EP3011069B1 - Resistor alloy, component produced therefrom and production method therefor - Google Patents

Resistor alloy, component produced therefrom and production method therefor Download PDF

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EP3011069B1
EP3011069B1 EP14734392.5A EP14734392A EP3011069B1 EP 3011069 B1 EP3011069 B1 EP 3011069B1 EP 14734392 A EP14734392 A EP 14734392A EP 3011069 B1 EP3011069 B1 EP 3011069B1
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resistance
component
temperature
resistance alloy
copper
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EP3011069A1 (en
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Daniel ZUCKERMANN
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IsabellenHuette Heusler GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/05—Alloys based on copper with manganese as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon

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  • the invention relates to a resistance alloy for an electrical resistance, in particular for a low-impedance current measuring resistor. Furthermore, the invention comprises a component manufactured therefrom and a corresponding production method.
  • Copper-manganese-nickel alloys have long been used as materials for precision resistors, in particular for low-resistance current measuring resistors ("shunts").
  • An example of such a copper-manganese-nickel alloy is the resistance alloy marketed by the applicant under the trade name Manganin® (eg Cu 84 Ni 4 Mn 12 ) with a copper content of 82-84%, a nickel content of 2% by mass. 4% and a mass fraction of manganese of 12-15%.
  • the known copper-manganese-nickel alloys meet all the requirements that are placed on resistance alloys for precision resistors, such as a low temperature coefficient of electrical resistivity, a low thermal power to copper and a high temporal constancy of electrical resistance.
  • the known copper-manganese-nickel alloys have good technological properties, in particular a good processing capability, which makes it possible to process these copper-manganese-nickel alloys into wires, tapes, films and resistance components.
  • a disadvantage of the known copper-manganese-nickel alloys is the limitation to relatively low electrical resistivities of at most 0.5 ( ⁇ ⁇ mm 2 ) / m.
  • nickel-chromium alloys For larger specific electrical resistances, for example, nickel-chromium alloys are known, which however also have various disadvantages. For one thing, nickel-chromium alloys are usually much more expensive than copper-manganese-nickel alloys. On the other hand, nickel-chromium alloys are difficult to handle in many respects in terms of production technology. For example, the hot workability of nickel-chromium alloys is relatively poor, and elaborate heat treatment processes are necessary for setting certain electrical-physical material properties. In addition, the working temperatures in the smelting process in the nickel-chromium alloys are 500K higher than in the copper-manganese-nickel alloys, which leads to higher energy costs and material wear of the work equipment. In addition, the otherwise desirable good acid resistance of nickel-chromium alloys poses major problems in the etch-making of resistor structures and makes the removal of heat-related oxides by pickling a costly and non-hazardous manufacturing step.
  • the copper-manganese-nickel-aluminum-magnesium alloy 29-5-1 which has a resistivity of 1 ( ⁇ ⁇ mm 2 ) / m and thereby meets the demand for a low temperature coefficient of resistivity .
  • this resistance alloy has a high thermo-power against copper at 20 ° C of +3 ⁇ V / K, resulting in high fault currents, which make this alloy unsuitable for precise metrological applications.
  • the prior art also includes Pashkov KE ET AL: "Special features of brazing often copper-manganese-nickel system with a powder brazing alloy", WELDING INTERNATIONAL, TAYLOR & FRANCIS, ABINGDON, GB, Vol. 24, No. 5, May 1, 2010 (2010 -05-01), pages 385-389, XP001554242, ISSN: 0950-7116, DOI: 10.1080 / 09507110903399273 Table 1, US 3 451 808 A . JP 2006-270078 A . JP 2009-242895 A , "Research on Precision Resistance Materials” Author: Hiroyuki HIRAYAMA, JP H04-48041 . JP S62-202038 . KR 1999-0048844 and U.S. 3,712,837 ,
  • a current measuring resistor having a resistive element made of a resistance alloy is known.
  • the resistance alloy here consists of a copper-manganese-nickel alloy, in particular with a copper content of 50-85 wt .-%, a manganese content of 12-30 wt .-% and a nickel content of 2-16% by weight.
  • a low temperature dependence of the resistance value of the resistance alloy should be achieved.
  • the invention is therefore based on the object, a correspondingly improved resistance alloy based on copper-manganese-nickel to provide, which has the highest possible specific electrical resistance, a low thermal power to copper, a low temperature coefficient of electrical resistance and a high temporal constancy of electrical resistivity and these properties with the initially described good technological properties (eg processability) of the known copper Manganese nickel alloys combined.
  • the mass fractions of the various alloying constituents are matched to one another in such a way that the resistance alloy according to the invention has a low thermopower with respect to copper, which is less than ⁇ 1 ⁇ V / K, ⁇ 0.5 ⁇ V / K or even ⁇ 0 at 20 ° C. 3 ⁇ V / K.
