US4113928A
Expired / Lapsed
US
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Method of preparing dense, high strength, and electrically conductive ceramics containing β"-alumina
Assignee: University of Utah Research Foundation Inc
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Filing: 1977-04-18
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Granted: 1978-09-12
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Expires: 1997-04-18
Abstract
Abstract Methods of preparing a dense and strong polycrystalline β"-alumina-containing ceramic body exhibiting an electrical resistivity for sodium ion conduction at 300° C of 9 ohm-cm or lower obtained directly after sintering and having a controlled fine microstructure exhibiting a uniform grain size under 50 micrometers. The invention more particularly relates to methods of uniformly distributing selected metal ions having a valence not greater than 2, e.g. lithium or magnesium, uniformly throughout the beta-type alumina composition prior to sintering to form β"-alumina. This uniform distribution allows more complete conversion of β-alumina to β"-alumina during sintering. As a result, the polycrystalline β"-alumina containing ceramic bodies obtained by methods of this invention exhibit high density, low porosity, high strength, fine grain size (i.e. no grains over 25-50 micrometers with an average size under 5-10 micrometers), low electrical resistivity and a high resistance to degradation by water vapor in an ambient atmosphere.
Inventors
- 👤 Anil V. Virkar
- 👤 Mark L. Miller
- 👤 Ivan B. Cutler
- 👤 Ronald S. Gordon
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 06:49
CPC Classifications
H; H01; H01M; H01M10/00; H01M10/36; H01M10/39; H01M10/3909; H01M10/3918; C; C01; C01F; C01F7/00; C01F7/02; C01F7/028; C04; C04B; C04B35/00; C04B35/01; C04B35/10; C04B35/111; C04B35/113; C01P; C01P2004/00; C01P2004/51; C01P2004/52; C01P2004/60; C01P2004/61; C01P2006/00; C01P2006/10; C01P2006/40; Y; Y02; Y02E; Y02E60/00; Y02E60/10
Claims Analysis
Total Claims: 28
Claim 1
Independent Claim
160 words
A method for preparing a dense, strong polycrystalline β"-alumina-containing ceramic body exhibiting (i) an electrical resistivity for sodium ion conduction at 300° C. of less than or equal to about 9 ohm-cm, and (ii) a fine, uniform microstructure and resultant fracture strength comparable to that achieved by hot pressing techniques, comprising: (A) preparing a powder mixture comprising aluminum oxide, sodium oxide and lithium oxide in stoichiometric proportions required to produce β"-alumina upon being heated to crystal forming temperatures, said lithium oxide being present in amounts ranging from about 0.1 to about 5 weight percent of the total of said mixture and being provided by a lithium aluminate compound having the formula Li 2 O:nAl 2 O 3 wherein n equals at least 5; (B) green forming said preparing mixture to the desired shape; and (C) sintering the green formed body at a temperature above about 1500° C. until desirable conversion to β"-alumina and near theoretical density for same are achieved.
Claim 2
Independent Claim
160 words
A method for preparing a dense, strong polycrystalline β"-alumina-containing ceramic body exhibiting (i) an electrical resistivity for sodium ion conduction at 300° C. of less than or equal to about 9 ohm-cm, and (ii) a fine, uniform microstructure and resultant fracture strength comparable to that achieved by hot pressing techniques, comprising: (A) preparing a powder mixture comprising aluminum oxide, sodium oxide and lithium oxide in stoichiometric proportions required to produce β"-alumina upon being heated to crystal forming temperatures, said lithium oxide being present in amounts ranging from about 0.1 to about 5 weight percent of the total of said mixture and being provided by a lithium aluminate compound having the formula Li 2 O:nAl 2 O 3 wherein n equals at least 5; (B) green forming said preparing mixture to the desired shape; and (C) sintering the green formed body at a temperature above about 1500° C. until desirable conversion to β"-alumina and near theoretical density for same are achieved.
