CA2164595A1 - Novel ceramic ferroelectric material - Google Patents
Novel ceramic ferroelectric materialInfo
- Publication number
- CA2164595A1 CA2164595A1 CA002164595A CA2164595A CA2164595A1 CA 2164595 A1 CA2164595 A1 CA 2164595A1 CA 002164595 A CA002164595 A CA 002164595A CA 2164595 A CA2164595 A CA 2164595A CA 2164595 A1 CA2164595 A1 CA 2164595A1
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- Prior art keywords
- strontium titanate
- alumina
- barium strontium
- dielectric constant
- low dielectric
- Prior art date
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- Abandoned
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q3/00—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system
- H01Q3/26—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the relative phase or relative amplitude of energisation between two or more active radiating elements; varying the distribution of energy across a radiating aperture
- H01Q3/30—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the relative phase or relative amplitude of energisation between two or more active radiating elements; varying the distribution of energy across a radiating aperture varying the relative phase between the radiating elements of an array
- H01Q3/34—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the relative phase or relative amplitude of energisation between two or more active radiating elements; varying the distribution of energy across a radiating aperture varying the relative phase between the radiating elements of an array by electrical means
- H01Q3/36—Arrangements for changing or varying the orientation or the shape of the directional pattern of the waves radiated from an antenna or antenna system varying the relative phase or relative amplitude of energisation between two or more active radiating elements; varying the distribution of energy across a radiating aperture varying the relative phase between the radiating elements of an array by electrical means with variable phase-shifters
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/10—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on aluminium oxide
- C04B35/111—Fine ceramics
- C04B35/117—Composites
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
- C04B35/462—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates
- C04B35/465—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates based on titanates based on alkaline earth metal titanates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
- C04B35/48—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates
- C04B35/49—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on zirconium or hafnium oxides, zirconates, zircon or hafnates containing also titanium oxides or titanates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Composite Materials (AREA)
- Inorganic Insulating Materials (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
A novel ceramic ferroelectric material having a low dielectric constant, low loss and high tunability. The material is a composite comprising Barium Strontium Titanate (BSTO) and a ceramic material having a low dielectric constant. The preferred composite is represented by Ba1-xSrxTiO3-Al2O3, wherein x is greater than 0.00, but less than or equal to 0.70, and wherein the percent weight ratio between Ba1-xSrxTiO3 and Al2O3 ranges from approximately 99 % - 40 % and 1 % - 60 %, respectively. The novel materials possess superior electronic properties; and they may be employed in various antenna systems.
Description
W094/29234 PCT~S94/05.138 ~ 2164~9~
NOVE~ C~MTC F~RRQ~T.~CTRIC MAT~RT~T.
~CRGRO~ND OF THE lNV~. lON
The need exists for the fabrication of ceramic materials having improved electronic properties which may be adjusted for a particular, intended use. The present invention deals with novel ceramic ferroelectric materials having ideal properties for use, for example, in phased array antenna systems.
SUBSTITUTE SHEET (RULE 26) W094/29~4 PCT~S94/05~8 Ferroelectric materials which are commonly used in the antenna arts are porous ceramics, whose properties are less than ideal for their intended application. Porous ceramics of the Bal xSrxTiO3 type are commonly employed in ceramic phase shifter antennas. However, these materials display certain deficiencies due to both the processing diffi-culties and expense, as well as their overall electronic and microwave properties. These deficiencies include electronic inhomogeneity, structural weakness, reproduc-ibility and processing control, and large loss tangents.
Barium Strontium Titanate (BaTiO3-SrTiO3), also referred to herein as BSTO, has been known to be used for its high dielectric constant (approximately ranging from 200 to 6,000) in various antenna applications. This is set forth by Richard W. Babbitt et al. in their publication, "Planar Microwave Electro-Optic Phase Shifters," Microwave Journal, Volume 35(6), (June 1992). This publication concludes `that there exists a need for additional research to be conducted in the materials art to yield materials having more desirable electronic properties.
Although the employ of BSTO in phase shifters is known, nowhere in the technical arena of ceramic art has there been any suggestion of modifying BSTO, or combining BSTO with additives, in the manner described herein.
SUBSTITUTE SHEET (RULE 26) WOg4/29~4 PCT~S94/05138 O ~ 9 ~
Moreover, the specific BSTO combinations, which have enhanced electronic properties, are deemed novel.
The present invention provides for improved materials which exhibit electronic properties which can be adjusted for use, for example, in any discrete element phase shifter design -- i.e. planar microstrip, wave guide geometries or parallel plate structure. The invention herein is superior to other currently used ferroelectric materials in the art.
