Piezeoelectric ceramic-polymer composites

• US 5,702,629 A
• Filed: 03/21/1996
• Issued: 12/30/1997
• Est. Priority Date: 03/21/1996
• Status: Expired due to Term

• Current Assignee: Alliedsignal Inc.
• Original Assignee: Alliedsignal Inc.
• Inventors: Baughman, Ray H., Iqbal, Zafar, Cui, Changxing, Kazmar, Theodore R., Dahlstrom, David K.
• Primary Examiner(s): KOSLOW, CAROL M
• Application Number:
  US08/618,690
• Time in Patent Office: 649 Days
• Field of Search: 252/62.9 R, 252/62.9 PI, 524/413, 310/313 R, 310/313 A, 310/311, 310/322, 310/357, 310/358, 310/317, 310/338
• US Class Current: 252/62.90R
• CPC Class Codes: H10N 30/045 by polarising
• CPC Class Codes: H10N 30/092 Forming composite materials
• CPC Class Codes: H10N 30/852 Composite materials, e.g. having 1-3 or 2-2 type connectivity

Abstract

Methods and compositions are described for the preparation of piezoelectric ceramic-polymer composites having improved properties for application in piezoelectric devices. These composites consist of piezoelectric particles embedded in a polymer matrix. The improvements of this invention result from discoveries of the effects of particle size, particle size dispersity, volumetric loading levels, ceramic dielectric constant, and polymer dielectric constant on performance. Various improved devices based on these compositions are also described.

Claims

1. A piezoelectric composite comprising a mixture of piezoelectric ceramic particles in a polymeric material, which polymeric material is continuous in three dimensions, wherein

(a) the weight-average diameter D of the piezoelectric ceramic particles ranges from 30 microns to 200 microns,

(b) at least 50 weight percent of the piezoelectric ceramic particles have an average diameter that is in the range from 0.5 D to 1.5 D,

(c) the dielectric constant of the piezoelectric ceramic particles at one kHz is less than about 700,

(d) the dielectric constant of the polymeric material at one kHz is above 2.8,

(e) the dielectric loss of the polymeric material at one kHz is less than 0.02, and

(f) the volume fraction of the piezoelectric ceramic in the composite is from 40% to 74%.

2. The composite of claim 1 wherein the polymeric material has a dielectric constant of above 5 and a dielectric loss of less than 0.02 at one kHz.

3. The composite of claim 1 wherein ceramic particles have a dielectric loss of less than 0.01, a Curie transition temperature that is above 200°

C. and wherein the volume percentage of ceramic particles in the mixture is from 50 to 60%.

4. The composite of claim 1 wherein the polymeric material comprises a polymer or copolymer having vinylidene fluoride monomer units, a polymer or copolymer having acrylonitrile monomer units, or mixtures thereof.

5. The composite of claim 1 wherein the polymeric material comprises a polymer selected from the group consisting of poly(oxymethylene), nylon 6, nylon 66, nylon 610, epoxies, polyurethanes, cellulose, and polymers derived from cellulose.

6. The composite of claim 1 wherein the ceramic particles comprise a substance selected from the group consisting of M_t M'"'"'_1-t NbO₃, wherein M and M'"'"' are selected from the group consisting of Na, Li, and K and t is less than unity;

Pb_x Q"_v (Ti_y Q_z Q'"'"'_u)O₃, wherein Q and Q'"'"' are selected from the group consisting of Zn, Nb, Zr, Sb, and Mn, Q" is selected from the group consisting of Bi, La, and Nb, x+v is about 1, y+z+u is about 1, and v is no more than about 0.05;

Na₀.5 Bi₀.5 TiO₃ ; and

Na₀.75 Pb₀.125 NbO₃.

7. The composite of claim 1 in which the ceramic particles comprise a substance selected from the group consisting of Pb_1-v Ca_v ! (Co_1/2 W_1/2)_w Ti_1-w !O₃, Pb_x Sm_y !(Ti_z Mn_1-z)O₃, PbNb₂ O₆, and mixtures thereof, wherein v is about 0.24, w is about 0.04, x is about 0.85, y is about 0.10 and z is about 0.98.

