High dielectric constant composite materials and methods of manufacture

• US 8,889,776 B2
• Filed: 03/23/2012
• Issued: 11/18/2014
• Est. Priority Date: 03/23/2011
• Status: Active Grant

• Current Assignee: Curators of the University of Missouri (University of Missouri)
• Original Assignee: Curators of the University of Missouri (University of Missouri)
• Inventors: Curry, Randy D., O'Connor, Kevin
• Primary Examiner(s): LEE, DORIS L
• Application Number:
  US13/428,950
• Publication Number:
  US 20120245016A1
• Time in Patent Office: 970 Days
• Field of Search: 524/430
• US Class Current: 524/430
• CPC Class Codes: B05D 1/005 Spin coating
• CPC Class Codes: B05D 1/40 Distributing applied liquids or other fluent materials by members moving relatively to surface
• CPC Class Codes: B29C 2035/0827 using UV radiation
• CPC Class Codes: B29C 39/003 characterised by the choice of material
• CPC Class Codes: B29C 43/003 characterised by the choice of material
• CPC Class Codes: B29K 2101/00 Use of unspecified macromolecular compounds as moulding material use of unspecified rubbers B29K2021/00
• CPC Class Codes: B29K 2509/02 Ceramics
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C04B 2235/483 Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
• CPC Class Codes: C04B 2235/5427 millimeter or submillimeter sized, i.e. larger than 0,1 mm
• CPC Class Codes: C04B 2235/5436 micrometer sized, i.e. from 1 to 100 micron
• CPC Class Codes: C04B 2235/5445 submicron sized, i.e. from 0,1 to 1 micron
• CPC Class Codes: C04B 2235/5454 nanometer sized, i.e. below 100 nm
• CPC Class Codes: C04B 2235/5472 Bimodal, multi-modal or multi-fraction
• CPC Class Codes: C04B 35/4682 based on BaTiO3 perovskite phase
• CPC Class Codes: C04B 35/6316 Binders based on silicon compounds
• CPC Class Codes: C08K 2003/2206 of calcium, strontium or barium
• CPC Class Codes: C08K 2003/2237 of titanium
• CPC Class Codes: C08K 3/013 Fillers, pigments or reinforcing additives
• CPC Class Codes: C08K 3/22 of metals
• CPC Class Codes: C08K 3/24 : Acids; Salts thereof C08K3/16 takes precedence
• CPC Class Codes: C08K 3/30 : Sulfur-, selenium- or tellurium-containing compounds
• CPC Class Codes: C08L 101/00 : Compositions of unspecified macromolecular compounds
• CPC Class Codes: H01B 19/00 : Apparatus or processes specially adapted for manufacturing insulators or insulating bodies manufacture of porcelain for electric insulation C04B33/26
• CPC Class Codes: H01B 3/12 : ceramics
• CPC Class Codes: H01G 4/206 : inorganic and synthetic material
• CPC Class Codes: H01Q 1/362 : for broadside radiating helical antennas
• CPC Class Codes: Y10T 29/49227 : Insulator making

Abstract

The present invention relates to composite materials with a high dielectric constant and high dielectric strength and to methods of producing the composite materials. The composite materials have high dielectric constants at a range of high frequencies and possess robust mechanical properties and strengths, such that they may be machined to a variety of configurations. The composite materials also have high dielectric strengths for operation in high power and high energy density systems. In one embodiment, the composite material is composed of a trimodal distribution of ceramic particles, including barium titanate, barium strontium titanate (BST), or combinations thereof and a polymer binder.

Claims

1. A composite material having a high dielectric constant and high dielectric strength, the composite material comprising:

a quadmodal distribution of high dielectric constant ceramic particles bonded together by a polymeric material, wherein the quadmodal distribution comprises at least one first ceramic particle having a first diameter in a first range between 40 μ

m and 220 μ

m, at least one second ceramic particle having a second diameter in a second range between 500 nm and 5 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 500 nm; and

,

wherein the polymeric material is polymerized in-situ from a polymeric precursor and binds directly to a surface of each of the high dielectric constant ceramic particles.

2. The composite material of claim 1, wherein the polymeric precursor is polymerized in-situ to form a polysilsesquioxane amongst the high dielectric constant ceramic particles.

3. The composite of claim 1, wherein the polymeric precursor is polymerized by at least one of heat, a chemical catalyst, or ultraviolet light.

4. The composite material of claim 1, wherein the ceramic particles are perovskites.

5. The composite material of claim 4, wherein the perovskites comprise barium titanate, strontium titanate, barium strontium titanate, lead zirconate titanate, lead magnesium niobate lead titanate, or combinations thereof.