BRIEF DESCRIPTION OF THE lNv~ ON
The subject matter of the present invention relates to the fabrication of specific ceramic materials which have sought after properties in, for example, phased array antenna systems. The sought after properties include (l) a low dielectric constant; (2) a low loss; and (3) high tunability. Dielectric constant is related to the energy storage in the material; whereas, the loss tangent is related to the power dissipation in the same material. In general, the dielectric function is a complex ~uantity with ~ ic"; and the loss tangent, tan ~ ' = O.Ol or less.
Tunability may be defined as ((dielectric constant with no applied voltage) - (dielectric constant with an applied voltage))/(dielectric constant with no applied SUBSTITUTE SHEET (RIJLE 26~
W094/29~4 PCT~S94/05138 2~45~
voltage). For simplicity purposes, tuna~ility can be represented as T
(X -- Y) (1) wherein, X = (dielectric constant with no applied voltage); and Y = (dielectric constant with an applied voltage).
The tunability of a material under an electric field of 7.0 KV/cm can range from 1-60% depending upon the composition of the materials employed.
The materials herein combine Barium Strontium Titanate (BaTiO3-SrTiO3) with Alumina (A12O3). These materials, encompassed by the present invention, are superior in that they are homogeneous, easily mach;n~hle, and possess superior electronic properties at both dc and microwave operating frequencies. Moreover, the materials herein have low water absorptivity. Typically these materials will absorb less than 2% by weight of water therein. Hence, the materials within the scope of the present invention are environmentally stable -- for example, they have good moisture and temperature stability.
Although other combinations of electrically active and inactive components have been commonly employed in conjunc-tion with piezoelectric materials, nowhere has the combina-SUBSTITUTE SHEET (RULE 26) W094/29~4 PCT~S94/05138 ~ ~16~9~
tion of the present invention been described. Morespecifically, the present invention is the first teaching wherein BSTO is combined with Alumina in order to adjust the electronic properties of a material. Specifically, nowhere has BSTO been combined with Alumina to adjust the electronic properties of the material for use in a phase array antenna system. Aside from the combination of BSTO
with Alumina being novel, its application in phase array antenna systems is an application never suggested in the prior art.
Replacing the currently employed materials with the novel ferroelectric composite described in the present invention will improve the overall performance of a phased array antenna system as well as reduce the cost, weight and size of the antenna per se.
Accordingly, it is an object of the present invention to provide a ferroelectric material suitable for, but not limited to, use in phased array antenna systems.
It is a further object of the present invention to fabricate a material exhibiting enhanced electronic properties.
It is still a further object of the present invention to provide a ferroelectric material having a low dielectric constant, a low loss and a high tunability.
SUBSTITUTE SHEET (RULE 26~
W094/29~4 PCT~S94/05~8 ~ 6 ~9S f It is a further object of the present invention to provide materials having electronic properties, wherein t said electronic properties can be adjusted in such a manner that they can be employed in any discrete element phase shifter design.
It is a further object of the present invention to provide a ferroelectric material which is easily machinable.
Still, it is a further object herein to provide a ferroelectric material which possesses superior electronic properties at both dc and microwave operating frequencies.
The means to achieve these and other objectives of the present invention will be apparent from the following detailed description of the invention and claims.
DETAILED DE8CRIPTION OF T~E lNv~ ON
The present invention encompasses the fabrication of novel ceramic materials having enhanced electronic properties. These materials are superior to other currently employed ferroelectric materials.
When one considers the optimization in the electronic properties of ceramic materials, the following parameters must be taken into consideration:
SlJBSTITUTE SHEET (RULE 26 WOg4/29~ PCT~S94/05138 ~ 6~59~
(1) Dielectric Constant: Ideally the dielectric constant should be low, ranging from approximately 30 to 200. This dielectric constant range does not decrease the phase shifting ability of the material if a sufficient length of material is used (then a high dielectric constant is not needed). As insertion loss (loss of energy getting into the ceramic) does not depend upon the dielectric constant, it is not effected by lowering the dielectric constant. Also, since the loss tangent (tan ~) increases with increasing dielectric constant (for these ferroelectric materials), lower dielectric constant materials tend to have lower loss tangents and therefore, less insertion loss.
(2) Low Loss: The loss tangent (intrinsic to the material) serves to dissipate or absorb the incident micro-wave energy and therefore is most effective in this device when the loss tangent is in the range of 0.01 or less. The low loss tangent serves to decrease the insertion loss and hence increase the phase shifter per decibel of loss.
NOVE~ C~MTC F~RRQ~T.~CTRIC MAT~RT~T.
~CRGRO~ND OF THE lNV~. lON
The need exists for the fabrication of ceramic materials having improved electronic properties which may be adjusted for a particular, intended use. The present invention deals with novel ceramic ferroelectric materials having ideal properties for use, for example, in phased array antenna systems.
