US2377910A - High dielectric constant ceramics - Google Patents
High dielectric constant ceramics Download PDFInfo
- Publication number
- US2377910A US2377910A US489382A US48938243A US2377910A US 2377910 A US2377910 A US 2377910A US 489382 A US489382 A US 489382A US 48938243 A US48938243 A US 48938243A US 2377910 A US2377910 A US 2377910A
- Authority
- US
- United States
- Prior art keywords
- dielectric constant
- barium titanate
- temperature
- fluoride
- high dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000919 ceramic Substances 0.000 title description 4
- 229910002113 barium titanate Inorganic materials 0.000 description 23
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 18
- 239000003989 dielectric material Substances 0.000 description 10
- 238000007792 addition Methods 0.000 description 9
- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 8
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 150000002222 fluorine compounds Chemical class 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004017 vitrification Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 229910052454 barium strontium titanate Inorganic materials 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
Classifications
-
- 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
- C04B35/468—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 based on barium titanates
- C04B35/4682—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 based on barium titanates based on BaTiO3 perovskite phase
Definitions
- the present invention relates to dielectric materials and particularly to ceramic dielectrics that are extremely resistant to extremes of temperature and to rapid changes of temperature.
- high dielectric constant materials are described in pending applications for patent, Ser. No. 465,387, filed November 12, 1942, and Ser. No. 482,613, filed April 10, 1943.
- the materials there described consist essentially of alkaline earth titanates with, in some instances, additions of other materials.
- These high dielectric constant materials are ceramic bodies which, when properly matured and fired, develop high dielectric constants at radio frequencies from 275 to 10,000 kilocycles.
- the properties developed by such alkaline earth titanates are very useful, but for certain specialized requirements, defects are These specialized applications usually involve the employment of the dielectric at extremes of temperature of -60 to +150 C. in which employment the change of temperature may be extremely rapid. Such rapid temperature changes and extremes are encountered in aircraft in flight and in automotive engines or components in close association with such engines. Under such extremely severe service conditions, the alkaline earth titanates such as barium titanate and barium-strontium titanate exh bit two important defects. First, these ceraIr. 38 will not withstand the necessary thermal sh JCk without shattering, and secondly, their dielectric constants fluctuate relatively wildly with wide variations in temperature.
- a standard laboratory test for such materials is the immersion of a standard size test specimen in boiling water for ten minutes, followed by rapid plunging into water in equilibrium with ice, in which bath it will remain for ten minutes.
- a satisfactory body should withstand at least 20 such cycles without shattering; the present invention provides compositions providing such bodies.
- Pure barium titanate usually fails completely in the first or second cycle. Although the temperature coefilcient of barium titanate is satisfactory up to 75 C. or 80 C., at this point the dielectric constant starts to rise rapidly and if the temperature rise is made sloy enough a pronounced peak of capacity, 3 to 5 times the room temper ature level, is obtained at 120 C. to 130 C. This change in capacity with temperature appears to be the incidence of an allotropic change involving a wide volume change.
- the novel results are accomplished by adding the fluorides of magnesium or calcium to barium titanate, mixing thoroughly and then shaking suitably after the addition of water.
- the formed piece is then fired on schedule to 2400 F. to 2450" F.
- the useful range of additions is between 1% and 10% of the fluoride, the amount used being to a certain extent dependent on the degree of suppression required.
- Essentially neutral temperature coefficients are obtained at 2% to 3% addition of MgFz and at 4% to 6% addition of CaFz.
- Ecrample 1 The following compositions pressed with the addition of 10% water, dried and then fired to 2450" C. The die size was such that the finished pieces were in the form of discs about were mixed,
- Table I Dielectric Body No. Composition 533 6 1 megacycle BaTiO; 1,350 BaTlOa plus 1 OaFa. 1, 220 1, 800 1, 320 1, 900 2, 580 2, 810 3, 020 3, 400 100 BaTiO; plus 3.0 MgF, 2,800 100 BaTiO; plus 4.0 MgFa 2,000 100 Ba'liO; plus 5.0 MgF; 1, 100
- Temperature coeflicient of dielectric constant is at 1 megacycle per second. Figures are in dielectric constant.
- the dielectric constant of barium titanate may be increased by addition of a fluoride of a metal of group 11 and a composition selected with a suitable temperature coefllcient.
- a dielectric material comprising barium titanate in major amount and a fluoride of a metal of group II in minor amount.