6. The composite material of claim 1, wherein the polymeric precursor functionalizes the surface of each of the high dielectric constant ceramic particles.

7. The composite material of claim 6, wherein the polymeric precursor is selected from silanes, zirconates, and titanates.

8. The composite material of claim 7, wherein the polymeric precursor is a trialkoxysilane selected from a group consisting of vinyltrimethoxysilane, triethoxyvinylsilane, aminopropyltriethoxysilane, and combinations thereof.

9. A composite material having a high dielectric constant and high dielectric strength, the composite material comprising:

a trimodal distribution of high dielectric constant ceramic particles bonded together by a polymeric material, wherein the trimodal distribution comprises at least one first ceramic particle having a first diameter in a first range between 40 μ

m and 220 μ

m, at least one second ceramic particle having a second diameter in a second range between 500 nm and 5 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 500 nm; and

,

the polymeric material is a gelling polymer, wherein the polymeric material is mixed with a solvent and the polymeric material absorbs at least a portion of the solvent to form a gel.

10. The composite material of claim 9, wherein the polymer is cooled to solidify after the composite material is formed.

11. The composite material of claim 9, wherein the solvent is removed from the gel after the composite material is formed.

12. The composite material of claim 9, wherein the polymeric material is melted in the solvent and then cooled to form the gel.

13. The composite material of claim 12, wherein the polymeric material is selected from agar, gelatin, carrageen, and combinations thereof.

14. The composite material of claim 9, wherein the composite is impregnated with a dielectric liquid to displace any remaining voids.

15. The composite material of claim 14, wherein the dielectric liquid is selected from water, alkylene carbonates, oils, or a combination thereof.

16. The composite material of claim 9, wherein the ceramic particles are perovskites.

17. The composite material of claim 16, wherein the perovskites comprise barium titanate, strontium titanate, barium strontium titanate, lead zirconate titanate, lead magnesium niobate-lead titanate, or combinations thereof.

18. A method for manufacturing a composite material having a high dielectric constant and high dielectric strength, the composite material including a quadmodal distribution of high dielectric constant ceramic particles and a polymeric material, where the polymeric material is mixed with the distribution of high dielectric constant ceramic particles and a polymer is formed in situ;

the method comprising;

mixing a ceramic powder distribution with a liquid polymer precursor into a paste;

placing the paste into a die;

compressing the paste; and

,

polymerizing the polymer precursor to form a polymer that binds directly to ceramic particles of the ceramic powder distribution;

wherein the high dielectric constant composite material comprises the ceramic powder distribution and the polymer.

19. The method of claim 18, wherein the ceramic powder distribution comprises at least one first ceramic particle having a first diameter in a first range between 40 μ

m and 220 μ

m, at least one second ceramic particle having a second diameter in a second range between 500 nm and 5 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 500 nm.

20. The method of claim 18, wherein the ceramic powder distribution comprises at least one first ceramic particle having a first diameter in a first range between 0.5 μ

m and 3 μ

m, at least one second ceramic particle having a second diameter in a second range between 65 μ

m and 150 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 200 nm.

21. The method of claim 18 further comprising:

compacting the ceramic powder distribution such that the compacted distribution has a packing factor of at least 80%.

22. The method of claim 18 further comprising:

impregnating the composite material with a dielectric liquid to fill voids in the composite material and eliminate air from the composite material.

23. The method of claim 18, further comprising:

spin coating the composite material.

24. The method of claim 18 further comprising:

solution casting the composite material.

25. The method of claim 18 wherein polymerizing the polymer precursor to form the polymer comprises at least one of heating the die containing the pressed paste for at least thirty minutes and cooling the high dielectric constant composite material, providing a chemical catalyst, or exposing the polymer precursor to ultraviolet light.

26. The method of claim 18 further comprising:

removing the composite material from the die;

machining the composite material into a desired shape;

sanding the composite material; and

,

applying one or more electrodes to the composite material.

27. The method of claim 18, wherein the paste is compressed by a die press.

28. The method of claim 27, wherein the paste is compressed by a pressure of about 30 tons per square inch.

29. The method of claim 18 further comprising:

mixing a first distribution of large ceramic particles, a second distribution of intermediate ceramic particles, and a third distribution of small ceramic particles to form the ceramic powder distribution.

30. The method of claim 29, wherein a diameter of the large ceramic particles is between 40 μ

m and 220 μ

m.

31. The method of claim 29, wherein a diameter of the intermediate ceramic particles is between 500 nm and 5 μ

m.

