US3674713A - Electric ceramic resistors having positive temperature coefficients and method of manufacturing same - Google Patents
Electric ceramic resistors having positive temperature coefficients and method of manufacturing same Download PDFInfo
- Publication number
- US3674713A US3674713A US6052A US3674713DA US3674713A US 3674713 A US3674713 A US 3674713A US 6052 A US6052 A US 6052A US 3674713D A US3674713D A US 3674713DA US 3674713 A US3674713 A US 3674713A
- Authority
- US
- United States
- Prior art keywords
- barium titanate
- fluoride
- ceramic
- percent
- calculated
- 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 claims description 37
- 238000004519 manufacturing process Methods 0.000 title claims description 12
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910002113 barium titanate Inorganic materials 0.000 claims abstract description 40
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 239000011737 fluorine Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000004408 titanium dioxide Substances 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000001939 inductive effect Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000004065 semiconductor Substances 0.000 claims description 3
- 229910052712 strontium Inorganic materials 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 101100273027 Dictyostelium discoideum cafA gene Proteins 0.000 description 1
- 241000244489 Navia Species 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001632 barium fluoride Inorganic materials 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- -1 for example Chemical compound 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 description 1
- 229910001637 strontium fluoride Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/022—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances
- H01C7/023—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient mainly consisting of non-metallic substances containing oxides or oxidic compounds, e.g. ferrites
- H01C7/025—Perovskites, e.g. titanates
-
- 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 invention relates to a method of manufacturing ceramic resistance bodies for electric resistors having a positive temperature coefficient of the electric resistivity, which bodies mainly consist of semiconductive barium titanate; the invention further relates to resistance bodies thus manufactured and resistors manufactured by means of said bodies (so-called FTC-resistors).
- FTC-resistors the resistance body of which consists of semiconductive barium titanate, the electric resistance of which can increase considerably when the temperature increases to and above the ferro-electric Curie-temperature are known per se.
- resistors the ceramic resistance bodies of which consist of barium titanate in which a part of the barium ions is replaced by la ions or Sb ions or part of the Ti ions by Nb ions.
- PlC-resistors can be manufactured the said temperature-dependence of the electric resistance of which is considerably larger than of known PTC- resistors on the basis of semiconductive titanate.
- PTCresistors manufactured according to the invention show a considerably stronger increase of the electric resistance than the known resistors on the basis of semiconductive barium titanate when the temperature is increased to and above the ferro-electric Curie-temperature, or the absolute increase of the electric resistance in a given temperature range is considerably larger than of those known resistors; often both effects occur in a FTC-resistor obtained with the use of the invention.
- These FTC-resistors often have a substantially constant temperature coefficient of the electric resistance over a large temperature range.
- the FTC-resistors according to the invention can advantageously be used in those cases where electric resistors having positive temperature coefficients can be used, for example, for current limiting and stabilization in thermoregulators and voltage stabilizers, for safeguarding electric motors and for temperature and radiation measurements.
- the invention relates to a method of manufacturing a ceramic resistance body consisting of substantially pure semiconductive barium titanate which has been made semiconductive with the use of the principle of the controlled valency from a powder which substantially consists of barium titanate or substantially of compounds which are converted into barium titanate upon heating in an oxygen-containing atmosphere, characterized in that before shaping the powder is intimately mixed with a fluoride of an element of the group consisting of Ca, Sr and Ba in a quantity corresponding to 0.5 at. percent of fluorine, calculated on barium titanate present in the ceramic resistance body, to a ceramic resistance body thus manufactured and PTC-resistors manufactured by means of said body.
- the ceramic resistance bodies thereof must consist of substantially pure semiconductive barium titanate and preferably of such a barium titanate which contains a small excess, up to 3 mol. percent and preferably 1.5 2.0 mol. percent, of titanium dioxide.
- a ceramic resistance body consisting of substantially pure semiconductive barium titanate is to be understood to mean herein such a body which consists for at least 95 mol. percent of barium titanate.
- barium titanate semiconductive For making barium titanate semiconductive the known methods may be used and at least one element which introduces semiconductivity with the use of the principle of the controlled valency may be incorporated in suitable quantifies.
- elements are antimony, bismuth, niobium, cerium, yttrium, rare earth metals, for example, lanthanum.
- a fluoride is preferably used calcium fluoride.
- the quantity of fluoride to be used corresponds to 0.5 10 at. percent of fluorine, calculated on barium titanate in the ceramic resistance body. This content preferably corresponds to l 8 at. percent of fluorine and in particular to 2 6 at. percent of fluorine.
- the manufacture of ceramic resistance bodies according to the invention may be carried out, for example, as follows:
- Powders of barium carbonate, titanium dioxide and antimony oxide, (Sb O are carefully mixed, for example, by grinding, and the mixture is heated in air at l,l00 C for 60 minutes.
- the resulting product is ground.
- the fluoride to be added for example, Calis intimately mixed with the resulting powder, for example, by grinding.
- the resulting pulverulent product is given the desired shape for example, of a rod, sheet or strip, for example, by compression.
- the body thus obtained is sintered in an oxygen-containing atmosphere to form a ceramic resistance body, for example, by heating in air at l,400 C for 60 minutes.
