US2616859A - Electrical resistor - Google Patents

Electrical resistor Download PDF

Info

Publication number
US2616859A
US2616859A US660423A US66042346A US2616859A US 2616859 A US2616859 A US 2616859A US 660423 A US660423 A US 660423A US 66042346 A US66042346 A US 66042346A US 2616859 A US2616859 A US 2616859A
Authority
US
United States
Prior art keywords
temperature
resistances
spinel
resistance
group
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
Application number
US660423A
Inventor
Verwey Evert Johannes Willem
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hartford National Bank and Trust Co
Original Assignee
Hartford National Bank and Trust Co
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hartford National Bank and Trust Co filed Critical Hartford National Bank and Trust Co
Application granted granted Critical
Publication of US2616859A publication Critical patent/US2616859A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C7/00Non-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
    • H01C7/04Non-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 negative temperature coefficient
    • H01C7/042Non-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 negative temperature coefficient mainly consisting of inorganic non-metallic substances
    • H01C7/043Oxides or oxidic compounds
    • H01C7/046Iron oxides or ferrites

Definitions

  • a y a I converting combinations of Products of a lower temperature coeiiicient p u may be obtained if more than approximately half 0 Feo*Fe2O3Mg9 A12O3 of the spinel phase consists of FesOi molecules.
  • the conductivity owing to the high percentage homo e eous sp Ip a -a' dw ch s not o of F9304 greatly increases it may in this case saturated with a secondpha 'at' a e p be desirable to influence the specific resistance of about 500 C. by the presence of a secondph'ase.
  • the cooling two last-mentioned proposals. process may be effected rapidlywhilst driving
  • the conductive out the atmosphere containing oxygen 'by means material of the resistances consists to this end of a relatively inert gas such as nitrogen.
  • the of mixed crystals of FesOiwith a spinel of the material may alsobe s-intered inan atmosphere type 2R OR O2, in which formula R repre in which the partial pressure" of the oxygen sents a bivalent and R a-tetravalent element- 40 decreases with temperature, i.e.
  • the resistance value as well as the temperature: lsinee" the content of, FeOi and hence the coefficient' of resistances thus: composed maybe molecular ratioFeO) reset may 'beadjust'ed by adjusted by the choice "offtheucontent' Of FeQO i: the choice of the sintering temperature" and of and the presence, ifuanyn of asecondphase in the the sinteri-nge atmosphere; the initial material sinteredl producin 2 used aforithei'resistances; according to the inven-
  • the temperature coeflicient it may 5,9 tion may be" any-forms of iron oxide and, if 3 be mentioned that this is highly negative in proddesired, iron powder, while the other constituents ucts consisting of a homogeneous spinel phase already referred to above may be used wholly or of which less than approximately half is built in part in the form of double-oxides.
  • the sintering process may be carried out in an atmosphere of pure nitrogen without the F8304 formed from F8203 being reduced further to the FeO.
  • the reproducibility of the resistance value is also very high.
  • the resistances exhibit even with high load a particular stability which is equivalent to that of the above-mentioned resistances manufactured on basis of F6304 and magnesium spinel or magnesium chromite.
  • the resistances according to the invention may be utilized, for example, for the suppression of current impulses, the stabilisation of the voltage or the compensation of the temperature coefficient of a circuit and, besides, for measuring temperatures.
  • Example I 0.375 gram-molecules of FezOa 1.5 gram-molecules of N temperature at the hottest place is about 110 C. These resistances are suited, for example, to taking up current impulses...
  • WhatIclaim Q 1 An electrical resistance having a negative temperature coefiicient of resistance consisting of 0.75 gram-molecules of T102 are ground with 7 22000 ohms cm. at 22 C., 900 ohms cm. 138 C. 200 ohms cm. 227 C., 50 ohms cm. 332 C.
  • the resistances thus manufactured are suitable, for example, for measuring temperatures.
  • the tubes are heated at 1320 C. in a furnace of 30 cms. length at a travelling speed of 1 cm. per minute whilst using a flow of pure nitrogen (oxygen content about 0.1%) of 5 litres per minute.
  • the resistance value of the tube unloaded is 1600 ohms, whereas with a load of 100 milliamps. it decreases to 81 ohms.
  • An electrical resistance having a negative temperature coefficient of resistance consisting of essentially mixed crystals. constituted by about 25 mol of F6304 and the balance ZNiO-TiOz.
  • Anelectrical resistance having a negative temperature coefiicient of resistance consisting essentially of mixed crystals constituted by about 37% mol of F6304 and the balance 2ZnO-Ti02.
  • a method of manufacturing an electrical resistance having a negative temperature coefiicient which comprises the steps of mixing about 25 to 50 mol of F6304 and 50 to mol of a spinel having the formula 2R O-R Oz, R being a metal selected from the group consisting of nickel and zinc, and R being a metal selected from the group consisting of titanium and tin, said spinel being formed by jointly heating the oxide of a metal of the first group with the oxide of the metal in the second group in the ratio of two mols of the former to one mol of the latter, and sintering the mixture in a nitrogen atmosphere at about 1300 C. for a sufficient time to produce mixed crystals constituted by about 25 to 50 mol of F6304 and the balance said spinel.

