US3679607A - Oxide resistor materials - Google Patents

Oxide resistor materials Download PDF

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Publication number
US3679607A
US3679607A US676515A US3679607DA US3679607A US 3679607 A US3679607 A US 3679607A US 676515 A US676515 A US 676515A US 3679607D A US3679607D A US 3679607DA US 3679607 A US3679607 A US 3679607A
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Prior art keywords
oxide
dioxide
ruthenium
composition
resistance
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Expired - Lifetime
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US676515A
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English (en)
Inventor
Hamish Carmichael Angus
Peter Edward Gainsbury
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Huntington Alloys Corp
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International Nickel Co Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01C—RESISTORS
    • H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
    • H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
    • H01C17/065—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base by thick film techniques, e.g. serigraphy
    • H01C17/06506—Precursor compositions therefor, e.g. pastes, inks, glass frits
    • H01C17/06513—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component
    • H01C17/06533—Precursor compositions therefor, e.g. pastes, inks, glass frits characterised by the resistive component composed of oxides
    • H01C17/0654—Oxides of the platinum group

Definitions

  • the present invention relates to electric resistance elements and more particularly to oxide resistors and to compositions for making oxide resistors.
  • Resistors consisting of a film of resistance material fused to a refractory, non-conducting base are known.
  • the non-conducting base may be glass or ceramic and the resistance material a mixture of conducting and nonconducting materials.
  • the resistance material has usually comprised specially treated metal powders and glass particles and the film has been formed by applying these powders and particles to the base as a dispersion in an organic vehicle by dipping, brushing, spraying or silkscreen printing and has subsequently been heat-treated to fuse it to the base.
  • severe difiiculties in the way of obtaining consistent results have arisen when such prior means were employed in efforts to consistently produce resistors having resistances greater than about 30,000 ohms per square.
  • the resistance of films containing an oxide, or oxides, for the electrically conducting phase decreases as the proportion of oxide increases.
  • films may consistently be prepared having resistances ranging 'from zero and then through increasing positive values.
  • the TCR of films of low oxide content having resistances in the upper part of the above-mentioned range may be satisfactory, it in some instances becomes unacceptably high and positive at resistances below about 1500 ohms per square.
  • a further object of the invention is to provide a composition for making oxide resistors.
  • Another object of the invention is to provide a process for Iproduction of oxide resistors.
  • FIGS. 1, 2, and 3 are charts depicting electrical characteristics of resistance, temperature coefficient of resistance and current noise, respectively, pertaining to resistors made with ruthenium dioxide compositions according to the invention and to other resistors made with ruthenium dioxide compositions not in accordance with the invention.
  • FIG. 4 is a plan view of an oxide resistor of the invention.
  • i IFIG. 5 is a cross sectional view of the resistor illustrated in FIG. 4.
  • the present invention contemplates a composition which is adapted to be applied to a refractory, non-conducting base and fired to form an electrical resistance and which comprises ruthenium dioxide or iridium dioxide or both having a crystallite size up to and not greater than about 500 angstroms (A.) and advantageously not -greater than 300 A., in admixture with glass, the proportion of oxide being up to about of the mixture.
  • This invention especially involves the surprising discovery that the TCR of an oxide-glass resistance film of a given composition depends largely upon the crystallite size of the oxide, being more negative and thus less positive for smaller crystallite sizes. The absolute value of the TCR of films having a positive TCR can thereby be reduced. Resistances made from compositions in accordance with the invention have TCR values more negative than those made from the oxides available commercially and characterized by much larger crystallites.
  • a further yadvantage of having the oxide particles of crystallite sizes not greater than 500 A. is that the current noise of the resistance film is significantly lower than with oxides with larger crystallites.
  • the TCR also depends on the size of the discrete particles of the oxide, having smaller positive 'values for smaller particles. To obtain the lowest values of TCR the particles should therefore be very line, the average particle size desirably being 0.2 to 3 microns.
  • the size of the non-conducting glass particles is not critical. An average size of about 3.5 microns is satisfactory for the glass particles.
  • composition is advantageously provided as a suspension of the mixture of oxide and glass in a liquid vehicle that is suitable for application to the refractory base by screen printing or other convenient methods.
  • the invention includes resistances made by the use of the composition.
  • One method according to the invention of making ruthenium dioxide with the requisite crystallite size is as follows. Ruthenium chloride solution containing approximately 5 grams per liter (g./l.) ruthenium is treated with sodium hydroxide until it is just alkaline, and then acidied with hydrochloric acid to pH 6-7. The resultant suspension of hydrated dioxide is washed several times with distilled water by decantation, then filtered on.
  • the suspension of hydrated dioxide is dialysed in an ion-selected membrane cell until the aqueous phase shows minimum conductivity (corresponding to the presence of less than parts per million sodium chloride), and the suspension of dioxide is then filtered. In either case the ltered dioxide is oven-dried at 110 C.
  • the dioxide thus produced is in the hydrated form and can be used in this form or can be rst heated to expel the water of crystallization. It has been found that the crystalline size increases if the dioxide is heated to too high a temperature and if this excess 500 C. there is a risk that the crystallite size will exceed 500 A.
