US2274592A - Resistance material and method of making the same - Google Patents

Resistance material and method of making the same Download PDF

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Publication number
US2274592A
US2274592A US280692A US28069239A US2274592A US 2274592 A US2274592 A US 2274592A US 280692 A US280692 A US 280692A US 28069239 A US28069239 A US 28069239A US 2274592 A US2274592 A US 2274592A
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United States
Prior art keywords
resistance
oxides
cobalt
nickel
manganese
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Expired - Lifetime
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US280692A
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English (en)
Inventor
Ernest F Dearborn
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AT&T Corp
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Bell Telephone Laboratories Inc
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Priority to US280692A priority Critical patent/US2274592A/en
Priority to GB10706/40A priority patent/GB540844A/en
Priority to FR867097D priority patent/FR867097A/fr
Priority to GB349041A priority patent/GB545679A/en
Application granted granted Critical
Publication of US2274592A publication Critical patent/US2274592A/en
Anticipated expiration legal-status Critical
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    • 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
    • H01C7/04—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 negative temperature coefficient
    • H01C7/042—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 negative temperature coefficient mainly consisting of inorganic non-metallic substances
    • H01C7/043—Oxides or oxidic compounds

Definitions

  • PatenteclFeh. 24,- 1942 RESISTANCE s PATENT MATERIAL Aim METHOD or MAKING 'rnn same OFFICE Ernest F. Dearborn, Yonkers, N. Y., assignor to Bell Telephone Laboratories,
  • This-invention relates to resistors and resistance materials which have high negative temperature coefficients of resistance, and to methods of making such resistors and resistance materials. More specifically, it relates to resistance materials made from combinations of metal oxides.
  • resistance materials having particularly desirable characteristics may be made from combinations of metal oxides.
  • series of units may be made having a wide range of specific resistance but all within a comparatively narrow range of high resistance-temperature coefficients. It has been found that/mixtures of nickel and manganese oxides when prop erly heat treated combine to produce a resistance material having particularly desirable resistance characteristics.
  • One object of this invention is to improve resistors and resistance materialsmade from oxidic material.
  • Anotherobject'of this invention is to improve the resistance characteristics of resistors and resistance materials containing manganese and nickel oxides.
  • One feature of this invention resides in the addition of cobalt oxide to the oxides of manganese and nickel in the formation of resistance materials.
  • the ratio of the oxides is controlled to obtain a desired specific resistance.
  • a solution containing a compound of the metallic element of one ofthe oxides is em-.
  • Fig. 1 is a sectional viewof a resistor illustrating one embodiment of the invention
  • F g. 2 is a sectional view of a different resistor illustrating another embodiment of the invention.
  • Fig. 3 is a curve showing the eifect on the resistance of the addition of cobalt oxide to aimixture of nickel and manganese oxides;
  • Fig. 4 is a triangular diagram showing constant resistance contours for difierent compositions of nickel, manganese and cobalt oxides
  • Fig. 5 is a similar triangular diagram with constant half temperature contours.
  • Figs. 6 and 'l are diagrams similar to those shown in Figs. 4 and 5 but for relative proportions of the metallic elements, Fig. 6 showing specific resistances and Fig. 7 half temperatures.
  • resistor units made from nickel and manganese oxides and containing the compound nickel-manganite exhibit minimum specific resistance for an atomic ratio of Mn/Ni between 2 to 1 and 4 to 1.
  • the resistance-temperature coeflicient or half temperature varies little from that of the minimum resistance material.
  • the term half temperature may be defined as the, temperature range over which the resistance is doubled or reduced by half. In specifyinghalf temperatures the range over which the measurement is taken should be given. A convenient range is from 0 to 25 C. and will be understood in this application unless otherwise specified.
  • the constituent oxides are usually employed in a finely divided state. Predetermined proportions of the three oxides are intimately mixed and' formed into bodies of suitable size and shape for the purpose intended.
  • the bodies are heat treated at temperatures ranging from 800 to 1450 C.-
  • the temperature and the atmosphere of heat treatment are regulated in accordance with the resistance desired. For example, an oxidizing atmosphere reduces theresistance, if the cobalt oxide content isbelow about per cent. If more than approximatelyfilO per cent cobalt oxide is used, the resistance is lowered by a reducing atmosphere. In general, for a given'composition, the higher the temperature of heat treatment the lower will be the resistance of the completed material or unit.
  • the resistance of the material is a function of the relative amounts of the metallic elements present after the three oxides are combined.
  • the atmosphere of heat treatment determines the amount of oxygen in the finished product, which also afiectsthe resistance value.
  • oxides of the three metals may be used and a suitable heat treatment employed for a given composition to give the desired resistance characteristics.
  • the resistor units may be made up in several forms two of which are shown in Figs. 1 and 2.
  • a bead type unit such as is shown in Fig. 1,
  • the finely divided oxides may be made by mixingthe finely divided oxides and forming a paste with a suitable binder.