SUBSTITUTE SHEET (RULE 26) W094/29~4 PCT~S94/05~8 Ferroelectric materials which are commonly used in the antenna arts are porous ceramics, whose properties are less than ideal for their intended application. Porous ceramics of the Bal xSrxTiO3 type are commonly employed in ceramic phase shifter antennas. However, these materials display certain deficiencies due to both the processing diffi-culties and expense, as well as their overall electronic and microwave properties. These deficiencies include electronic inhomogeneity, structural weakness, reproduc-ibility and processing control, and large loss tangents.
Barium Strontium Titanate (BaTiO3-SrTiO3), also referred to herein as BSTO, has been known to be used for its high dielectric constant (approximately ranging from 200 to 6,000) in various antenna applications. This is set forth by Richard W. Babbitt et al. in their publication, "Planar Microwave Electro-Optic Phase Shifters," Microwave Journal, Volume 35(6), (June 1992). This publication concludes `that there exists a need for additional research to be conducted in the materials art to yield materials having more desirable electronic properties.
Although the employ of BSTO in phase shifters is known, nowhere in the technical arena of ceramic art has there been any suggestion of modifying BSTO, or combining BSTO with additives, in the manner described herein.
SUBSTITUTE SHEET (RULE 26) WOg4/29~4 PCT~S94/05138 O ~ 9 ~
Moreover, the specific BSTO combinations, which have enhanced electronic properties, are deemed novel.
The present invention provides for improved materials which exhibit electronic properties which can be adjusted for use, for example, in any discrete element phase shifter design -- i.e. planar microstrip, wave guide geometries or parallel plate structure. The invention herein is superior to other currently used ferroelectric materials in the art.
BRIEF DESCRIPTION OF THE lNv~ ON
The subject matter of the present invention relates to the fabrication of specific ceramic materials which have sought after properties in, for example, phased array antenna systems. The sought after properties include (l) a low dielectric constant; (2) a low loss; and (3) high tunability. Dielectric constant is related to the energy storage in the material; whereas, the loss tangent is related to the power dissipation in the same material. In general, the dielectric function is a complex ~uantity with ~ ic"; and the loss tangent, tan ~ ' = O.Ol or less.
Tunability may be defined as ((dielectric constant with no applied voltage) - (dielectric constant with an applied voltage))/(dielectric constant with no applied SUBSTITUTE SHEET (RIJLE 26~
W094/29~4 PCT~S94/05138 2~45~
voltage). For simplicity purposes, tuna~ility can be represented as T
(X -- Y) (1) wherein, X = (dielectric constant with no applied voltage); and Y = (dielectric constant with an applied voltage).
The tunability of a material under an electric field of 7.0 KV/cm can range from 1-60% depending upon the composition of the materials employed.
The materials herein combine Barium Strontium Titanate (BaTiO3-SrTiO3) with Alumina (A12O3). These materials, encompassed by the present invention, are superior in that they are homogeneous, easily mach;n~hle, and possess superior electronic properties at both dc and microwave operating frequencies. Moreover, the materials herein have low water absorptivity. Typically these materials will absorb less than 2% by weight of water therein. Hence, the materials within the scope of the present invention are environmentally stable -- for example, they have good moisture and temperature stability.
Although other combinations of electrically active and inactive components have been commonly employed in conjunc-tion with piezoelectric materials, nowhere has the combina-SUBSTITUTE SHEET (RULE 26) W094/29~4 PCT~S94/05138 ~ ~16~9~
tion of the present invention been described. Morespecifically, the present invention is the first teaching wherein BSTO is combined with Alumina in order to adjust the electronic properties of a material. Specifically, nowhere has BSTO been combined with Alumina to adjust the electronic properties of the material for use in a phase array antenna system. Aside from the combination of BSTO
with Alumina being novel, its application in phase array antenna systems is an application never suggested in the prior art.
Replacing the currently employed materials with the novel ferroelectric composite described in the present invention will improve the overall performance of a phased array antenna system as well as reduce the cost, weight and size of the antenna per se.
Accordingly, it is an object of the present invention to provide a ferroelectric material suitable for, but not limited to, use in phased array antenna systems.
It is a further object of the present invention to fabricate a material exhibiting enhanced electronic properties.
It is still a further object of the present invention to provide a ferroelectric material having a low dielectric constant, a low loss and a high tunability.
SUBSTITUTE SHEET (RULE 26~
W094/29~4 PCT~S94/05~8 ~ 6 ~9S f It is a further object of the present invention to provide materials having electronic properties, wherein t said electronic properties can be adjusted in such a manner that they can be employed in any discrete element phase shifter design.