- a dielectric material comprising barium titanate in major amount and calcium fluoride in minor amount.
- a dielectric material comprising barium titanate in major amount and magnesium fluoride in minor amount.
- a dielectric material comprising barium titanate and a fluoride of a metal of group 11, said metal fluoride being less than 10% of the total composition.
- a dielectric material comprising barium titanate and calcium fluoride, the calcium fluoride constituting less than 10% of the total composition.
- a dielectric material comprising barium titanate and magnesium fluoride, the magnesium fluoride constituting less than 10% of the tota composition.
- a dielectric material comprising barium titanate and calcium fluoride, the calcium fluoride constituting from 2% to 5% of the total composition.
- a dielectric material comprising barium titanate and magnesium fluoride, the magnesium fluoride constituting from 1.5% to 4% of the total composition.
- the method of regulating the dielectric constant of barium titanate which comprises mixing with barium titanate a fluoride of a metal of group II and heating the mixture until vitriflcation occurs.
- the method of regulating the dielectric constant of barium titanate which comprises mixing with barium titanate a fluoride of a metal of group II in an amount less than 10% of the total composition and heating the mixture until vitrification occurs.
- the method of regulating the dielectric constant of barium titanate which comprises mixing barium titanate and calcium fluoride and heating the mixture until vitrification occurs, the calcium fluoride being less than 10% of the composition.
- the method of regulating the dielectric constant of barium titanate which comprises mixing barium titanate and magnesium fluoride and heating the mixture until vitrification occurs, the magnesium fluoride being less than 10% of the composition.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Insulating Materials (AREA)
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL68779D NL68779C (en(2012)) | 1943-06-02 | ||
| US489382A US2377910A (en) | 1943-06-02 | 1943-06-02 | High dielectric constant ceramics |
| DEN3614A DE909817C (de) | 1943-06-02 | 1951-03-14 | Keramischer Koerper mit hoher Dielektrizitaetskonstante |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US489382A US2377910A (en) | 1943-06-02 | 1943-06-02 | High dielectric constant ceramics |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2377910A true US2377910A (en) | 1945-06-12 |
Family
ID=23943629
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US489382A Expired - Lifetime US2377910A (en) | 1943-06-02 | 1943-06-02 | High dielectric constant ceramics |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US2377910A (en(2012)) |
| DE (1) | DE909817C (en(2012)) |
| NL (1) | NL68779C (en(2012)) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2438761A (en) * | 1944-04-04 | 1948-03-30 | Hartford Nat Bank & Trust Comp | Manufacture of ceramic materials of high permittivity |
| US2473556A (en) * | 1943-03-15 | 1949-06-21 | Carl A Wiley | Device for controlling oscillating circuits |
| US2484636A (en) * | 1947-09-26 | 1949-10-11 | Bell Telephone Labor Inc | Modulation system |
| US2504178A (en) * | 1947-04-28 | 1950-04-18 | Sprague Electric Co | Electrical condenser |
| US2526207A (en) * | 1946-04-27 | 1950-10-17 | Rca Corp | Capacitor for frequency modulation |
| US2555959A (en) * | 1946-10-18 | 1951-06-05 | Bell Telephone Labor Inc | Nonlinear reactance circuits utilizing high dielectric constant ceramics |
| DE894261C (de) * | 1948-09-30 | 1953-10-22 | United Insulator Company Ltd | Verfahren zur Herstellung eines gesinterten keramischen Koerpers |
| US2695239A (en) * | 1951-02-28 | 1954-11-23 | Erie Resistor Corp | Barium titanate capacitors |
| US2695240A (en) * | 1953-01-09 | 1954-11-23 | Erie Resistor Corp | Method of preparing barium titanate ceramics with flattened temperature characteristics |