32. The method of claim 29, wherein a diameter of the small ceramic particles is between 2 nm and 500 nm.

33. A method for manufacturing a composite material having a high dielectric constant and comprising a ceramic powder distribution and a polymer binder, the method comprising:

mixing a first distribution of large ceramic particles, a second distribution of intermediate ceramic particles, a third distribution of other intermediate ceramic particles, and a fourth distribution of small ceramic particles to form the ceramic powder distribution;

compacting the ceramic powder distribution such that the compacted distribution has a packing factor of at least 80%;

mixing the ceramic powder distribution with a liquid polymer precursor to form a paste;

placing the paste into a die;

compressing the paste; and

,

polymerizing the polymer precursor to form the polymer binder that binds directly to a surface of each of the ceramic particles of the ceramic powder distribution, wherein the polymer precursor is polymerized by heating the die containing the pressed paste for at least thirty minutes and cooling the high dielectric constant composite material, providing a chemical catalyst, exposing the polymer precursor to ultraviolet light, or combinations thereof.

34. The method of claim 33 further comprising:

removing the composite material from the die;

machining the composite material into a desired shape;

sanding the composite material; and

,

applying one or more electrodes to the composite material.

35. A method for manufacturing a composite material having a high dielectric constant and high dielectric strength, the composite material including a quadmodal distribution of ceramic powder, the method comprising:

mixing the ceramic powder distribution with a melted polymer in a solvent to form a paste;

placing the paste into a die;

compressing the paste; and

,

cooling the mixture to allow the melted polymer to solidify;

wherein the high dielectric constant composite material comprises the ceramic powder distribution and the polymer.

36. The method of claim 35, wherein the ceramic powder distribution comprises at least one first ceramic particle having a first diameter in a first range between 40 μ

m and 220 μ

m, at least one second ceramic particle having a second diameter in a second range between 500 nm and 5 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 500 nm.

37. The method of claim 35, wherein the ceramic powder distribution comprises at least one first ceramic particle having a first diameter in a first range between 0.5 μ

m and 3 μ

m, at least one second ceramic particle having a second diameter in a second range between 65 μ

m and 150 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 200 nm.

38. The method of claim 35 further comprising:

compacting the ceramic powder distribution such that the compacted distribution has a packing factor of at least 80%.

39. The method of claim 35 further comprising:

impregnating the composite material with a dielectric liquid to fill voids in the composite material and eliminate air from the composite material.

40. The method of claim 35 further comprising:

spin coating the composite material.

41. The method of claim 35 further comprising:

solution casting the composite material.

42. The method of claim 35 further comprising:

removing the composite material from the die;

heating the composite material below the melting temperature of the polymer to remove the solvent;

impregnating the composite with a dielectric fluid to fill voids;

machining the composite material into a desired shape;

sanding the composite material;

applying one or more electrodes to the composite material; and

sealing the composite.

43. The method of claim 35, wherein the paste is compressed by a die press.

44. The method of claim 43, wherein the paste is compressed by a pressure of about 30 tons per square inch.

45. The method of claim 35 further comprising:

mixing a first distribution of large ceramic particles, a second distribution of intermediate ceramic particles, a third distribution of other intermediate ceramic particles, and a fourth distribution of small ceramic particles to form the ceramic powder distribution.

46. The method of claim 45, wherein a diameter of the large ceramic particles is between 40 μ

m and 220 μ

m.

47. The method of claim 45, wherein a diameter of the intermediate ceramic particles is between 500 nm and 5 μ

m.

48. The method of claim 45, wherein a diameter of the small ceramic particles is less between 2 nm and 500 nm.

49. A composite material having a high dielectric constant and high dielectric strength, the composite material comprising:

a trimodal distribution of high dielectric constant ceramic particles bonded together by a polymeric material, wherein the trimodal distribution comprises 65 to 80% of at least one first ceramic particle having a first diameter in a first range between 40 μ

m and 220 μ

m, 15% to 20% of at least one second ceramic particle having a second diameter in a second range between 500 nm and 5 μ

m, and 5% to 15% of at least one third ceramic particle having a third diameter in a third range between 2 nm and 500 nm; and

,

wherein the polymeric material is polymerized in-situ from a polymeric precursor and binds directly to a surface of each of the high dielectric constant ceramic particles.

50. A composite material having a high dielectric constant and high dielectric strength, the composite material comprising:

a trimodal distribution of high dielectric constant ceramic particles bonded together by a polymeric material, wherein the trimodal distribution comprises 65 to 80% of at least one first ceramic particle having a first diameter in a first range between 40 μ

m and 220 μ

m, 15% to 20% of at least one second ceramic particle having a second diameter in a second range between 500 nm and 5 μ

m, and 5% to 15% of at least one third ceramic particle having a third diameter in a third range between 2 nm and 500 nm; and

,

the polymeric material is a gelling polymer, wherein the polymeric material is mixed with a solvent and the polymeric material absorbs at least a portion of the solvent to increase the volume or the polymeric material.