It is a further object of the present invention to provide a ferroelectric material which is easily machinable.
Still, it is a further object herein to provide a ferroelectric material which possesses superior electronic properties at both dc and microwave operating frequencies.
The means to achieve these and other objectives of the present invention will be apparent from the following detailed description of the invention and claims.
DETAILED DE8CRIPTION OF T~E lNv~ ON
The present invention encompasses the fabrication of novel ceramic materials having enhanced electronic properties. These materials are superior to other currently employed ferroelectric materials.
When one considers the optimization in the electronic properties of ceramic materials, the following parameters must be taken into consideration:
SlJBSTITUTE SHEET (RULE 26 WOg4/29~ PCT~S94/05138 ~ 6~59~
(1) Dielectric Constant: Ideally the dielectric constant should be low, ranging from approximately 30 to 200. This dielectric constant range does not decrease the phase shifting ability of the material if a sufficient length of material is used (then a high dielectric constant is not needed). As insertion loss (loss of energy getting into the ceramic) does not depend upon the dielectric constant, it is not effected by lowering the dielectric constant. Also, since the loss tangent (tan ~) increases with increasing dielectric constant (for these ferroelectric materials), lower dielectric constant materials tend to have lower loss tangents and therefore, less insertion loss.
(2) Low Loss: The loss tangent (intrinsic to the material) serves to dissipate or absorb the incident micro-wave energy and therefore is most effective in this device when the loss tangent is in the range of 0.01 or less. The low loss tangent serves to decrease the insertion loss and hence increase the phase shifter per decibel of loss.
(3) Hiqh Tunability: The tunability of a particular material effects the material's electronic properties by how much the dielectric constant changes with applied voltage. The amount of phase shifting ability is directly related to the tunability; therefore, higher tunabilities SlJBSrlTUTE SHEET (RULE 26) W094/29~4 PCT~S94/05138 ~6 ~S~
are desired. The tunability can be increased to some extent by decreasing the sample thickness. The insertion loss is inversely related to the tunability so that the larger the tunability, the smaller the insertion loss.
Optimum electronic properties would have tunabilities ranging from 4 to 50% (depending upon other factors, dielectric constant and loss tangent).
The materials within the scope of the present invention fall within the optimum characteristics outlined above. These materials are Ba1_xSrxTiO3-Al203, wherein x is greater than 0.0 but less than or equal to 0.70. This formulation may be referred to as Barium Strontium Titanate and Alumina. The weight ratios of Barium Strontium Titanate (BSTO) to Alumina may range from 99% wt. - 40% wt.
BSTO to 1% wt. - 60% wt. Alumina. A typical composition within the present invention may comprise 70% by weight BSTO (wherein x = 0.35) and 30% by weight Alumina (A1203).
This composition has a dielectric constant of 55.2, a loss tangent of 0.007 and a tunability of 8.0 (applied electric field = 32.8 KV/cm).
Alumina is used herein to adjust the electronic properties of BSTO. Specifically, it effects the material's dielectric constant and dielectric loss to meet the requirements for various applications -- for example, SUBSTITUTE SI~EET (RULE 26) W094/29~4 PCT~S94/05138 9 ~
in the antenna arts. The electronic properties of the formulation herein can be adjusted for use in any discrete element phase shifter design, such as planar microstrip, wave guide geometries or for use in a parallel plate structure.
It has been found that the electronic properties of BST0 Alumina are reproducible to within 2%. Hence, once a specific formulation of BST0 Alumina is determined to be suitable for a specific purpose, the material can be accurately reproduced.
The preparation of BST0 Alumina may be accomplished by obtaining powders of Barium Titanate and Strontium Titanate. These powders are ball milled in a conventional manner in an organic solvent. This particular mixture is then air-dried and calcined at approximately 200 degrees below the sintering temperature for several hours. The resultant BST0 is then mixed with Alumina in the desired weight percentage and re-ball milled in an organic solvent with a binder. The final mixture is then air-dried, once again, and dry-pressed at approximately 7,000 p.s.i. The final samples are sintered in air.
Table 1 sets forth the various properties of BST0 Alumina, wherein the formulation is represented by o. 65SrO. 35Tio3 - Alumina.
.
SUBSTITUTE SHEE~ (RULE 2~) W094/29~4 PCT~S94/05138 !--T~BLE 1 Alumina Content (wt.%) DensitY (q/cc) ~ Porosity ~ Absorption 1.00 5.314 '~ 4.24 0.55 5.00 5.046 4.16 0.64 10.0 4.820 7.93 1.30 30.0 4.018 8.19 1.58 60.0 3.458 7.65 1.73 80.0 3.496 4.54 1.00 The electronic properties of some of the formulations within the present invention are set forth in Tables 2 and 3. The representative formulations for which electronic properties are tabulated are for BST0 at Ba = 0.65 and Ba =
0.60 with varying Alumina content.