Landscapes

  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Description

Patented Nov. 4, 1952 i 1 I UNITED STATES PATENT OFFICE ELECTRICAL RESISTOR V Evert Johannes Willem Verwey, Eindhoven, N ethe'rlands, assignor, by mesne assignments, to
Hartford National Bank and Trust Company, Hartford, Conn., as trustee No Drawin Application April 8, 1946, Serial'No.
660,423. In Belgium March 16, 1945 Section I PubIic' Law 690, August 8, 1946 Patent expires March 16, 1965 4- Claims. (01. 252-490) For the manufacture of, electric resistances of about 500 C. If this condition is fulfilled any there were described different combinations of separation of a second phase at temperatures Fe3O4 with other double-oxides of the spinel type over 500 C., which; would produce undesirable according to the formula: R O. R2 O;, in which variations in the resistance properties, cannot R 1 is a bivalent and Rm is a trivalent element 5 occur. At lower temperatures the speed of sep- Furthermore it is. known that with high load aration is so small that no dimculty is encounparticularly stable resistancesmay beobtained by tered in this respect. a y a I converting combinations of Products of a lower temperature coeiiicient p u, may be obtained if more than approximately half 0 Feo*Fe2O3Mg9 A12O3 of the spinel phase consists of FesOi molecules. n a s'int r ed mass wh c s of As the conductivity owing to the high percentage homo e eous sp Ip a -a' dw ch s not o of F9304, greatly increases it may in this case saturated with a secondpha 'at' a e p be desirable to influence the specific resistance of about 500 C. by the presence of a secondph'ase. For this pur- A a b chO s.m op t r y in pose use may be made, .for example, of semithe manufac of products according 0 the conductive or insulating compoundswhich do not last-mentioned proposal was the high sinterins' dissolve or dissolve only with difficulty in the temperature of from 1500 to 1600 C.,- which was spinel phase, for example Mgo and ZIOz.
troublesome in practice By" the'us'e offusing For'the'manufactur'e of resistances according a e t is awba 011 13 be v a V y to the invention the required material is finely well without detrimentally affecting the resist- 7 divided and intimately mixed-and subsequently ance properties and more particularly the stagiven the'd'esired shape ing-a manner customary bility. in ceramic technics, whereafter sintering to; com- It is true that accord n o h' f p p al pactness' may be 'efiected at a temperature of the sintering temperature may b'e reduced to about 1300* C. The conditions inthe sintering about l400 C. by substitution Crzoc for A1203 in and coolingvprocesses, that is to say the temperthe combination of FeO Fe2O3 -MgO- A 12Os ature' and the partial pressure of the oxygen in but this temperature, too, is still disturbingly the surrounding gas as well as the composition high especially in view of the requ-irements which of the initial inixtu'rearechosen to be such that the furnaces have in this case: to satisfy with themolecula'r ratio of the FeaOli to the other manufacture on a large sca1e.