  • a preferred embodiment of a resistance alloy according to the invention is Cu 65 Ni 10 Mn 25 with a mass fraction of copper of 65%, a mass fraction of nickel of 10% and a mass fraction of manganese of 25%.
  • Another embodiment of a resistance alloy according to the invention is Cu 64 Ni 10 Mn 25 Sn 1 with a mass fraction of copper of 64%, a mass fraction of nickel of 10%, a mass fraction of manganese of 25% and a mass fraction of tin of 1%.
  • Another embodiment of a resistance alloy according to the invention is Cu 62 Ni 11 Mn 27 with a mass fraction of copper of 62%, a mass fraction of nickel of 11% and a mass fraction of manganese of 27%.
  • Another embodiment of a resistance alloy according to the invention is Cu 61 Ni 11 Mn 27 Sn 1 with a mass fraction of copper of 61%, a mass fraction of manganese of 27%, a mass fraction of nickel of 11% and a mass fraction of tin of 1%.
  • the specific electrical resistance is preferably in the range of 0.5 ( ⁇ ⁇ mm 2 ) / m to 2 ( ⁇ ⁇ mm 2 ) / m.
  • the specific electrical resistance of the resistance alloy according to the invention preferably has a high temporal constancy with a relative change of less than ⁇ 0.5% or ⁇ 0.25%, in particular within a period of 3000 hours and a temperature of at least + 140 ° C. , where the higher temperature of at least + 140 ° C accelerates the aging process.
  • the resistance alloy according to the invention preferably has a low thermal power to copper, which at 20 ° C is preferably less than ⁇ 0.5 ⁇ V / K or even none as ⁇ 0.3 ⁇ V / K.
  • the resistivity is relatively constant in temperature with a low temperature coefficient of preferably less than ⁇ 50 ⁇ 10 -6 K -1 , ⁇ 35 ⁇ 10 -6 K -1 , ⁇ 30 ⁇ 10 -6 K -1 or ⁇ 20 ⁇ 10 -6 K -1 , especially in a temperature range from + 20 ° C to + 60 ° C.
  • the resistance alloy has a resistance-temperature curve representing the relative resistance change as a function of the temperature, wherein the resistance-temperature curve has a second zero crossing, preferably at a temperature of more than + 20 ° C, + 30 ° C or + 40 ° C and / or at a temperature of less than + 110 ° C, + 100 ° C or + 90 ° C.
  • the mechanical properties of the resistance alloy according to the invention include a mechanical tensile strength of at least 500 MPa, 550 MPa or 580 MPa. Moreover, the resistance alloy according to the invention preferably has a yield strength of at least 150 MPa, 200 MPa or 260 MPa, while the elongation at break is preferably greater than 30%, 35%, 40% or even 45%.
  • the resistance alloy is preferably soft solderable and / or brazeable.
  • the resistance alloy according to the invention can be produced in various forms of delivery, for example as a wire (for example round wire, flat wire), as a band, as a sheet, as a rod, as a tube or as a foil.
  • the invention is not limited in terms of forms of delivery to the above-mentioned forms of delivery.
  • the invention also includes an electrical or electronic component with a resistance element of the resistance alloy according to the invention.
  • a resistance element of the resistance alloy according to the invention may be a resistor, in particular a low-impedance current measuring resistor, as it itself, for example EP 0 605 800 A1 is known.
  • the invention also includes a corresponding manufacturing method according to the independent claim 7 as it is already known from the above Description of the resistance alloy according to the invention results.
  • the resistance alloy can be subjected to an artificial thermal aging process, wherein the resistance alloy is heated from an initial temperature to an aging temperature. This process can be repeated several times as part of the aging process, wherein the resistance alloy is repeatedly heated periodically to the aging temperature and cooled back to the starting temperature.
  • the aging temperature may be, for example, in the range of + 80 ° C to + 300 ° C, while the starting temperature is preferably less than + 30 ° C or + 20 ° C.
  • FIG. 1 shows a phase diagram of a copper-manganese-nickel alloy, wherein the mass fraction of copper is indicated on the axis top left, while the mass fraction of nickel is reproduced on the axis top right. The mass fraction of manganese, however, is found on the lower axis.
  • phase diagram shows in hatched form a region 1 in which the resistance alloy tends to harden.
  • the resistance alloy has a specific electrical resistance in this line, which is independent of the temperature.
  • phase diagram also shows a region 3, which characterizes the resistance alloy according to the invention, wherein the mass fraction of manganese in the region 3 is between 23% and 28%, while the mass fraction of nickel in the region 3 is between 9% and 13%.
  • FIG. 2 shows a simplified perspective view of a current sense resistor 4 according to the invention, as it itself already out EP 0 605 800 A1 is known, so that reference is made to avoid repetition of this patent application, the content of which is attributable to the present description in its entirety.
  • the current measuring resistor 4 essentially consists of two plate-shaped connection parts 5, 6 made of copper and a resistance element 7 arranged therebetween of the resistance alloy according to the invention, which may be, for example, Cu 65 Ni 10 Mn 25 .
  • FIG. 3 shows the temperature-dependent course of the relative resistance change DR / R20 as a function of the temperature.
  • FIG. 4 shows the long-term stability of the resistance alloy according to the invention. It can be seen that the relative change in resistance dR over a period of 3000 hours is substantially less than 0.25%.