Claim 3
Dependent Claim
78 words
A method in accordance with claim 1 wherein said powder mixture is prepared by (A) preparing a mixture of (1) aluminum oxide; (2) sodium oxide or a sodium salt capable of decomposing to form sodium oxide; and (3) said lithium aluminate compound in such proportion that the reaction mixture will provide the necessary stoichiometric amounts of aluminum oxide, sodium oxide and lithium oxide to form β"-alumina; and (B) calcining said mixture at a temperature above about 1100° C.
Claim 4
Dependent Claim
32 words
A method in accordance with claim 2 wherein said green formed body is sintered at a temperature of between about 1500° C. and about 1600° C. for less than about 10 minutes.
Claim 5
Dependent Claim
38 words
A method in accordance with claim 3, wherein said β"-alumina containing ceramic body is subjected to a post-sinter anneal at a temperature of less than about 1600° C. to further reduce its electrical resistivity to sodium ion conduction.
Claim 6
Dependent Claim
48 words
A method in accordance with claim 2, wherein (i) said lithium aluminate compound is represented by the formula Li 2 O:5Al 2 O 3 and (ii) said green formed body is sintered at a temperature between about 1560° and about 1600° C. for less than about 10 minutes.
Claim 7
Dependent Claim
44 words
A method in accordance with claim 5 wherein said β"-alumina containing ceramic body is subjected to a post-sinter anneal at a temperature of less than about 1600° C. for less than about 1 hour to further reduce its electrical resistivity to sodium ion conduction.
Claim 8
Dependent Claim
100 words
A method in accordance with claim 1 wherein said powder mixture is prepared by (A) preparing a mixture of (1) aluminum oxide; and (2) sodium oxide or a sodium salt capable of decomposing to form sodium oxide, said sodium salt being included in said mixture in an amount sufficient to provide the necessary stoichiometric amount of sodium oxide; (B) calcining said mixture at a temperature above 1100° C.; and (C) mixing said lithium aluminate compound with the calcined mixture in such proportions that the reaction mixture contains stoichiometric amounts of aluminum oxide, sodium oxide and lithium oxide to form β"-alumina.
Claim 9
Dependent Claim
32 words
A method in accordance with claim 7 wherein said green formed body is sintered at a temperature of between about 1500° C. and about 1600° C. for less then about 10 minutes.
Claim 10
Dependent Claim
38 words
A method in accordance with claim 7 wherein said β"-alumina containing ceramic body is subjected to a post-sinter anneal at a temperature of less than about 1600° C. to further reduce its electrical resistivity to sodium ion conduction.
Claim 11
Dependent Claim
48 words
A method in accordance with claim 7, wherein (i) said lithium aluminate compound is represented by the formula Li 2 O:5Al 2 O 3 and (ii) said green formed body is sintered at a temperature between about 1560° and about 1600° C. for less than about 10 minutes.
Claim 12
Dependent Claim
23 words
A method in accordance with claim 1 wherein said green formed body is sintered at a temperature between about 1500° and 1600° C.
Claim 13
Dependent Claim
30 words
A method in accordance with claim 1 wherein said green formed body is sintered at a temperature between about 1560° and about 1600° C. for less than about 10 minutes.
Claim 14
Dependent Claim
20 words
A method in accordance with claim 12 wherein said body is sintered for between about 1 and about 3 minutes.
Claim 15
Dependent Claim
25 words
A method in accordance with claim 1 wherein n of said lithium aluminate compound Li 2 O--nAl 2 O 3 equals from 5 to 11.
Claim 16
Dependent Claim
24 words
A method in accordance with claim 1 wherein said lithium aluminate compound is represented by the formula Li 2 O:5Al 2 O 3 .
Claim 17
Dependent Claim
44 words
A method in accordance with claim 15 wherein said β"-alumina containing ceramic body is subjected to a post-sinter anneal at a temperature of less than about 1600° C. for less than about 1 hour to further reduce its electrical resistivity to sodium ion conduction.
Claim 18
Dependent Claim
38 words
A method in accordance with claim 1 wherein said β"-alumina containing ceramic body is subjected to a post-sinter anneal at a temperature of less than about 1600° C. to further reduce its electrical resistivity to sodium ion conduction.