BST0 (Ba = O.65) nd Alu~ina Alumina Dialectric Los~ Tun~bility El~ctric Content wt.% Const~nt Tan~ent~ ~Percent) Fiel~
~V/cm) 1.0 4850 0.00939.8 7.32 10.0 967 0.01727.2 ll.9 30.0 55.2 0.007 8.0 32.8 60.0 18.8 0.002 2.7 32.0 SUBStIME SHEET ~RULE 26') W094/2g~4 PCT~S94/05138 21~95 BST0 (Ba = O.60) and Alumina Alumina Dielectric ~088 Tunability Electric Content wt.% Con~tant Tanqent* IPercent) Field ~RV/cm) 5.0 1751 0.014 55.3 2S.l 10.0 - 860 0.011 34.615.4 20.0 201 0.017 19.824.6 22.0 135 0.015 14.427.2 30.0 49.7 0.010 5.1322.1 * Note: The magnitude of the loss tangents reported approach ~he limit of measurement capability of the test apparatus; therefore, actual loss tangents are in some cases less than these values.
If the antenna application does not require exceedingly high tunability (where tunability can be increased with a decrease in sample thickness for a given externally applied electric field), then the compositions with lower dielectric constants are probably likely to produce less impedance mismatch and may possess lower loss tangents.
Powder forms of Barium Titanate and Strontium Titanate were obtained from Ferro Corp., Transelco Division, Pen Yan, N.Y. (product nos. 219-6 and 218, respectively). The powders were stoichiometrically mixed in a slurry of ethanol and ball-milled using alumina 3/16" grinding media.
This was performed for 24 hours. The mixture was subse-SUBSTITUTE SHEET (RULE 26~
W094t29~4 PCT~S94/05138 ~64~9~ 1~
quently air dried and calcined for 5 hours at approximately1100 C. The resulting BSTO was mixed with powder Alumina (ALCOA Industrial Chemicals, Bauxite AR, distributed by Whittaker, Clark, and Daniels, South Plainfield, N.J., product no. A16-SG) in the proper weight percent. This mixture was then re-ball milled in a slurry of ethanol using a 3/16" alumina grinding media for an additional 24 hours.
To the resulting BSTO/Alumina mixture, Rhoplex B-60A
(Rohm and Haas Co., Philadelphia, Pennsylvania), which is a 3% wt. organic binder consisting of an aqueous emulsion of acrylic polymer, was added to improve green body strength and to permit sample fabrication in greater ~;m~ncions.
(Green body strength refers to the ability of unfired material to remain intact and to withstand handling; it also implies better densities in the unfired pieces.) Other binders and plasticizers may be added at this point to allow extrusion molding or for fabrication of tape-cast sheets of material.
The mixture is then air-dried and dry-pressed to a pressure of approximately 7,000 p.s.i. Sintering schedules are ascertained by employing a deflectometer such as a Mitutoyo digimatic indicator and miniprocessor (Mitutoyo Corp., Paramus, N.J.). The final samples were fired in SUBSTlTllTE SHEET (RULE 2~) W094/2g~4 PCT~S94/05~8 ~ 9 ~
various furnaces and the densities of the samples were found to be reproducible to within 1 to 2%.
The properties of the resulting BSTO - Alumina samples are set forth in Table 1, above.
While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention. For example, the invention may be modified to include ceramic-ceramic composites of BSTO and other low dielectric constant materials depending upon the particular requirements of the intended application. Among some of the other low dielectric constant materials which may be combined with BSTO are zirconia, magnesia, alumina microballoons, alumina fibers or fabric, silicon dioxide and other low dielectric const nt, low dielectric loss oxides. (Alumina micro-balloons are hollow spheres of approximately 1-5 microns in diameter and are already sintered components (BSTO/ceramic) -- the electronic properties of a composite employing alumina microballoons will most likely differ from composites employing alumina powder. Alumina fibers or fabric, when employed in the composite within the scope of the present invention, may possess electronic properties .~
Sl)BSTITlJTE SHEET (RULE 2~
W094/29234 PCT~S94/05138 2~
different from composites which employ alumina powder.
This is due to the fact that this form of alumina is most likely to be in sintered form; and the fibers or fabric alumina produce different connectivity between the BSTO
particles.) It is, therefore, intended that the claims herein are to include all such obvious changes and modifications as fall within the true spirit and scope of this invention.
SUBSTITUTE SHEET (RULE 2
are desired. The tunability can be increased to some extent by decreasing the sample thickness. The insertion loss is inversely related to the tunability so that the larger the tunability, the smaller the insertion loss.