8. The composite of claim 2 wherein the weight-average diameter D of the particles of the piezoelectric ceramic is from 40 microns to 150 microns, wherein at least 80 weight percent of the particles of the ceramic have an average diameter that is in the range from 0.7 D to 1.3 D, and wherein the ratio of maximum particle diameter to minimum particle diameter is smaller than 1.3 for at least 50 weight percent of the ceramic particles.

9. The composite of claim 1 wherein said polymeric material has a dielectric constant of above 10 and a dielectric loss of less than 0.01 at one kHz and a melting point of above 150°

C.

10. A shaped article comprising the composite of claim 1 wherein the thickness of the shaped article is greater than or equal to 1 mm.

11. A shaped article comprising the composite of claim 1 wherein the ceramic particles have a weight-average particle size that is less than one-tenth of the smallest linear dimension of the shaped article.

12. The composite of claim 1 which is poled, wherein the piezoelectric ceramic particles have a ratio of -d₃₃ to (d₃₁ +d₃₂) that exceeds 5, wherein d₃₃ is the piezoelectric charge coefficient for stress applied in the poled direction, and d₃₁ and d₃₂ are the piezoelectric charge coefficients for stress applied in the directions orthogonal to the poled direction.

13. The composite of claim 12, wherein the piezoelectric ceramic has a ratio of -d₃₃ to (d₃₁ +d₃₂) that exceeds 10 and wherein the dielectric constant of the ceramic is less than 200 at one kHz.

14. The composite of claim 1 that contains from 45 to 60 volume percent of ceramic particles, wherein the ceramic particles form a continuous network of mechanically touching particles in one, two, or three dimensions.

15. The composite of claim 14, wherein the ceramic particles form a continuous network of mechanically touching particles in three dimensions.

16. The composite of claim 1 having a pore volume of less than about 1.0 volume percent.

23. A pressure sensor comprising the composite of claim 1 that is in the shape of a plate or cylinder and at least two electrodes electrically connected to the composite.

24. A piezoelectric actuator comprising the composite of claim 1.

25. The piezoelectric actuator of claim 24 which is an acoustic projector.

17. A process of making a composite comprising forming a mixture of piezoelectric ceramic particles in a polymeric material, which polymeric material is continuous in three dimensions, wherein

(a) the weight-average diameter D of the piezoelectric ceramic particles ranges from 30 microns to 200 microns,

(b) at least 50 weight percent of the piezoelectric ceramic particles have an average diameter that is in the range from 0.5 D to 1.5 D,

(c) the dielectric constant of the piezoelectric ceramic particles at one kHz is less than about 500,

(d) the dielectric constant of the polymeric material at one kHz is above 2.8,

(e) the dielectric loss of the polymeric material at one kHz is less than 0.025, and

(f) the volume fraction of the piezoelectric ceramic in the composite is from 40% to 74%,

wherein said piezoelectric ceramic particles are in the form of a free-flowing sintered powder obtained by heating a free-flowing mixture of ceramic-forming metal oxide powders at a temperature of at least about 400°

C. for a sufficient time that would sinter a compacted disk of said free-flowing mixture of ceramic-forming metal oxide powders, and wherein said mixture of piezoelectric ceramic powder and polymeric material is melt processed at a pressure of at least 5,000 psi to produce a shaped form.

18. The process of claim 17, wherein said piezoelectric particles are made by spray drying a calcinated mixture of oxides and wherein said piezoelectric particles comprise a substance selected from the group consisting of M_t M'"'"'_1-t NbO₃, wherein M and M'"'"' are selected from the group consisting of Na, Li, and K and t is less than unity;

Pb_x Q"_v (Ti_y Q_z Q'"'"'_u)O₃, wherein Q and Q'"'"' are selected from the group consisting of Zn, Nb, Zr, Sb, and Mn, Q" is selected from the group consisting of Bi, La, and Nb, x+v is about 1, y+z+u is about 1, and v is no more than about 0.05;

Na₀.5 Bi₀.5 TiO₃ ; and

Na₀.75 Pb₀.125 NbO₃.