- I spinelsinithe mass' is adjusted-in connection with The present invention purports further to the resistance properties'desired. In-order that reduce the sintering tmperaturewhilst obtainduring the subsequent cooling process this ratio ing a product equivalent'to that according to-the may be retained aswell'aspossible, the cooling two last-mentioned proposals. process may be effected rapidlywhilst driving According to the invention,, the conductive out the atmosphere containing oxygen 'by means material of the resistances consists to this end of a relatively inert gas such as nitrogen.- The of mixed crystals of FesOiwith a spinel of the material may alsobe s-intered inan atmosphere type 2R OR O2, in which formula R repre in which the partial pressure" of the oxygen sents a bivalent and R a-tetravalent element- 40 decreases with temperature, i.e. an atmosphere AS Such y be m t n 9111 titanates and Stanof nitrogen" containing superheated water vapor nat s with sp l stru r f xample M z i i, which i qis'soeiable intc x' en" and hydrogen, Zn2TiO4, NizTiOr and ZneSnOi or theirmixed the rate of-dissociation being'dependentupon the crystals temperature? p The resistance value as well as the temperature: lsinee" the content of, FeOi and hence the coefficient' of resistances thus: composed maybe molecular ratioFeO) reset may 'beadjust'ed by adjusted by the choice "offtheucontent' Of FeQO i: the choice of the sintering temperature" and of and the presence, ifuanyn of asecondphase in the the sinteri-nge atmosphere; the initial material sinteredl producin 2 used aforithei'resistances; according to the inven- As regards the temperature coeflicient it may 5,9 tion may be" any-forms of iron oxide and, if 3 be mentioned that this is highly negative in proddesired, iron powder, while the other constituents ucts consisting of a homogeneous spinel phase already referred to above may be used wholly or of which less than approximately half is built in part in the form of double-oxides. up from F3304 molecules and which is not over- Besides, it is of particular advantage that, saturated with a second phase at a temperature owing to the circumstance already favourable per se that the sintering temperature may be reduced to approximately 1300 0., the sintering process may be carried out in an atmosphere of pure nitrogen without the F8304 formed from F8203 being reduced further to the FeO. Thus the reproducibility of the resistance value is also very high. '7
Furthermore, the difliculties encountered in the manufacture of resistances according to the previous proposals are materially decreased. Thus, for example, the use of electric furnaces having a molybdenum winding in a protecting gas is possible since the latter at an operating temperature of approximately 1300 C. have a satisfactory period of life which is appreciably higher than at temperatures of approximately 1400 C. which had to be applied in sintering resistances on basis of F8304 and magnesium chromite. Such advantages also occur with furnaces of any other type.
Owing to the circumstance that according to the invention, a product of high compactness is obtained, the resistances exhibit even with high load a particular stability which is equivalent to that of the above-mentioned resistances manufactured on basis of F6304 and magnesium spinel or magnesium chromite.
The resistances according to the invention may be utilized, for example, for the suppression of current impulses, the stabilisation of the voltage or the compensation of the temperature coefficient of a circuit and, besides, for measuring temperatures.