Optimum electronic properties would have tunabilities ranging from 4 to 50% (depending upon other factors, dielectric constant and loss tangent).
The materials within the scope of the present invention fall within the optimum characteristics outlined above. These materials are Ba1_xSrxTiO3-Al203, wherein x is greater than 0.0 but less than or equal to 0.70. This formulation may be referred to as Barium Strontium Titanate and Alumina. The weight ratios of Barium Strontium Titanate (BSTO) to Alumina may range from 99% wt. - 40% wt.
BSTO to 1% wt. - 60% wt. Alumina. A typical composition within the present invention may comprise 70% by weight BSTO (wherein x = 0.35) and 30% by weight Alumina (A1203).
This composition has a dielectric constant of 55.2, a loss tangent of 0.007 and a tunability of 8.0 (applied electric field = 32.8 KV/cm).
Alumina is used herein to adjust the electronic properties of BSTO. Specifically, it effects the material's dielectric constant and dielectric loss to meet the requirements for various applications -- for example, SUBSTITUTE SI~EET (RULE 26) W094/29~4 PCT~S94/05138 9 ~
in the antenna arts. The electronic properties of the formulation herein can be adjusted for use in any discrete element phase shifter design, such as planar microstrip, wave guide geometries or for use in a parallel plate structure.
It has been found that the electronic properties of BST0 Alumina are reproducible to within 2%. Hence, once a specific formulation of BST0 Alumina is determined to be suitable for a specific purpose, the material can be accurately reproduced.
The preparation of BST0 Alumina may be accomplished by obtaining powders of Barium Titanate and Strontium Titanate. These powders are ball milled in a conventional manner in an organic solvent. This particular mixture is then air-dried and calcined at approximately 200 degrees below the sintering temperature for several hours. The resultant BST0 is then mixed with Alumina in the desired weight percentage and re-ball milled in an organic solvent with a binder. The final mixture is then air-dried, once again, and dry-pressed at approximately 7,000 p.s.i. The final samples are sintered in air.
Table 1 sets forth the various properties of BST0 Alumina, wherein the formulation is represented by o. 65SrO. 35Tio3 - Alumina.
.
SUBSTITUTE SHEE~ (RULE 2~) W094/29~4 PCT~S94/05138 !--T~BLE 1 Alumina Content (wt.%) DensitY (q/cc) ~ Porosity ~ Absorption 1.00 5.314 '~ 4.24 0.55 5.00 5.046 4.16 0.64 10.0 4.820 7.93 1.30 30.0 4.018 8.19 1.58 60.0 3.458 7.65 1.73 80.0 3.496 4.54 1.00 The electronic properties of some of the formulations within the present invention are set forth in Tables 2 and 3. The representative formulations for which electronic properties are tabulated are for BST0 at Ba = 0.65 and Ba =
0.60 with varying Alumina content.
BST0 (Ba = O.65) nd Alu~ina Alumina Dialectric Los~ Tun~bility El~ctric Content wt.% Const~nt Tan~ent~ ~Percent) Fiel~
~V/cm) 1.0 4850 0.00939.8 7.32 10.0 967 0.01727.2 ll.9 30.0 55.2 0.007 8.0 32.8 60.0 18.8 0.002 2.7 32.0 SUBStIME SHEET ~RULE 26') W094/2g~4 PCT~S94/05138 21~95 BST0 (Ba = O.60) and Alumina Alumina Dielectric ~088 Tunability Electric Content wt.% Con~tant Tanqent* IPercent) Field ~RV/cm) 5.0 1751 0.014 55.3 2S.l 10.0 - 860 0.011 34.615.4 20.0 201 0.017 19.824.6 22.0 135 0.015 14.427.2 30.0 49.7 0.010 5.1322.1 * Note: The magnitude of the loss tangents reported approach ~he limit of measurement capability of the test apparatus; therefore, actual loss tangents are in some cases less than these values.
If the antenna application does not require exceedingly high tunability (where tunability can be increased with a decrease in sample thickness for a given externally applied electric field), then the compositions with lower dielectric constants are probably likely to produce less impedance mismatch and may possess lower loss tangents.
Powder forms of Barium Titanate and Strontium Titanate were obtained from Ferro Corp., Transelco Division, Pen Yan, N.Y. (product nos. 219-6 and 218, respectively). The powders were stoichiometrically mixed in a slurry of ethanol and ball-milled using alumina 3/16" grinding media.
