "active" devices for the generation of sound and mechanical displacements. A wide variety of materials exhibit the effect, including single crystals, ceramics and polymers. It has also been shown that multi-phase materials, or composites, can be piezoelectric. This invention relates to the improvement of such materials and more specifically to dispersions of a powder of a piezoelectric phase in an inactive insulating matrix such as a polymer. Such a composite is, by convention, known as a 0-3 piezoelectric composite.
It is well known that dispersions of conventional piezoelectric materials in a polymer can show favourable piezoelectric properties.
Dispersions in polymers of single crystal piezoelectric materials such as lithium sulphate as well as ceramics such as PZT-4 and PZT-5 (well known to those skilled in the art) and lead titanate have all ben used with greater and lesser degrees of success. These piezoelectrics are all linear materials operated well below their Curie temperature. In order to make a dispersion of a material such as this exhibit piezoelectricity, it is necessary to pole the composite electrically after fabrication. This entails the application of a large electric field to the composite in order to align the polar axes of the individual crystallites.
According to the invention, there is provided a piezoelectric composite material comprising a powder of a composition which exhibits a field-enforced ferroelectric phase transition, the said powder being supported as a dispersion in a matrix of an electrical insulation material.
The powder may consist of an oxide of composition substantially Pbl-3x12 Lax (Zry Tii#y)O3.
The matrix of electrical insulation material may be an epoxy resin material.
The invention also comprises a method of preparing a piezoelectric composite material.
By way of example, some particular embodiments of the invention will now be described with reference to the accompanying drawings, in which:
Figure 1 shows a matrix body of the composite material arranged for the poling by an electric field,
Figure 2 is a graph of a polarization/field hysteresis loop, for a particular sample of the composite material, and,
Figure 3 is a further graph showing strain/field for 0-3 composite materials.
This invention relates to the use of dispersions into insulating dielectrics of materials which show a forced ferroelectric phase transition when an electric field is applied. These materials are not piezoelectric in the normal sense, in that in the zero-field state they are non-polar. However, when a field is applied, they undergo a phase transition to a ferroelectric phase. At this phase transition, there is a large change in the volumes of the particles dispersed in the composite and the composite as a whole will undergo a change in volume and therefore linear dimensions.
A sample matrix body of the material arranged for poling is shown in Figure 1. The composite body 1 has a rectangular shape with a length dimension 2. The body is provided with electrodes 3 on its upper and lower faces and, to these electrodes, electrical connection wires 4 are attached. When a suitable applied voltage is connected between the wires 4 the poling effect will take place.
An example of a suitable piezoelectric material is a ceramic with the composition: Pb1#3x/2 Lax (Zry Til.y)03, ------------ (1)
where x = 0.082, y = 0.70
This ceramic is given the code PLZT8.2/70/30. At room temperature, the ceramic exhibits the polarization/field hysteresis loop shown in Figure 2.
Figure 2 is a graph which shows applied potential in KV.mm-1 on the horizontal axis. and on the vertical axis shows electrical charge on a scale of microcoulombs per square centimetre.
It can be seen that there is a large step up in the charge released from the sample at an applied field of about lKV.mm-1 on increasing the field and a corresponding step down at 0.2KV.mm-1 on decreasing the field. These two steps correspond to the forced transition into and out of the ferroelectric phase respectively.
If a powder of such a ceramic is dispersed into a polymer matrix, for example an epoxy resin such as CY1308/HY1308 manufactured by Ciba-Geigy, then a 0-3 composite is formed. If a slab of this composite is taken and a field applied according to the configuration shown in Figure 1, then the displacement and hence the strain in a direction normal to the applied field can be measured and recorded. This strain is shown in Figure 3.
Figure 3 is a graph which shows electrical field strength in KV.mm-1 on the horizontal axis, and on the vertical axis shows strain in units of lO**-6.
For comparison purposes the strain in a similar composite using PZT-5 ceramic as the active phase is shown. It can be seen that the strains which are generated in the PLZT composite are up to six times higher than those generated in the PZT-5 composite. This means that much higher displacements could be generated for a given field in a composite using the PLZT ceramic than in a composite using the conventional PZT-5 ceramic. The PLZT composite also has the advantage over the conventional composite that it does not require poling electrically.
It will readily be appreciated that this invention is not restricted to the particular PLZT composition given in formula'(l) above. Quite wide variations in x and y in this formulation can be made and the forced ferroelectric phase transition will still be observed. Any of the compositions which show this double loop behaviour can be used in this type of composite to considerable effect. In addition, there are other examples of ferroelectric which show double-loop forced ferroelectric behaviour.Such examples are: Pub99 Nb02 [ (Zrl-ySny) l-x Tix ] .98 O3 where y > .40 & x < .065 and Pb.95-3x/2SR.05Lax(Zr.70-ySn.30Tiy) O3 where .06 > x > .02 & .15 < y < .20
The oxide ceramic powders are prepared by one of several methods according to the composition of the solid solution required and its chemical reactivity. These methods are:a) Conventional Solid State Reaction in which the constituent oxides and/or their precursors are mechanically blended and mixed, calcined in the range 700 to 1100C and milled to a fine powder and refired at a higher temperature to complete the formation of a single phase solid solution. This was naturally cooled to room temperature or was quenched, ground and sieved to a preselected particle size range.