- the resulting resistance body may be provided in known manner with ohmic electrodes and supply wires for the manufacture of PT C-resistors.
- Ceramic resistance bodies to be investigated (wafers, diameter 7.5 mms, thickness 1.85 mms) were provided with ohmic electrodes as a result of which no contact resistances occur. The electric resistance was measured at different temperatures.
- the basic composition of the ceramic bodies was the followmg:
- the ceramic bodies according to the present invention are of a fine crystallinity. Applicants suppose that this is due to a limitation of crystal growth by the influence of fluoride. Due to this the bodies show a high breakdown voltage. The high order of reproducibility in the manufacture of the resistors is also due to the said effect.
- an electric ceramic resistor having a positive temperature coefficient of electrical resistance and comprising a barium titanate body and a metal capable of inducing semiconductivity into said barium titanate and provided with at least one ohmic contact electrode, the improvement wherein said semi-conductive body contains 0.5 to at. percent inclusive of fluorine in the form of barium, calcium or strontium fluoride calculated on the barium titanate.
- a ceramic resistance body consisting of semiconductive barium titanate comprising the steps, first shaping a powder consisting substantially of barium-titanate or compounds heat-convertable to barium titanate and a compound of a metal capable of inducing semiconductivity into the barium titanate into a shaped mass and then sintering the resultant shaped mass by heating in oxygen, the improvement which comprises adding to the powder before shaping at least one fluoride of an element selected from the group consisting of Ca, Sr and Ba in a quantity corresponding to 0.5-10 at. percent of fluorine, calculated on the barium titanate present in the ceramic resistance body.
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Ceramic Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Thermistors And Varistors (AREA)
- Compositions Of Oxide Ceramics (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL6516534A NL6516534A (enrdf_load_stackoverflow) | 1965-12-18 | 1965-12-18 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3674713A true US3674713A (en) | 1972-07-04 |
Family
ID=19794963
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US6052A Expired - Lifetime US3674713A (en) | 1965-12-18 | 1970-01-26 | Electric ceramic resistors having positive temperature coefficients and method of manufacturing same |
Country Status (8)
Country | Link |
---|---|
US (1) | US3674713A (enrdf_load_stackoverflow) |
AT (1) | AT270807B (enrdf_load_stackoverflow) |
BE (1) | BE691370A (enrdf_load_stackoverflow) |
CH (1) | CH495609A (enrdf_load_stackoverflow) |
FR (1) | FR1505751A (enrdf_load_stackoverflow) |
GB (1) | GB1171756A (enrdf_load_stackoverflow) |
NL (1) | NL6516534A (enrdf_load_stackoverflow) |
SE (1) | SE318642B (enrdf_load_stackoverflow) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975307A (en) * | 1974-10-09 | 1976-08-17 | Matsushita Electric Industrial Co., Ltd. | PTC thermistor composition and method of making the same |
CN115784736A (zh) * | 2022-11-24 | 2023-03-14 | 江苏省陶瓷研究所有限公司 | 一种表面无橘红色斑点、高阻温的ptc加热陶瓷及其制备方法 |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3794949A (en) * | 1973-02-01 | 1974-02-26 | Texas Instruments Inc | Solid state motor starting apparatus |
DE3681566D1 (de) * | 1985-12-06 | 1991-10-24 | Hitachi Ltd | Keramiksinter mit hohem waermeausdehnungskoeffizient und ein verbundkoerper aus demselben und metall. |
-
1965
- 1965-12-18 NL NL6516534A patent/NL6516534A/xx unknown
-
1966
- 1966-12-15 SE SE17207/66A patent/SE318642B/xx unknown
- 1966-12-15 CH CH1791266A patent/CH495609A/de not_active IP Right Cessation
- 1966-12-15 AT AT1155666A patent/AT270807B/de active
- 1966-12-16 GB GB56451/66A patent/GB1171756A/en not_active Expired
- 1966-12-16 FR FR87738A patent/FR1505751A/fr not_active Expired
- 1966-12-16 BE BE691370D patent/BE691370A/xx unknown
-
1970
- 1970-01-26 US US6052A patent/US3674713A/en not_active Expired - Lifetime
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3975307A (en) * | 1974-10-09 | 1976-08-17 | Matsushita Electric Industrial Co., Ltd. | PTC thermistor composition and method of making the same |
CN115784736A (zh) * | 2022-11-24 | 2023-03-14 | 江苏省陶瓷研究所有限公司 | 一种表面无橘红色斑点、高阻温的ptc加热陶瓷及其制备方法 |
CN115784736B (zh) * | 2022-11-24 | 2024-01-26 | 江苏省陶瓷研究所有限公司 | 一种表面无橘红色斑点、高阻温的ptc加热陶瓷及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE1665226B2 (de) | 1975-08-07 |
CH495609A (de) | 1970-08-31 |
GB1171756A (en) | 1969-11-26 |
NL6516534A (enrdf_load_stackoverflow) | 1967-06-19 |
SE318642B (enrdf_load_stackoverflow) | 1969-12-15 |
FR1505751A (fr) | 1967-12-15 |
BE691370A (enrdf_load_stackoverflow) | 1967-06-16 |
AT270807B (de) | 1969-05-12 |
DE1665226A1 (de) | 1971-01-21 |
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