This was performed for 24 hours. The mixture was subse-SUBSTITUTE SHEET (RULE 26~
W094t29~4 PCT~S94/05138 ~64~9~ 1~
quently air dried and calcined for 5 hours at approximately1100 C. The resulting BSTO was mixed with powder Alumina (ALCOA Industrial Chemicals, Bauxite AR, distributed by Whittaker, Clark, and Daniels, South Plainfield, N.J., product no. A16-SG) in the proper weight percent. This mixture was then re-ball milled in a slurry of ethanol using a 3/16" alumina grinding media for an additional 24 hours.
To the resulting BSTO/Alumina mixture, Rhoplex B-60A
(Rohm and Haas Co., Philadelphia, Pennsylvania), which is a 3% wt. organic binder consisting of an aqueous emulsion of acrylic polymer, was added to improve green body strength and to permit sample fabrication in greater ~;m~ncions.
(Green body strength refers to the ability of unfired material to remain intact and to withstand handling; it also implies better densities in the unfired pieces.) Other binders and plasticizers may be added at this point to allow extrusion molding or for fabrication of tape-cast sheets of material.
The mixture is then air-dried and dry-pressed to a pressure of approximately 7,000 p.s.i. Sintering schedules are ascertained by employing a deflectometer such as a Mitutoyo digimatic indicator and miniprocessor (Mitutoyo Corp., Paramus, N.J.). The final samples were fired in SUBSTlTllTE SHEET (RULE 2~) W094/2g~4 PCT~S94/05~8 ~ 9 ~
various furnaces and the densities of the samples were found to be reproducible to within 1 to 2%.
The properties of the resulting BSTO - Alumina samples are set forth in Table 1, above.
While particular embodiments of the present invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from this invention. For example, the invention may be modified to include ceramic-ceramic composites of BSTO and other low dielectric constant materials depending upon the particular requirements of the intended application. Among some of the other low dielectric constant materials which may be combined with BSTO are zirconia, magnesia, alumina microballoons, alumina fibers or fabric, silicon dioxide and other low dielectric const nt, low dielectric loss oxides. (Alumina micro-balloons are hollow spheres of approximately 1-5 microns in diameter and are already sintered components (BSTO/ceramic) -- the electronic properties of a composite employing alumina microballoons will most likely differ from composites employing alumina powder. Alumina fibers or fabric, when employed in the composite within the scope of the present invention, may possess electronic properties .~
Sl)BSTITlJTE SHEET (RULE 2~
W094/29234 PCT~S94/05138 2~
different from composites which employ alumina powder.
This is due to the fact that this form of alumina is most likely to be in sintered form; and the fibers or fabric alumina produce different connectivity between the BSTO
particles.) It is, therefore, intended that the claims herein are to include all such obvious changes and modifications as fall within the true spirit and scope of this invention.
SUBSTITUTE SHEET (RULE 2
Claims (20)
1. A ceramic ferroelectric composite material comprising Barium Strontium Titanate and a ceramic material having a low dielectric constant;
wherein said Barium Strontium Titanate and said ceramic material are present in amounts to provide a composite having a low dielectric constant, low loss tangent and high tunability.
wherein said Barium Strontium Titanate and said ceramic material are present in amounts to provide a composite having a low dielectric constant, low loss tangent and high tunability.
2. The ceramic ferroelectric composite material of claim 1, wherein said ceramic material having a low dielectric constant is selected from the group consisting of alumina, zirconia, magnesia, silicon dioxide and other low dielectric constant, low dielectric loss oxides.
3. The ceramic ferroelectric composite material of claim 1, wherein said Barium Strontium Titanate is Ba1-xSrxTiO3, wherein x is greater than 0.0 but less than or equal to 0.70.
4. The ceramic ferroelectric composite material of claim 3, wherein said Barium Strontium Titanate is Ba1-xSrxTiO3, wherein x = 0.35 to 0.40.
5. The ceramic ferroelectric composite material of claim 4, wherein the weight ratio of said Barium Strontium Titanate to said ceramic material having a low dielectric constant ranges from approximately 99% - 40% Barium Strontium Titanate to approximately 1% - 60% said ceramic material having a low dielectric constant.
6. The ceramic ferroelectric composite material of claim 4, wherein said ceramic material having a low dielectric constant is alumina.
7. The ceramic ferroelectric composite material of claim 5, wherein said ceramic material having a low dielectric constant is alumina.
8. The ceramic ferroelectric composite material of claim 7, wherein the ratio of Barium Strontium Titanate to alumina is approximately 70% wt. Barium Strontium Titanate to approximately 30% wt. alumina.
9. A ceramic ferroelectric composite material consisting essentially of Barium Strontium Titanate, said Barium Strontium Titanate represented as Ba1-xSrxTiO3, wherein x is greater than 0.0 but less than or equal to 0.70; and alumina;
wherein said Barium Strontium Titanate and alumina are present in amounts to provide a composite having a low dielectric constant, low loss tangent and high tunability.
wherein said Barium Strontium Titanate and alumina are present in amounts to provide a composite having a low dielectric constant, low loss tangent and high tunability.