  • ruthenium dioxide produced by the method described above
  • some other methods are found to lead to unsatisfactory high average crystallite sizes of 1000 A. or more.
  • These unsatisfactory methods include heating ruthenium powder in air and precipitating ruthenium dioxide from a solution of sodium ruthenate.
  • a typical commercially-avaih able RuO, powder has an average particle size of about 7 microns, i.e., 70,000 angstroms. v
  • One method of producing iridium dioxide of therequisite crystallite size comprises adding sodium bromate to iridium chloride solution, adjusting the pH to 7 by the addition of sodium carbonate, and boiling the solution for one hour. Hydrated iridium dioxide is precipitated and is liltered, washed free of the ,chloride and dried. The hydrated oxide is then dehydrated by heating in air for one hour at 700 C. and ground. In this heating step it is important not to go too high a temperature, in order to avoid the risk of excessively in creasing the crystallite size.
  • lParticles of a batch (Batch I) of ruthenium dioxide (Oxide A), produced according to the aforedescribed method comprising treatment of ruthenium chloride with sodium hydroxide, acidification, ltration and washing, when examined in an electron microscope were found to contain well-defined crystallites, which usually took an irregular, basically hexagonal, shape but often approached a spheroidal form.
  • Another batch of ruthenium dioxide (Batch II of Oxide B) was produced by the same method and small crystallite sizes in somewhat differently sized particles were obtained.
  • a ruthenium dioxide Batch III was also made by the method of making Batches I and II and dioxides from a portion of Batch III and from another portion of Batch II were each heated to 500 C. until the water of crystallization was removed, thereby providing Oxides C and D, respectively, which were similarly formed into resistors.
  • Particles of iridium dioxide (Oxide E) produced from iridium chloride according to the aforedescribed method were similarly formed into a resistor.
  • Oxide I Ruthenium dioxide precipitated from sodium ruthenate solution with methyl alcohol and heated to 500 C.
  • Crystallite sizes and particle sizes of Oxides A through E, which are in accordance with the invention, and of Oxides F through I, which are not in accordance with the invention, are setforth in -the following table along with TCR valuesA pertaining to resistors made with the corresponding oxides. Crystallite sizes are the average of the largest and smallest dimensions or the averagediameters of the spherical crystallites.
  • e -Additional resistors were prepared using the ruthenium dioxides, Oxide B and Oxide H and varying the proportions of oxide and glass, all other variables being kept constant.
  • the resistance, TCR and rcurrent noise were measured for each of theresistances by standard techniques, and the results are illustrated graphically in the accompanying drawing, the variation of resistance with ruthenium dioxide content of the film being shown in FIG. 1, the vvariation of theTCR with ruthenium dioxide content being shown in FIG. 2 and the variation of the current noise with ruthenium dioxide content being shown in FIG. 3.
  • FIG 2 shows that Curve B-2, which relates TCR and composition for the resistances according to the invention made from Oxide B, lies wholly below Curve H-Z that relates TCR and composition of resistances made from Oxide H, which was of larger crystallite size. It is preferred in practice that lm resistors should have'a TOR not exceeding 300 p.p.m./ C., and it is apparent that by means of the invention this can be achieved down to much lower values of the resistance than in the case of resistors made from commercially-available oxides.
  • FIG. 3 the values of current noise in decibels are plotted as ordinates.
  • the reduction in noise achieved by means of the invention is clearly evident for widely varying proportions of oxide, as illustrated by Curves B3 and H-3 with the points along Curve B3 pertaining to resistances according to the invention made from Oxide B and with the points along Curve H-3 pertaining to resistances made from Oxide H.
  • FIG. 4 shows fired resistor 1, made using a ruthenium dioxide composition in accordance with the invention, fused on ceramic substrate 2 between conductive leads 3 and 4.
  • FIG. 5 is a cross sectional view, along the section 5 5 shown on FIG. 4, illustrative of ruthenium dioxide particles 6 in glass matrix 7. It is to be understood that inasmuch as the crystallites may grow during ring of the resistor, the initial crystallite size of the dioxide in the composition prior to firing is not per se necessarily a characteristic of the red resistor even though engendering highly important results in the nal product.
  • a composition adapted to be appliedto a refractory, non-conducting base and red to form an electrical resistance comprising a mixture of powdered glass and about 2% to about 90% of dioxide selected from the group consisting of ruthenium dioxide, iridium dioxide and mixtures thereof with said dioxide having a crystallite size up to about 500 angstroms.
  • composition as set forth in claim 1 wherein the proportion of dioxide is about 10% to about 60%.
  • a composition as set forth in claim 6 wherein the proportion of dioxide is about 10% to about 60%.
  • a resistor comprising a non-conducting base having fused to its surface an electrically resisting film formed from the composition set forth in claim 1.
  • a resistor comprising a non-conducting base having fused to its surface an electrically resisting lm formed from the compostion set forth in claim 6.
  • composition containing metal oxide particles and glass particles is applied to a substrate and red to produce a resistance element from the glass and metal oxide composition
  • improvement comprising providing in said composition dioxide particles having a ne crystallite size of up to about 500 angstroms rand selected from the group consisting of ruthe'nium dioxide, iridium dioxide and mixtures thereof.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Adjustable Resistors (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
  • Conductive Materials (AREA)
US676515A 1966-10-24 1967-10-19 Oxide resistor materials Expired - Lifetime US3679607A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB47690/66A GB1148926A (en) 1966-10-24 1966-10-24 Resistors

