CA1048303A - Precision resistors using amorphous alloys - Google Patents

Precision resistors using amorphous alloys

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Publication number
CA1048303A
CA1048303A CA75240247A CA240247A CA1048303A CA 1048303 A CA1048303 A CA 1048303A CA 75240247 A CA75240247 A CA 75240247A CA 240247 A CA240247 A CA 240247A CA 1048303 A CA1048303 A CA 1048303A
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CA
Canada
Prior art keywords
resistance
metal alloys
amorphous
amorphous metal
precision resistors
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
Application number
CA75240247A
Other languages
French (fr)
Inventor
Gerald R. Bretts
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.)
Allied Corp
Original Assignee
Allied Chemical Corp
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 Allied Chemical Corp filed Critical Allied Chemical Corp
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Publication of CA1048303A publication Critical patent/CA1048303A/en
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/02Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C45/00Amorphous alloys
    • C22C45/008Amorphous alloys with Fe, Co or Ni as the major constituent
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01CRESISTORS
    • H01C3/00Non-adjustable metal resistors made of wire or ribbon, e.g. coiled, woven or formed as grids
    • H01C3/005Metallic glasses therefor

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Non-Adjustable Resistors (AREA)
  • Apparatuses And Processes For Manufacturing Resistors (AREA)
  • Soft Magnetic Materials (AREA)
  • Conductive Materials (AREA)

Abstract

INVENTION: PRECISION RESISTORS USING AMORPHOUS ALLOYS
INVENTOR: GERALD R. BRETTS
ABSTRACT OF THE DISCLOSURE
Precision resistors are disclosed which utilize as re-sistant elements amorphous metal alloys having the composition MaXb, where M is at least one of the elements selected from the group consisting of iron, nickel, cobalt, chromium and vanadium, X is at least one of the elements selected from the group consisting of phosphorus and boron, "a" ranges from about 75 to 85 atom percent and "b" ranges from about 15 to 25 atom percent. Compared with polycrystalline metal alloys, amorphous metal alloys evidence a superior resistivity, are mechanically stronger and show a higher thermal stability of resistance.

Description

~114~33~3 :: ~ ~
PRECISION RESISTORS USING AMORPHOUS ALLOYS
Background of the Invention 1. Field of the Invention The invention is concerned with precision resistors and, more particularly, with precision resistors utilizing amorphous metal alloys as resistance elements.
2. Description of the Prior Art .~
Resistors for electrical instruments can be divided `
into two arbitrary classifications based on permissible error~
those employed in precision instrumentation in which the overall error is considerably less than 1% and those employed where less . . : -precision is needed. This application is devoted to resistors falliny in the former classification. ~ -..~ .
Precision resistors include resistance elements, which in turn are composed of materials having many requirements that must be satisfied for optimum performance. Advantageously, the ;~
resistivity should be high in ordex to minimize the size of the ~ -resistor. Typical resistance material for use in precision re-sistors requires a resistivity between 50 and ~30 michrohm-cm.
Resistance material must have a small or negligible thermoelectric potential against copper because copper is usually the connecting material. Preferred thermal emf values are about 1 microvolt/ C.
Assuming a wire-wound resistor configuration, coefficients of expansion of both the resistance element and the insulator on which it is wound must be considered, because stresses can be established that will cause changes in both the resistance and ~ ;
the temperature coefficient of resistance. Preferred values of thermal expansion of the resistance element are approximately 13 microinches/C~ The stability or the maintenance of nominal resistance within narrow limits over a long period of time is ..

~4~3t~3 perhaps the most important requirement for ultraprecision resistors.
Finally, the temperature coefficient for precision resistors should be low in order to avoid temperature effects on resistance. The ideal material for precision resistors should have a zero or near zero temperature coefficient for the specific working range.
.. ~, Investigations have revealed a number of polycrystalline metal alloys suitable for use as resistance material. NevertheleSs, new compositions are con-tinually sought in which the foregoing properties are improved.
The physical properties of amorphous metal alloys have also been the subject of investigation. Studies have recently ~ ~ ;
disclosed compositions such as IFe,Ni)75P15 C10 and Ni41Pd41B18 having high resistivities; see, e.g., Vol. 42A, PhysLcs Letters, pp. 407-409 (1973) and Vol. 7, Physical Review B, pp. 3215-3225 (1973). However, these compositions evidence an unacceptably ;
high temperature coefficient of resistivity for useful precision resistor applications.
Summary of the Invention In accordance with the invention, precision resistors utilize certain amorphous metal alloys as resistance elements.
The metal alloys are at least 50~ amorphous, as determined by X-ray diffraction, and preferably at least 80~ amorphous, and more preferably, at least 95% amorphous. The amorphous metal alloys typically consist essentially of about 70 to 87 atom percent of at least one transition metal element and about 13 to 30 atom percent of at least one of the metalloid elements of aluminum, antimony, beryllium, boron, germanium, carbon, indium, phosphorus, silicon and tin. Preferably, the composi- ;
tion can be represenced as MaXb, where M is at least one of the elements of iron, nickel, cobalt, chromium and vanadium, X is ~ ;