Example I 0.375 gram-molecules of FezOa 1.5 gram-molecules of N temperature at the hottest place is about 110 C. These resistances are suited, for example, to taking up current impulses...
WhatIclaim Q 1 1. An electrical resistance having a negative temperature coefiicient of resistance consisting of 0.75 gram-molecules of T102 are ground with 7 22000 ohms cm. at 22 C., 900 ohms cm. 138 C. 200 ohms cm. 227 C., 50 ohms cm. 332 C.
The resistances thus manufactured are suitable, for example, for measuring temperatures.
Example II 4.5 gram-molecules of FezO;
10.2 gram-molecules of ZnO 5.1 gram-molecules of TiOz are ground with ethyl acetate for 16 hours and with the use of a 10% nitrocellulose solution in ethyl glycol extruded into tubes of 6.3 mms. long having an external diameter of 8 mms. and an internal diameter of 4.5 mms. Subsequently,
the tubes are heated at 1320 C. in a furnace of 30 cms. length at a travelling speed of 1 cm. per minute whilst using a flow of pure nitrogen (oxygen content about 0.1%) of 5 litres per minute.
The resistance value of the tube unloaded is 1600 ohms, whereas with a load of 100 milliamps. it decreases to 81 ohms. With this load the essentially mixed crystals constituted by 25 to 50 mol of FeaO4 and the balance a spinel having the formula 2R O-R O2, R being a bivalent metal selectedfrom the group consisting of nickel and,zinc and B being a tetravalent metal selected from the group consisting of titanium and tin.
2. An electrical resistance having a negative temperature coefficient of resistance consisting of essentially mixed crystals. constituted by about 25 mol of F6304 and the balance ZNiO-TiOz.
3. Anelectrical resistance having a negative temperature coefiicient of resistance consisting essentially of mixed crystals constituted by about 37% mol of F6304 and the balance 2ZnO-Ti02.
4. A method of manufacturing an electrical resistance having a negative temperature coefiicient which comprises the steps of mixing about 25 to 50 mol of F6304 and 50 to mol of a spinel having the formula 2R O-R Oz, R being a metal selected from the group consisting of nickel and zinc, and R being a metal selected from the group consisting of titanium and tin, said spinel being formed by jointly heating the oxide of a metal of the first group with the oxide of the metal in the second group in the ratio of two mols of the former to one mol of the latter, and sintering the mixture in a nitrogen atmosphere at about 1300 C. for a sufficient time to produce mixed crystals constituted by about 25 to 50 mol of F6304 and the balance said spinel.
EVERT J OHANNES WILLEM VERWEY.
REFERENCES CITED The following references are of record in the file of this patent:
UNITED STATES PATENTS Number Name Date 648,518 Och May 1, 1900 860,997 Steinmetz July 23, 1907 1,911,396 Saklatwalla et al. May 30, 1933 2,027,277 Habann Jan. 7, 1936 2,068,294 Korinth et al Jan. 19, 1937 2,370,443 Biefeld Feb. 27, 1945 2,371,660 Wainer Mar. 20, 1945 2,418,467 Ellis Apr. 8, 1947 2,468,458 Padmos et a1 Apr. 26, 1949 2,475,864 Verwey et al. July 12, 1949 FOREIGN PATENTS Number Country Date 506,964 Great Britain 1939 OTHER REFERENCES Kawai-Studies on FerritesJournal of the Soc. of Chem. Ind., Japan, vol. 37, No. 4, pg. 1743, pub. 1934.
Mellor Comprehensive Treatise on Inorganic and Theoretical Chemistry, vol. 13, pg. 732, pub. Longmans, Green & 00., N. Y., 1934. 8 "Iiiackhs Chem. Dictionary, 2nd Ed. 1937, pg.