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US3679607A true US3679607A (en) 1972-07-25

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US676515A Expired - Lifetime US3679607A (en) 1966-10-24 1967-10-19 Oxide resistor materials

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US (1) US3679607A (es)
BE (1) BE705550A (es)
DE (1) DE1640563A1 (es)
GB (1) GB1148926A (es)
NL (2) NL6714387A (es)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3899449A (en) * 1973-05-11 1975-08-12 Globe Union Inc Low temperature coefficient of resistivity cermet resistors
US3914514A (en) * 1973-08-16 1975-10-21 Trw Inc Termination for resistor and method of making the same
US4006278A (en) * 1973-05-11 1977-02-01 Globe-Union Inc. Low temperature coefficient of resistivity cermet resistors
US4101708A (en) * 1977-03-25 1978-07-18 E. I. Du Pont De Nemours And Company Resistor compositions
DE2846577A1 (de) * 1977-10-31 1979-05-10 Philips Nv Verfahren zur herstellung von widerstandsmaterial und durch dieses verfahren hergestellte widerstandskoerper
US5021194A (en) * 1986-11-14 1991-06-04 Hitachi, Ltd. Thick film resistor material and thermal head obtained therefrom
CN110322984A (zh) * 2018-03-29 2019-10-11 住友金属矿山株式会社 厚膜电阻用组成物、厚膜电阻用膏体及厚膜电阻

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4322477A (en) * 1975-09-15 1982-03-30 Trw, Inc. Electrical resistor material, resistor made therefrom and method of making the same
JPS58223301A (ja) * 1982-06-21 1983-12-24 住友金属鉱山株式会社 抵抗体用ペースト及びその製造方法
NL8500905A (nl) * 1985-03-28 1986-10-16 Philips Nv Werkwijze voor het vervaardigen van een inrichting met een elektrische weerstandslaag en toepassing van de werkwijze.

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3899449A (en) * 1973-05-11 1975-08-12 Globe Union Inc Low temperature coefficient of resistivity cermet resistors
US4006278A (en) * 1973-05-11 1977-02-01 Globe-Union Inc. Low temperature coefficient of resistivity cermet resistors
US3914514A (en) * 1973-08-16 1975-10-21 Trw Inc Termination for resistor and method of making the same
US4101708A (en) * 1977-03-25 1978-07-18 E. I. Du Pont De Nemours And Company Resistor compositions
DE2846577A1 (de) * 1977-10-31 1979-05-10 Philips Nv Verfahren zur herstellung von widerstandsmaterial und durch dieses verfahren hergestellte widerstandskoerper
US4397774A (en) * 1977-10-31 1983-08-09 U.S. Philips Corporation Method of preparing resistance material and resistor bodies produced therewith
US5021194A (en) * 1986-11-14 1991-06-04 Hitachi, Ltd. Thick film resistor material and thermal head obtained therefrom
US5109238A (en) * 1986-11-14 1992-04-28 Hitachi, Ltd. Thick film resistor material and thermal head obtained therefrom
CN110322984A (zh) * 2018-03-29 2019-10-11 住友金属矿山株式会社 厚膜电阻用组成物、厚膜电阻用膏体及厚膜电阻
CN110322984B (zh) * 2018-03-29 2022-09-16 住友金属矿山株式会社 厚膜电阻用组成物、厚膜电阻用膏体及厚膜电阻

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Publication number Publication date
DE1640563A1 (de) 1970-08-27
BE705550A (es) 1968-04-24
GB1148926A (en) 1969-04-16
NL6714387A (es) 1968-04-25
NL137152C (es)

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