Claim 19
Dependent Claim
48 words
A method in accordance with claim 1 wherein (i) said lithium aluminate compound is represented by the formula Li 2 O:5Al 2 O 3 and (ii) said green formed body is sintered at a temperature between about 1560° and about 1600° C. for less than about 10 minutes.
Claim 20
Dependent Claim
35 words
A method in accordance with claim 18 wherein said powder mixture is prepared by calcining a mixture of said alumina, said sodium salt and said lithium aluminate compound at a temperature above about 1100° C.
Claim 21
Dependent Claim
38 words
A method in accordance with claim 18 wherein said powder mixture is prepared by calcining a mixture of said alumina, said sodium salt at a temperature above about 1100° C. and then mixing said lithium aluminate compound therewith.
Claim 22
Dependent Claim
44 words
A method in accordance with claim 18 wherein said β"-alumina containing ceramic body is subjected to a post-sinter anneal at a temperature of less than about 1600° C. for less than about 1 hour to further reduce its electrical resistivity to sodium ion conduction.
Claim 23
Independent Claim
169 words
A method for preparing a dense, strong polycrystalline β"-alumina-containing ceramic body exhibiting (i) an electrical resistivity for sodium ion conduction at 300° C. of less than or equal to about 9 ohm-cm, and (ii) a fine, uniform microstructure and resultant high fracture strength comprising: (A) preparing a partially deflocculated slurry of alpha or beta alumina in an aqueous solution containing a soluble sodium salt and lithium salts or mixtures thereof, the anions of which are subject to decomposition and/or vaporization at temperatures below about 1300° C. to form sodium oxide and lithium oxide which in combination with said aluminum oxide will provide a stoichiometric composition suitable for formation of β→-alumina upon sintering: (B) spray drying said slurry to form a powder. (C) calcining said powder at a temperature below about 1300° C. to obtain said stoichiometric composition; (D) green forming said powder to form a green body of the desired shape; and (E) sintering said body at a temperature above about 1500° C. for at least about 1 minute.
Claim 24
Independent Claim
169 words
A method for preparing a dense, strong polycrystalline β"-alumina-containing ceramic body exhibiting (i) an electrical resistivity for sodium ion conduction at 300° C. of less than or equal to about 9 ohm-cm, and (ii) a fine, uniform microstructure and resultant high fracture strength comprising: (A) preparing a partially deflocculated slurry of alpha or beta alumina in an aqueous solution containing a soluble sodium salt and lithium salts or mixtures thereof, the anions of which are subject to decomposition and/or vaporization at temperatures below about 1300° C. to form sodium oxide and lithium oxide which in combination with said aluminum oxide will provide a stoichiometric composition suitable for formation of β→-alumina upon sintering: (B) spray drying said slurry to form a powder. (C) calcining said powder at a temperature below about 1300° C. to obtain said stoichiometric composition; (D) green forming said powder to form a green body of the desired shape; and (E) sintering said body at a temperature above about 1500° C. for at least about 1 minute.
Claim 25
Dependent Claim
27 words
A method in accordance with claim 22 wherein said slurry includes a lithium salt selected from the group consisting of lithium nitrate, lithium oxalate and lithium chloride.
Claim 26
Dependent Claim
13 words
A method in accordance with claim 22 wherein said slurry includes magnesium-aluminum spinel.
Claim 27
Dependent Claim
29 words
A method in accordance with claim 22 wherein said green body is sintered at a temperature of about 1560° to about 1600° C. for less than about 10 minutes.
Claim 28
Dependent Claim
20 words
A method in accordance with claim 22 wherein said slurry is stabilized by the addition of isooctyl phenoxy polyethoxy ethanol.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1981-09-11 | 1982-03-13 | 1982-09-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1985-09-11 | 1986-03-13 | 1986-09-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1989-09-11 | 1990-03-13 | 1990-09-12 | $7700.00 | Window Closed / Lapsed |