  • a preferred binder comprises a nitrate solution such as 6010;, to the nickel-manganese oxide mixtureisshownbythecurveof l?ig. 3.
  • Figs. 4 and 5 are shown triangular diagrams indicating the relative amounts of the Y three oxides contained in any given unit.
  • cobalt nitrate of one of the metals involved, for example, cobalt nitrate.
  • the powdered oxides may also be mixed with water.
  • the paste is formed into small beads ill on parallel wires ll of refractory conductive material, such as platinum.
  • the beads are then dried and heat treated.
  • account should be taken of the metallic content of the binder.
  • the cobalt oxide should be adjusted so that the sum of the cobalt therein and the cobalt obtained from the nitrate during heat treatment will be in the proper amount.
  • a unit of the disc or plate type such as shown in Fig. 2, may be made by intimately mixing the finely divided oxides and pressing them into a body 20.
  • the heat treatment for this type of unit is similar to that employed for the bead unit.
  • Contact electrodes may be applied to opposite faces of the disc or plate by any adequate means.
  • a suitable connection can be made by applying metallic paste to the surfaces and embedding conductive leads 22 therein. The units are then heated to solidify the paste into electrodes 2
  • the conductive leads 22 may also be applied as follows: Metallic paste is applied to the unit and heated to solidify it, a sprayed metallic layer,'as from a Schoop spray, is applied over this and the leads soldered thereto.
  • the body 20 is made relatively thin, so that the current path between the electrodes 2
  • the contour lines passthrough points of equal, resistance and in Fig. 5 through points of equal half temperature.
  • the resistance designations are in ohms and the half temperatures in degrees centigrade measured between 0 and 25 C.
  • a composition having a particular resistance and half "temperature may be determined.
  • the diagrams illustrated in these figures are for a bead unit, 0.03 inch in diameter, heat treated at 1300 C. in oxygen, the constituents being NiO, MnzO: and C0203.
  • Other similar diagrams may, for convenience, be made for other of the oxides of nickel, manganese and cobalt, other sizes of units and diflerent heat treatments. Diagrams such as those illustrated in Figs.
  • Figs. 4 and 5 indicates that the proportions of the constituents may be so adjusted that for a half temperature range between 10 and 20 0., units may be obtained having resistances ranging from about 15,000 ohms'to l0 megohms, which in terms of specific resistance is from about 3,000 to 2x10 ohm-centimeters.
  • resistors of the type disclosed, for many purposes lies in their comparatively low half temperatures.
  • a material in accordance with this invention, comprising any combination of the oxides of nickel, manganese and cobalt will produce resistors having a half temperature below 70 C.
  • a very large por- 4 Referring further to the diagrams atur.
  • the combined oxides of nickel, manganese and cobalt in accordance with this invention is jpredominantly electronic, allowing their use for of mercury or better is suitable.
  • unit having about 0.5 per cent nickel, 55 per cent manganese and 44.5 per cent cobalt has a half temperature of about 14 C. or one having percentages of 2, 95 and 3, respectively, for nickel, manganese and cobalt has a 20 C. half temper- Moreover, for a combination in which the nickel is over about 33 per cent, a 20 C. or lower half temperature is obtainable for a wide range of ratios of manganese to cobalt.
  • the specific resistance for these combinations is relatively high being of the order of 2x10 ohmcentimeters or higher.
  • a minimum specific resistance of the order of 5x10 ohm-centimeters may be obtained with a half temperature within the range 14 to 20 C. with compositions containing from approximately 3 to 10 per cent nickel, to '70 per cent manganese and 25 to 75 per cent cobalt. For applications in which a higher half such units is a small bead type of about-0.03. inch diameter. 30,000 ohms at 25 C. and a half temperature of about 18 C. measured between 0' and 25 C., and comprises 23 per cent mo, 47 per 'cent M04 and per cent CoaOa.
  • a negative resistance-temperature coem-' cient resistance material consisting of oxides of nickel, manganese and cobalh heat treated ;be tween 800 and 1450 C., the major portion of said material comprising said oxides in combination, the metals being in the approximate proportions corresponding respectively to 23 percent N10, 47 per cent M104 and 30 per cent C0203.
  • the method of making a negative resistance-temperature coefllclent resistance material that comprises mixing finely divided oxides of nickel, manganese and cobalt, and combining th oxides by heat treating the mixture at a temperature between 800 and 1450 in a controlled atmosphere.
  • the method of making a negative resistance-temperature coefilcient resistance unit that comprises intimately mixing finely divided oxides mixture into a body, and combining the oxides by heat treating the body in an atmosphere free from reducing agents at a temperature between 800 and 1450 C.
  • manganese and cobalt intimately mixed and heat temperature is suitable, a material having a mintreated between 800 and 1450 C., the constituentsb'eing in the proportion of more than about 45 per cent of the oxide of manganese, up to about 30 per cent of the oxide of cobalt, and the remainder the oxide of nickel, the major portion of said material comprising the oxides in combination.
  • a negative resistance-temperature coefficient material consisting of oxides of nickel, manganese and cobalt intimately mixed and heat treated between 300 and 1450 C., the major part of said material comprising the oxides in combination.
  • a negative resistance-temperature coeiiicient resistance material consisting of oxides of nickel, manganese and cobalt, heat treated beof the oxide of cobalt with' the oxides of manganose and nickel in the approximate ratio oi 4 to 1 to 2 to 1, the major portion of said-material comprising the oxides in combination.