b) Solution Growth in which the constituent oxide components are dissolved in a molten salt, for example NaCl-KCl eutectics, at temperatures in the range 600-1000C and then slowly cooled to about 500C during which time the required composition has crystallised exsolution and is subsequently removed from the solvent by repeated washing in hot water. The crystalline powder is filtered and sieved to the desired size range which utilises solution chemistry.
c) Partial Chemical Precipitation in which the more refractory oxide constituents are atomically mixed by dissolving their soluble organic precursors, for example alkoxides in an alcohol, and precipitating a mixed hydroxide. for example SnxTiyZrz(OH)4, where x+y+z= 1, by slow hydrolysis. The reactive precipitate is dried to the mixed oxides, and blended with the other constituents then prefired, ground, refired and milled and sieved as in a).
d) Sol-Gel Process by which the cations of interest are taken into solution via organic precursors providing for higher purity, better homogeneity, lower processing temperatures and better control of properties. The mixed metal alkoxides are partially hydrolysed to sol monomer units, for example Me(OR)x (OH), and then polymerised to chain and 3-D networks which immobilise the solvent to yield a gel, for example (OR), Me-O-Me (OR),, where Me represents the mixed cations. The gel is then dried to a fine powder and fired to form a well-reacted single phase solid solution.
Powders of ceramics with these compositions can also be used in 0-3 active composites.
It will also be readily appreciated that such composites are not restricted to the use of CY1308/HY1308 epoxy resin as the matrix material. Many other polymer or glass systems could equally well be used and may exhibit advantages in certain circumstances where it is desired to have a composite which possesses certain elastic or dielectric properties. It should be noted here, however, that it is necessary to choose a material which possesses an electrical resistivity which is similar to that of the ferroelectric phase. This is to ensure that a significant proportion of the applied electric field is actually experienced by the ceramic particles. Examples of suitable matrix phases include epoxy resins, polyurethanes, natural rubbers, synthetic nitrile rubbers, silicone rubbers, polyester resins, and glasses such as borosilicate materials.
Claims (7)
1. A piezoelectric composite material comprising a powder of a composition which exhibits a field-enforced ferroelectric phase transition, the said powder being supported as a dispersion in a matrix of an electrical insulation material.
2. A composite material as claimed in Claim 1, where the powder consists of an oxide of composition substantially Pbl-3x/2Lax(ZryTil-y) 03 where x=0.082 and y=0.70.
3. A composite material as claimed in Claim 1, where the powder consists of an oxide of composition substantially Pub.99 Nb.02 [ (Zr1##Sn#J1.# T#x ] .98 O3 where y > .40 & x < .065.
4. A composite material as claimed in Claim 1, where the powder consists of an oxide of composition substantially Pb.95-3x/2Sr.05Lax(Zr.70 vSn.30Tiy) O3 where. 06 > x > .02 & .15 < y < .20.
5. A composite material as claimed in any one of Claims 1 to 4, in which the matrix material is an epoxy resin such as Ciba-Geigy
CY1308/HY 1308.
6. A method of preparing a composite material as claimed in any one of Claims 1 to 5, the method comprising the step of forming an oxide powder by a conventional solid state reaction, sol-gel process or a solution growth and precipitation method.
7. A composite material substantially as hereinbefore described.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8924987A GB2237928A (en) | 1989-11-06 | 1989-11-06 | Piezoelectric composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB8924987A GB2237928A (en) | 1989-11-06 | 1989-11-06 | Piezoelectric composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| GB8924987D0 GB8924987D0 (en) | 1989-12-28 |
| GB2237928A true GB2237928A (en) | 1991-05-15 |
Family
ID=10665790
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8924987A Withdrawn GB2237928A (en) | 1989-11-06 | 1989-11-06 | Piezoelectric composite material |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2237928A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281470A (en) * | 1991-03-01 | 1994-01-25 | Cci Co., Ltd. | Vibration damper |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0219895A1 (en) * | 1985-09-20 | 1987-04-29 | North American Philips Corporation | Method of manufacturing piezoelectric ceramic elements |
| US4826616A (en) * | 1987-09-08 | 1989-05-02 | Toyokako Kabushiki Kaisha | Piezoelectric pressure-sensitive element and method for making same |
-
1989
- 1989-11-06 GB GB8924987A patent/GB2237928A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0219895A1 (en) * | 1985-09-20 | 1987-04-29 | North American Philips Corporation | Method of manufacturing piezoelectric ceramic elements |
| US4826616A (en) * | 1987-09-08 | 1989-05-02 | Toyokako Kabushiki Kaisha | Piezoelectric pressure-sensitive element and method for making same |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5281470A (en) * | 1991-03-01 | 1994-01-25 | Cci Co., Ltd. | Vibration damper |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8924987D0 (en) | 1989-12-28 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 730A | Proceeding under section 30 patents act 1977 | ||
| WAP | Application withdrawn, taken to be withdrawn or refused ** after publication under section 16(1) |