51. A composite material having a high dielectric constant and high dielectric strength, the composite material comprising:

a distribution of high dielectric constant ceramic particles, where the distribution of high dielectric constant ceramic particles is a quadmodal distribution; and

a polymeric material, wherein the polymeric material is mixed with the distribution of high dielectric constant ceramic particles and a polymer is formed in situ.

52. The composite material of claim 51, wherein the dielectric constant is greater than 20.

53. The composite material of claim 51, wherein the ceramic particles have a diameter in a range from about 2 nm to about 2000 μ

m.

54. The composite material of claim 51, wherein a diameter of the ceramic particles of a largest distribution of the quadmodal distribution is between 40 μ

m and 220 μ

m.

55. The composite material of claim 51, wherein a diameter of the ceramic particles of at least one intermediary distribution of the quadmodal distribution is between 500 nm and 5 μ

m.

56. The composite material of claim 51, wherein a diameter of the ceramic particles of a smallest distribution of the quadmodal distribution is in a range between 2 nm and 500 nm.

57. The composite material of claim 51, wherein the quadmodal distribution comprises at least one first ceramic particle having a first diameter in a first range between 40 μ

m and 220 μ

m, at least one second ceramic particle having a second diameter in a second range between 500 nm and 5 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 500 nm.

58. The composite material of claim 51, wherein the quadmodal distribution comprises at least one first ceramic particle having a first diameter in a first range between 0.5 μ

m and 3 μ

m, at least one second ceramic particle having a second diameter in a second range between 65 μ

m and 150 μ

m, and at least one third ceramic particle having a third diameter in a third range between 2 nm and 200 nm.

59. The composite material of claim 51, wherein the ceramic particles are perovskites.

60. The composite material of claim 51, wherein the polymeric material substantially fills a void space between two or more of the high dielectric constant ceramic particles.

61. The composite material of claim 51, wherein the polymeric material binds directly to a surface of the high dielectric constant ceramic particles.

62. The composite material of claim 51, wherein all surface portions of each of the ceramic particles not in contact with another surface portion of another ceramic particle are contacted with the polymeric material or a dielectric liquid filler.

63. The composite material of claim 51, wherein the polymeric material is an inorganic-organic coupling agent.

64. The composite material of claim 51, wherein the distribution of high dielectric constant ceramic particles has a first volume fraction of 50% or greater and the polymeric material has a second volume fraction of 50% or less.

65. The composite material of claim 64, wherein the perovskites comprise barium titanate, strontium titanate, barium strontium titanate, lead zirconate titanate, lead magnesium niobate-lead titanate, or combinations thereof.

66. The composite material of claim 51, wherein the polymeric material forms a gel that swells by absorbing a solvent.

67. The composite material of claim 66, wherein the polymeric material is a biopolymer.

68. The composite material of claim 67, wherein the polymeric material is selected from a group including agar, gelatin, carrageen, or combinations thereof.

69. The composite material of claim 51, wherein the polymeric material is formed from a polymer precursor derived from coupling agents including silanes, titanates, zirconates, or combinations thereof.

70. The composite material of claim 69, wherein the polymer precursor reacts to form a polysilsesquioxane.

71. The composite material of claim 69, wherein the polymer precursor is formed from a trialkoxysilane selected from a group consisting of triethoxyvinylsilane, vinyltrimethoxysilane, and aminopropyltriethoxysilane.

72. The composite material of claim 51, wherein the composite material is compressed in a die press.

73. The composite material of claim 72, wherein a precursor of the polymeric material is mixed with the distribution of high dielectric constant ceramic particles before compression in the die press.

74. The composite material of claim 73, wherein the precursor is polymerized and cross-linked in-situ.

75. The composite material of claim 74, wherein the precursor is polymerized by at least one of heat, a chemical catalyst, or ultraviolet light.

76. The composite material of claim 51 further comprising a dielectric fluid.

77. The composite material of claim 76, wherein the dielectric fluid is impregnated into the composite material to displace any voids remaining in the composite material.

78. The composite material of claim 76, wherein the dielectric fluid has a high dielectric constant.

79. The composite material of claim 78, wherein the dielectric fluid is selected from a group consisting of water, an alkylene carbonate, an oil, or combinations thereof.

80. The composite material of claim 79, wherein the dielectric fluid includes silane, titanate, zirconate, or combinations thereof.