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3~3 is at least one of the elements of phosphorus and boron, "a" ranges ~i from about 75 to 85 atom percent and "b" ranges from about 15 to 25 .
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percent. Used as precision resistance elements, these amorphous ~--metal alloys evidence generally superior properties, as compared ~ ~
with well-known polycrystalline metal alloys utilized in the prior ;-art.
Detailed Description of the Invention A theory has not yet been developed to correlate many macroscopic physical properties of polycrystalline metal alloys ;~
and of amorphous metal alloys having substantially the same composition. Many of the physical properties of previously dis-closed amorphous metal alloys tend to change at elevated tempera-tures. In contrast to this, however, a class of amorphous metal ~
alloys, whose compositions are given below, exhibit the high resis- ~ -tivity and, unexpectedly, the low temperature coefficient of resis-tivity, high stability of resistance and other desirable properties required for use in precision resistors.
Amorphous metal alloys utilized in the invention consist essentially of about 70 to 87 atom percent of at least one transi-tion metal element and about 13 to 30 atom percent of at least one of the metalloid elements of aluminum, antimony, beryllium, ;
boron, germanium, carbon, indium, phosphorus, silicon and tin.
Transition metal elements are those listed in Groups IB to VIIB
and VIII of the Periodic Table. More specifically, the composi tion may be represented by the formula MaXb, where M is at least ~`
one of the elements of iron, nickel, cobalt, chromium and vanadium, ;~;
X is at lea~t one of the elements of phosphorus and boron, "a" ~-ranges from about 75 to 85 atom percent, and "b" ranges from ~;
about 15 to 25 atom percent. Typical compositions include Fe40-40 14B6~ Fe32Ni36crl4pl2B6, Fe25Ni2sC20CrlOB20~ Fe40Nil5C5M ~
Crl7B18l and FessNigCo5Cr1sB17. The purity of all elements described is that found in normal commercial practice.

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. . . -~¢3483~

The amorphous metal alloys are formed by cooling a melt ~
at a rate of about 105 to 106C/ sec~ These amorphous ~lloys axe ~ ~;
usually at least 50% amorphous, as measured by X-ray di~fraction, ~- -when processed in this manner and may be utilized in some applica-tions. It is preferred, however, that the amorphous alloy be at least 80% amorphous, and more preferably, at least 95% amorphous to realize maximal performance as resistance elements in precision resistors. ~;
A variety of well-known techniques are available for 10 fabricating splat-quenched foils and rapid-quenched continuous -ribbon, wire, sheet, etc. of amorphous metal alloys. Typically, when used in precision resistance applications, these alloys conveniently take the form of wire or ribbon. The wire and ribbon are conveniently prepared by casting molten material ; directly onto a chill surface or into a quenching medium of some sort. Such processing techniquesconsiderably reduce the cost of ~ ;
fabrication, since no intermediate wire-drawing procedures are ~.
required. The alloys may also take the form of vapor deposited films, such as by electron beam evaporation or vacuum sputtering and of films formed by plasma spraying.
In the prior art, stress relief processing is required in order to fabricate resistance elements. In constrast, further processing steps for stress relief are not required to fabricate precision resistors utilizing amorphous metal alloy materials.
These amorphous metal alloys also evidence high mechani~
cal strength. The tensile strength typically is about 30n,000 to 600,000 psi, as compared with polycrystalline alloys, which usually range from about 30,000 to 200,000 psi. For example, the poly-crystalline composition Ni76Crl7Si4Mn3 has a tensile strength 30 ranging from 175,000 to 200,000 psi.

.... . . . .

~ 3~33~33 The resistivity of -the amorphous metal alloys is on ~he order of about 170 microhm-cm, as compared with the best available material having a resistivity of 136 microhm-cm (Fe72cr23Alscoo.s)~ This means that smaller dimensions can be utilized to achieve the same resistance value where amorphous metal alloy composltions are involved.
A typical temperature coefficient of resistance for precision resistors is about ~10 ppm/C over the range of 20 to ;
45C (Cu85Mnl0Ni4). Over the temperature range of 20 to 100C, the temperature coefficient of a good precision resistor is +150 ppm/C. In contrast, the same value for some amorphous metal alloy compositions is about 2 ppm/C over the range of 25 to 200C.
Perhaps the greatest advantage that the amorphous metal alloys offers is the temperature range over which the change in the temperature coefficient of resistance is small.
The thermal emf against copper is measured to be about +3.0 microvolts/C over the range of 25C to 200C. This compares favorably with prior art materials such as Ni60Crl6Fe24 (~0.8 micro-volts/C over the range of 0 to 75C) and Ni35Cr20Fe45 (-3 micro-volts/C over the range of 0 to 100C). Likewise, the thermal expansion of amorphous metal alloy compositions is about 13 micro- ~;~
inches/C, again comparable to the best prior art alloys.
Precision resistors employing amorphous metal alloys may advantageously take the form of either fixed or variable resistors.
Examples `
1. Resistance measurements were made on several amorphous specimens, as indicated below, employing the four-point ;~
probe method as described by G. T. Meaden, in Electrical Resistance 30 of Metals, Plenum Press (N.Y.), 1965, pp. 147 et seq. In each measurement, the two ends of a ribbon of material about 1 meter ; , ' , ' " ' ~''.