| US2823361A (en) * | 1946-07-31 | 1958-02-11 | John J Hopkins | Inductance unit |
| US2935411A (en) * | 1956-03-29 | 1960-05-03 | Sprague Electric Co | High dielectric constant ceramics |
| US3000745A (en) * | 1955-02-25 | 1961-09-19 | Welwyn Electrical Lab Ltd | Vitreous materials |
| DE977062C (de) * | 1946-03-22 | 1965-01-07 | Philips Nv | Piezoelektrisches Element |
| US3248328A (en) * | 1963-01-25 | 1966-04-26 | Westinghouse Electric Corp | Piezoelectric ceramic composition of lead titanate and 0.1 to 5 mole percent calciumfluoride |
| US3340074A (en) * | 1964-03-16 | 1967-09-05 | Corning Glass Works | Barium titanate materials |
| DE1293070B (de) * | 1962-09-12 | 1969-04-17 | Int Standard Electric Corp | Ferroelektrisches Element und Verfahren zu seiner Herstellung |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE958698C (de) * | 1951-03-15 | 1957-02-21 | Siemens Ag | Verfahren zur Herstellung einer biegsamen Glasfolie fuer elektrotechnische Zwecke |
| NL253240A (en(2012)) * | 1959-07-01 | |||
| DE1173009B (de) * | 1960-03-03 | 1964-06-25 | Philips Patentverwaltung | Keramische Dielektrikum auf der Basis von Barium-Titanat |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE684932C (de) * | 1934-06-06 | 1939-12-08 | Steatit Magnesia Akt Ges | Elektrischer Isolierkoerper |
| DE699112C (de) * | 1934-10-20 | 1940-11-22 | Steatit Magnesia Akt Ges | Elektrischer Isolierkoerper |
| DE723426C (de) * | 1935-03-03 | 1942-08-06 | Steatit Magnesia Ag | Elektrischer Isolierkoerper aus einem dicht gesinterten Gemisch von Titandioxyd, Zirkondioxyd und erdalkalischen Flussmitteln |
| US2420692A (en) * | 1943-04-10 | 1947-05-20 | Titanium Alloy Mfg Co | Ceramic dielectric composition |
-
0
- NL NL68779D patent/NL68779C/xx active
-
1943
- 1943-06-02 US US489382A patent/US2377910A/en not_active Expired - Lifetime
-
1951
- 1951-03-14 DE DEN3614A patent/DE909817C/de not_active Expired
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2473556A (en) * | 1943-03-15 | 1949-06-21 | Carl A Wiley | Device for controlling oscillating circuits |
| US2438761A (en) * | 1944-04-04 | 1948-03-30 | Hartford Nat Bank & Trust Comp | Manufacture of ceramic materials of high permittivity |
| DE977062C (de) * | 1946-03-22 | 1965-01-07 | Philips Nv | Piezoelektrisches Element |
| US2526207A (en) * | 1946-04-27 | 1950-10-17 | Rca Corp | Capacitor for frequency modulation |
| US2823361A (en) * | 1946-07-31 | 1958-02-11 | John J Hopkins | Inductance unit |
| US2555959A (en) * | 1946-10-18 | 1951-06-05 | Bell Telephone Labor Inc | Nonlinear reactance circuits utilizing high dielectric constant ceramics |
| US2504178A (en) * | 1947-04-28 | 1950-04-18 | Sprague Electric Co | Electrical condenser |
| US2484636A (en) * | 1947-09-26 | 1949-10-11 | Bell Telephone Labor Inc | Modulation system |
| DE894261C (de) * | 1948-09-30 | 1953-10-22 | United Insulator Company Ltd | Verfahren zur Herstellung eines gesinterten keramischen Koerpers |
| US2695239A (en) * | 1951-02-28 | 1954-11-23 | Erie Resistor Corp | Barium titanate capacitors |
| US2695240A (en) * | 1953-01-09 | 1954-11-23 | Erie Resistor Corp | Method of preparing barium titanate ceramics with flattened temperature characteristics |
| US3000745A (en) * | 1955-02-25 | 1961-09-19 | Welwyn Electrical Lab Ltd | Vitreous materials |
| US2935411A (en) * | 1956-03-29 | 1960-05-03 | Sprague Electric Co | High dielectric constant ceramics |
| DE1293070B (de) * | 1962-09-12 | 1969-04-17 | Int Standard Electric Corp | Ferroelektrisches Element und Verfahren zu seiner Herstellung |
| US3248328A (en) * | 1963-01-25 | 1966-04-26 | Westinghouse Electric Corp | Piezoelectric ceramic composition of lead titanate and 0.1 to 5 mole percent calciumfluoride |
| US3340074A (en) * | 1964-03-16 | 1967-09-05 | Corning Glass Works | Barium titanate materials |
Also Published As
| Publication number | Publication date |
|---|---|
| NL68779C (en(2012)) | |
| DE909817C (de) | 1954-04-26 |
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