Claims (1)

1. AN ELECTRICAL RESISTANCE HAVING A NEGATIVE TEMPERATURE COEFFICIENT OF RESISTANCE CONSISTING OF ESSENTIALLY MIXED CRYSTALS CONSTITUTED BY 25 TO 50 MOL % OF FE3O4 AND THE BALANCE A SPINEL HAVING THE FORMULA 2RIIO.RIVO2, R22 BEING A BIVALENT METAL SELECTED FROM THE GROUP CONSISTING OF NICKEL AND ZINC AND RIV BEING A TETRAVALENT METAL SELECTED FROM THE GROUP CONSISTING OF TITANIUM AND TIN.
US660423A 1945-03-16 1946-04-08 Electrical resistor Expired - Lifetime US2616859A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BE2616859X 1945-03-16

Publications (1)

Publication Number Publication Date
US2616859A true US2616859A (en) 1952-11-04

Family

ID=3895955

Family Applications (1)

Application Number Title Priority Date Filing Date
US660423A Expired - Lifetime US2616859A (en) 1945-03-16 1946-04-08 Electrical resistor

Country Status (1)

Country Link
US (1) US2616859A (en)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2941931A (en) * 1958-12-22 1960-06-21 Chicago Dev Corp Compounds of zirconium and methods of preparing same
US2962452A (en) * 1957-06-12 1960-11-29 Gen Motors Corp Ceramic semi-conductor compositions
US3028656A (en) * 1955-09-13 1962-04-10 Plessey Co Ltd Ceramic material and method of producing the same
US3044867A (en) * 1957-05-15 1962-07-17 Messrs Aktiebolaget Svenska Me Method for the production of metallicceramic materials
US3121065A (en) * 1960-08-03 1964-02-11 Greger Herbert Hans Electrically conductive ceramic tile
US3342753A (en) * 1962-03-30 1967-09-19 Philips Corp Method for making electrically conductive vitreous materials
US3393448A (en) * 1965-12-22 1968-07-23 Owens Illinois Inc Method for making thermistors
US3479631A (en) * 1965-12-22 1969-11-18 Owens Illinois Inc Thermistors
US3928837A (en) * 1973-09-27 1975-12-23 Bosch Gmbh Robert Ceramic oxide resistor element
US4305287A (en) * 1979-05-12 1981-12-15 Licentia Patent-Verwaltungs-Gmbh Apparatus for controlling energy conversion
US4700169A (en) * 1984-03-29 1987-10-13 Kabushiki Kaisha Toshiba Zinc oxide varistor and method of making it
US20100065743A1 (en) * 2006-12-14 2010-03-18 Commissariat A L'energie Atomique Use of a combination of iron monoxide and spinel oxides as a sensitive material for detecting infrared radiation

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US648518A (en) * 1899-09-16 1900-05-01 Karl Ochs Electrical resistance.
US860997A (en) * 1900-12-28 1907-07-23 Gen Electric Lightning-arrester.
US1911396A (en) * 1932-11-29 1933-05-30 Southern Mineral Products Corp Process of treating titaniferous ores
US2027277A (en) * 1929-08-16 1936-01-07 Habann Erich Contact device
US2068294A (en) * 1931-02-07 1937-01-19 Ig Farbenindustrie Ag Inorganic colored pigment and a process of preparing the same
GB506964A (en) * 1937-06-21 1939-06-07 Tool Metal Mfg Company Ltd Improvements in and relating to hard compositions
US2370443A (en) * 1936-12-28 1945-02-27 Biefeld Karl Nonmetallic electric resistance material and process for producing same
US2371660A (en) * 1941-02-07 1945-03-20 Titanium Alloy Mfg Co Composition and article for electric use
US2418467A (en) * 1943-09-24 1947-04-08 Bell Telephone Labor Inc Treatment of finely divided magnetic material
US2468458A (en) * 1949-04-26 Method of manufactubing resistance
US2475864A (en) * 1944-03-29 1949-07-12 Hartford Nat Bank & Trust Co Electric resistance element

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2468458A (en) * 1949-04-26 Method of manufactubing resistance
US648518A (en) * 1899-09-16 1900-05-01 Karl Ochs Electrical resistance.
US860997A (en) * 1900-12-28 1907-07-23 Gen Electric Lightning-arrester.
US2027277A (en) * 1929-08-16 1936-01-07 Habann Erich Contact device
US2068294A (en) * 1931-02-07 1937-01-19 Ig Farbenindustrie Ag Inorganic colored pigment and a process of preparing the same
US1911396A (en) * 1932-11-29 1933-05-30 Southern Mineral Products Corp Process of treating titaniferous ores
US2370443A (en) * 1936-12-28 1945-02-27 Biefeld Karl Nonmetallic electric resistance material and process for producing same
GB506964A (en) * 1937-06-21 1939-06-07 Tool Metal Mfg Company Ltd Improvements in and relating to hard compositions
US2371660A (en) * 1941-02-07 1945-03-20 Titanium Alloy Mfg Co Composition and article for electric use
US2418467A (en) * 1943-09-24 1947-04-08 Bell Telephone Labor Inc Treatment of finely divided magnetic material
US2475864A (en) * 1944-03-29 1949-07-12 Hartford Nat Bank & Trust Co Electric resistance element