83~
in length were clamped with copper leads and connected in series to an ammeter, a current source, and a variable resistor of about 2 x 103 ohms. A few inches in from each end, brass springs were clamped and a connection was made to a potentiometer. The resis-tance of the ribbons was about 50 ohms. By using this technique, contact and lead resistances have no effect on the measurement.
Resistivity (p) was calculated from the relationship p = AR/Q
where R is the measured resistance, A is the cross-sectional area 1~ of the ribbon and "Q" is its length.
Measurements of temperature coefficient of resistance ~, (TC) were made between 25C and 200C, employing the relationship ~ ;
TC = (R-Ro)/~O(t-to)~
where R is the resistance at tC and Ro is the resistance at the reference temperature llto~ (here, 25C). A four-point probe employing a digital ammeter was used.
A determination of isothermal aging effects on electri- ;
cal resistance was made at 150C, using a two-point probe and a digital ohmeter. This measurement indicates thermal stability.
The results for three examples of amorphous metal alloys are tabulated in the Table below. Sample 1 had a composition of Fe40Mi40P14B6 (the subscripts are in atom percent). Measurements were made on ribbon of Sample 1 having dimensions 0.0015 inch thick by 0.061 inch~wide. Sample 2 had a composition Fe32Ni36Cr P12B6. Measurements were made on ribbon of Sample 2 having dimensions 0.0016 inch thick by 0.0675 inch wide. Sample 3 had p on Fe25Ni25C20CrlOB20- MeaSurements were made on ribbon of Sample 3 having dimensions 0.0018 inch thick by 0.039 inch wide.
`' 30 3~3 TABLE
Physical Properties Measured for Amorphous Metal Alloys in Precision Resistor Applicat~ons Temperature Resistivity Temperature Coefficient Stability at _mple p, microhm-cm of Resistance, ppm/C 150C,%/1000 hr. ;
1 183 -32 0,3 2 176 +145 (25-125C) 0.3 3 170 ~2.0 0.4 The thermal emf of Sample 3 was measured against copper and was found to be 3.0 microvolts/C over the range of 25 to 200C and 2.7 microvolts/C over the range of 25 to 100C. The thermal expansion of this material was found to be 12.6 micro-inch/C.
2. A variable resistor was constructed, using D-wire of compositlon Fe40Ni40P14B6 as the resistance element and a conventional graphite slider contact. The D-wire, which in . .
cross-section is half an ellipse, had dimensions as follows: the 20- major axis was 0.033 inch and one-half the minor axis was 0.010 lnch. The D-wire was wound on a polymethyl methacrylate core having dimensions of 2.5 inch diameter and 10.0 inch length.
Copper leads were clamped to both ends of the D-wire. The active length of the resistance element was 301.6 inch. The measured resistance was 400.42 ohms. This value remained constant over 100 operations of the slider contact. The value remained stable after nearly 4000 hours. There was no visible sign of wear of the resistance element.

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Claims (3)

What is claimed is:
1. A precision resistor including a resistance element, characterized in that the resistance element is composed of at least 50% amorphous metal alloy having the composition MaXb, where M
is at least one of the elements selected from the group consisting of iron, nickel, cobalt, chromium and vanadium, X is at least one of the elements selected from the group consisting of phosphorus and boron, "a" ranges from about 75 to 85 atom percent and "b" ranges from about 15 to 25 atom percent.
2. The precision resistor of claim 1 in which the resistance element is composed of at least 80% amorphous metal alloy.
3. The precision resistor of claim 2 in which the resistance element is of at least 95% amorphous metal alloy.
CA75240247A 1974-11-29 1975-11-24 Precision resistors using amorphous alloys Expired CA1048303A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US52817974A 1974-11-29 1974-11-29

Publications (1)

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CA1048303A true CA1048303A (en) 1979-02-13

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Country Link
JP (1) JPS5177856A (en)
CA (1) CA1048303A (en)
DE (1) DE2552806A1 (en)
FR (1) FR2293042A1 (en)
GB (1) GB1530910A (en)
NL (1) NL7513557A (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58153752A (en) * 1982-03-08 1983-09-12 Takeshi Masumoto Ni-cr alloy material
JPS6134901A (en) * 1984-07-26 1986-02-19 スタツクス工業株式会社 Resistor for audio device
EP0192703B1 (en) * 1984-08-31 1989-11-02 AT&T Corp. Nickel-based electrical contact

Also Published As

Publication number Publication date
JPS5177856A (en) 1976-07-06
GB1530910A (en) 1978-11-01
NL7513557A (en) 1976-06-01
DE2552806A1 (en) 1976-08-12
FR2293042A1 (en) 1976-06-25

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