10. The ceramic ferroelectric composite material of claim 9, wherein said Barium Strontium Titanate is Ba1-xSrxTiO3, wherein x =0.35 to 0.40.
11. The ceramic ferroelectric composite material of claim 10, wherein the weight ratio of said Barium Strontium Titanate to alumina ranges from approximately 99% - 40%
Barium Strontium Titanate to approximately 1% - 60%
alumina.
Barium Strontium Titanate to approximately 1% - 60%
alumina.
12. The ceramic ferroelectric composite material of claim 11, wherein the ratio of Barium Strontium Titanate to alumina is approximately 70% wt. Barium Strontium Titanate to approximately 30% wt. alumina.
13. A method for providing enhanced phase shifting ability to a phased array antenna system, wherein said method comprises employing in a phased array antenna system a phase shifting device comprising therein a ceramic ferroelectric composite material comprising Barium Strontium Titanate and a ceramic material having a low dielectric constant;
wherein said Barium Strontium Titanate and said ceramic material are present in amounts to provide a composite having a low dielectric constant, low loss tangent and high tunability.
wherein said Barium Strontium Titanate and said ceramic material are present in amounts to provide a composite having a low dielectric constant, low loss tangent and high tunability.
14. A method in accordance with claim 13, wherein said ceramic material having a low dielectric constant is selected from the group consisting of alumina, zirconia, magnesia, silicon dioxide and other low dielectric constant, low dielectric loss oxides.
15. A method in accordance with claim 13, wherein said Barium Strontium Titanate is Ba1-xSrxTiO3, wherein x is greater than 0.0 but less than or equal to 0.70.
16. A method in accordance with claim 15, wherein said Barium Strontium Titanate is Ba1-xSrxTiO3, wherein x = 0.35 to 0.40.
17. A method in accordance with claim 16, wherein the weight ratio of said Barium Strontium Titanate to said ceramic material having a low dielectric constant ranges from approximately 99% - 40% Barium Strontium Titanate to approximately 1% - 60% said ceramic material having a low dielectric constant.
18. A method in accordance with claim 16, wherein said ceramic material having a low dielectric constant is alumina.
19. A method in accordance with claim 17, wherein said ceramic material having a low dielectric constant is alumina.
20. A method in accordance with claim 19, wherein the ratio of Barium Strontium Titanate to alumina is approxi-mately 70% wt. Barium Strontium Titanate to approximately 30% wt. alumina.
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US08/076,291 | 1993-06-09 | ||
US08/076,291 US5312790A (en) | 1993-06-09 | 1993-06-09 | Ceramic ferroelectric material |
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CA002164595A Abandoned CA2164595A1 (en) | 1993-06-09 | 1994-05-12 | Novel ceramic ferroelectric material |
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US (3) | US5312790A (en) |
EP (1) | EP0705231A4 (en) |
JP (1) | JPH08511501A (en) |
KR (2) | KR960702824A (en) |
AU (1) | AU7200094A (en) |
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-
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- 1993-06-09 US US08/076,291 patent/US5312790A/en not_active Expired - Lifetime
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1994
- 1994-03-07 US US08/207,447 patent/US5486491A/en not_active Expired - Fee Related
- 1994-03-07 US US08/207,446 patent/US5427988A/en not_active Expired - Lifetime
- 1994-05-12 WO PCT/US1994/005138 patent/WO1994029234A1/en not_active Application Discontinuation
- 1994-05-12 JP JP7501779A patent/JPH08511501A/en active Pending
- 1994-05-12 CA CA002164595A patent/CA2164595A1/en not_active Abandoned
- 1994-05-12 KR KR1019950705561A patent/KR960702824A/en not_active Application Discontinuation
- 1994-05-12 EP EP94921180A patent/EP0705231A4/en not_active Withdrawn
- 1994-05-12 AU AU72000/94A patent/AU7200094A/en not_active Abandoned
- 1994-05-24 KR KR1019950705523A patent/KR960702823A/en not_active Application Discontinuation
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US5312790A (en) | 1994-05-17 |
EP0705231A4 (en) | 1996-07-24 |
JPH08511501A (en) | 1996-12-03 |
EP0705231A1 (en) | 1996-04-10 |
US5486491A (en) | 1996-01-23 |
KR960702824A (en) | 1996-05-23 |
AU7200094A (en) | 1995-01-03 |
WO1994029234A1 (en) | 1994-12-22 |
KR960702823A (en) | 1996-05-23 |
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