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3028656A (en) * 1955-09-13 1962-04-10 Plessey Co Ltd Ceramic material and method of producing the same
US3044867A (en) * 1957-05-15 1962-07-17 Messrs Aktiebolaget Svenska Me Method for the production of metallicceramic materials
US2962452A (en) * 1957-06-12 1960-11-29 Gen Motors Corp Ceramic semi-conductor compositions
US2941931A (en) * 1958-12-22 1960-06-21 Chicago Dev Corp Compounds of zirconium and methods of preparing same
US3121065A (en) * 1960-08-03 1964-02-11 Greger Herbert Hans Electrically conductive ceramic tile
US3342753A (en) * 1962-03-30 1967-09-19 Philips Corp Method for making electrically conductive vitreous materials
US3393448A (en) * 1965-12-22 1968-07-23 Owens Illinois Inc Method for making thermistors
US3479631A (en) * 1965-12-22 1969-11-18 Owens Illinois Inc Thermistors
US3928837A (en) * 1973-09-27 1975-12-23 Bosch Gmbh Robert Ceramic oxide resistor element
US4305287A (en) * 1979-05-12 1981-12-15 Licentia Patent-Verwaltungs-Gmbh Apparatus for controlling energy conversion
US4700169A (en) * 1984-03-29 1987-10-13 Kabushiki Kaisha Toshiba Zinc oxide varistor and method of making it
US20100065743A1 (en) * 2006-12-14 2010-03-18 Commissariat A L'energie Atomique Use of a combination of iron monoxide and spinel oxides as a sensitive material for detecting infrared radiation
US9376346B2 (en) * 2006-12-14 2016-06-28 Commissariat A L'energie Atomique Use of a combination of iron monoxide and spinel oxides as a sensitive material for detecting infrared radiation

Similar Documents

Publication Publication Date Title
US2616859A (en) Electrical resistor
JPH08217536A (en) Semiconductor porcelain composition having positive temperature coefficient of resistance and production thereof
WO1986003051A1 (en) Oxide semiconductor for thermistor and a method of producing the same
US3373120A (en) Semiconductive ceramic compositions with positive temperature coefficient of resistance
US2703354A (en) Alkaline earth manganate ceramics
GB1251453A (en)
JPH068210B2 (en) Varistor material and its manufacturing method
US3836483A (en) Oxide varistor
US2468458A (en) Method of manufactubing resistance
JPH08162302A (en) Thermistor and its manufacture
JPH0142613B2 (en)
US1019568A (en) Method of making resistance material.
US2475864A (en) Electric resistance element
JP3213647B2 (en) Negative thermistor composition and negative thermistor
US2524611A (en) Electric resistance and method of making
SU1138838A1 (en) Material for temperature-sensitive resistors
JPS5823402A (en) Method of producing nonlinear resistor
JP3213643B2 (en) Negative thermistor composition and negative thermistor
JPS59232966A (en) Electroconductive zirconia sintered body
SU1600560A1 (en) Method of manufacturing barium titanate base positive tc thermistors
JPS63122101A (en) Voltage nonlinear resistor
JPH05301766A (en) Barium titanate-based semiconductive porcelain and its production
JPH07230902A (en) Semiconductor ceramic element
JPS6330763B2 (en)
JPS6031792B2 (en) Barium titanate semiconductor porcelain