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  • Engineering & Computer Science (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Electromagnetism (AREA)
  • Thermistors And Varistors (AREA)
  • Non-Adjustable Resistors (AREA)
US280692A 1939-06-23 1939-06-23 Resistance material and method of making the same Expired - Lifetime US2274592A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
US280692A US2274592A (en) 1939-06-23 1939-06-23 Resistance material and method of making the same
GB10706/40A GB540844A (en) 1939-06-23 1940-06-21 Resistance materials and methods of making the same
FR867097D FR867097A (fr) 1939-06-23 1940-09-10 Résistances électriques
GB349041A GB545679A (en) 1939-06-23 1941-03-14 Resistance composition and method of making it

Applications Claiming Priority (1)

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US280692A US2274592A (en) 1939-06-23 1939-06-23 Resistance material and method of making the same

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FR (1) FR867097A (fr)
GB (1) GB540844A (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2626445A (en) * 1950-06-07 1953-01-27 Steatite Res Corp Heavy-metal oxide resistors and process of making same
US2645700A (en) * 1949-08-27 1953-07-14 Bell Telephone Labor Inc Semiconductor of mixed nickel, manganese, and iron oxides
US2694050A (en) * 1949-09-01 1954-11-09 Bell Telephone Labor Inc Thermally sensitive resistor
DE1040660B (de) * 1952-09-22 1958-10-09 Siemens Ag Heissleiter mit hohem Temperaturkoeffizienten
US4160227A (en) * 1977-03-18 1979-07-03 Hitachi, Ltd. Thermistor composition and thick film thermistor
US5865930A (en) * 1992-04-10 1999-02-02 Candescent Technologies Corporation Formations of spacers suitable for use in flat panel displays

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2645700A (en) * 1949-08-27 1953-07-14 Bell Telephone Labor Inc Semiconductor of mixed nickel, manganese, and iron oxides
US2694050A (en) * 1949-09-01 1954-11-09 Bell Telephone Labor Inc Thermally sensitive resistor
US2626445A (en) * 1950-06-07 1953-01-27 Steatite Res Corp Heavy-metal oxide resistors and process of making same
DE1040660B (de) * 1952-09-22 1958-10-09 Siemens Ag Heissleiter mit hohem Temperaturkoeffizienten
US4160227A (en) * 1977-03-18 1979-07-03 Hitachi, Ltd. Thermistor composition and thick film thermistor
US6489718B1 (en) 1982-04-10 2002-12-03 Candescent Technologies Corporation Spacer suitable for use in flat panel display
US5865930A (en) * 1992-04-10 1999-02-02 Candescent Technologies Corporation Formations of spacers suitable for use in flat panel displays
US5916396A (en) * 1992-04-10 1999-06-29 Candescent Technologies Corporation Formation of spacers suitable for use in flat panel displays
US5985067A (en) * 1992-04-10 1999-11-16 Candescent Technologies Corporation Formation of spacers suitable for use in flat panel displays
US6157123A (en) * 1992-04-10 2000-12-05 Candescent Technologies Corporation Flat panel display typically having transition metal oxide in ceramic core or/and resistive skin of spacer

Also Published As

Publication number Publication date
GB540844A (en) 1941-10-31
FR867097A (fr) 1941-09-26

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