19. A process for the preparation of a shaped, piezoelectric composite article comprising

(I) dispersing a free-flowing powder of piezoelectric ceramic particles into a solution of a solvent and a polymeric material,

(II) forming a composite by steps comprising at least one of (i) and (ii):

(i) adding a non-solvent for the polymeric material to the solvent and separating formed solids from the mixture of said solvent and non-solvent; and

(ii) evaporating the solvent from the solution to form a composite, and

(III) pressing the composite into a shaped form at a temperature of above 200°

C. and at a pressure of at least about 10,000 psi, wherein

(a) the weight-average diameter D of the piezoelectric ceramic particles is from 30 microns to 200 microns,

(b) at least about 50 weight percent of the piezoelectric ceramic particles have an average diameter that is in the range from 0.5 D to 1.5 D,

(c) the dielectric constant of the piezoelectric ceramic at one kHz is less than 500,

(d) the dielectric constant of the polymeric material at one kHz is above 2.8,

(e) the dielectric loss of the polymeric material at one kHz is less than 0.025, and

(f) the volume fraction of the piezoelectric ceramic in the composite is from 40% to 74%.

20. The process of claim 19 wherein the polymer comprises a material selected from the group consisting of a polymer or copolymer having vinylidene fluoride monomer units, a polymer or copolymer having acrylonitrile monomer units, or mixtures thereof and wherein the ceramic particles comprise a material selected from the group consisting of Pb_1-v Ca_v ! (Co_1/2 W_1/2)_w Ti_1-w !O₃, Pb_x Sm_y !(Ti_z Mn_1-z)O₃, PbNb₂ O₆, and mixtures thereof, wherein v is about 0.24, w is about 0.04, x is about 0.85, y is about 0.10 and z is about 0.98.

21. A process of poling a composite article having edges, which composite article comprises a mixture of ceramic particles in a polymeric material, which process comprises placing the composite article in an electrical path between a corona discharge and ground so that the edges of said composite are shielded from the corona discharge by an insulating material positioned on the edge of the composite article, wherein a side of said composite article opposite to the corona discharge is contacted with a metallic conductor, the composite article is positioned in a heated bath containing a fluid, the field applied to the composite article from the corona discharge is above about 120 kV/cm, and the temperature of the bath is at least about 30°

C. below the highest melting temperature of the polymeric material.

22. The process of claim 21 in which the composite article is placed in an electrical path between a corona discharge and ground so that the edges of the composite are shielded from the influence of the corona discharge by a cylindrical insulating material on an edge of the composite, wherein two opposite sides of said composite article are contacted with a metallic conductor, the composite article is positioned in a heated bath containing a fluid, the field applied to the composite article is above about 120 kV/cm, the temperature of the bath is at least about 30°

C. below the highest melting temperature of the polymeric material, and the composite article is in the shape of a cylinder.

26. A process for forming a composite comprising forming a mixture of piezoelectric ceramic particles in a monomer or prepolymer, followed by reaction of said monomer or prepolymer to produce a polymeric matrix material that is continuous in three dimensions, wherein

(a) the weight-average diameter D of the piezoelectric ceramic particles ranges from 30 microns to 200 microns,

(b) at least 50 weight percent of the piezoelectric ceramic particles have an average diameter that is in the range from 0.5 D to 1.5 D,

(c) the dielectric constant of the piezoelectric ceramic particles at one kHz is less than about 700,

(d) the dielectric constant of the polymeric material at one kHz is above 2.8,

(e) the dielectric loss of the polymeric material at one kHz is less than 0.02, and

(f) the volume fraction of the piezoelectric ceramic in the composite is from 40% to 74%.

27. The process of claim 26, wherein the said polymeric matrix material comprises an epoxy composition.