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Description

Die Erfindung betrifft eine Widerstandslegierung für einen elektrischen Widerstand, insbesondere für einen niederohmigen Strommesswiderstand. Weiterhin umfasst die Erfindung ein daraus hergestelltes Bauelement und ein entsprechendes Herstellungsverfahren.The invention relates to a resistance alloy for an electrical resistance, in particular for a low-impedance current measuring resistor. Furthermore, the invention comprises a component manufactured therefrom and a corresponding production method.

Kupfer-Mangan-Nickel-Legierungen finden schon seit langem Anwendung als Materialien für Präzisionswiderstände, insbesondere für niederohmige Strommesswiderstände ("shunts"). Ein Beispiel einer solchen Kupfer-Mangan-Nickel-Legierung ist die von der Anmelderin unter dem Markennamen Manganin® vertriebene Widerstandslegierung (z.B. Cu84Ni4Mn12) mit einem Massenanteil von Kupfer von 82-84%, einem Massenanteil von Nickel von 2-4% und einem Massenanteil von Mangan von 12-15%. Die bekannten Kupfer-Mangan-Nickel-Legierungen erfüllen alle Anforderungen, die an Widerstandslegierungen für Präzisionswiderstände gestellt werden, wie beispielsweise ein niedriger Temperaturkoeffizient des spezifischen elektrischen Widerstands, eine geringe Thermokraft gegen Kupfer und eine hohe zeitliche Konstanz des elektrischen Widerstands. Darüber hinaus besitzen die bekannten Kupfer-Mangan-Nickel-Legierungen gute technologische Eigenschaften, insbesondere eine gute Verarbeitungsfähigkeit, die es ermöglicht, diese Kupfer-Mangan-Nickel-Legierungen zu Drähten, Bändern, Folien und Widerstandsbauteilen zu verarbeiten. Ein Nachteil der bekannten Kupfer-Mangan-Nickel-Legierungen ist jedoch die Begrenzung auf relativ geringe spezifische elektrische Widerstände von höchstens 0,5 (Ω·mm2)/m.Copper-manganese-nickel alloys have long been used as materials for precision resistors, in particular for low-resistance current measuring resistors ("shunts"). An example of such a copper-manganese-nickel alloy is the resistance alloy marketed by the applicant under the trade name Manganin® (eg Cu 84 Ni 4 Mn 12 ) with a copper content of 82-84%, a nickel content of 2% by mass. 4% and a mass fraction of manganese of 12-15%. The known copper-manganese-nickel alloys meet all the requirements that are placed on resistance alloys for precision resistors, such as a low temperature coefficient of electrical resistivity, a low thermal power to copper and a high temporal constancy of electrical resistance. In addition, the known copper-manganese-nickel alloys have good technological properties, in particular a good processing capability, which makes it possible to process these copper-manganese-nickel alloys into wires, tapes, films and resistance components. However, a disadvantage of the known copper-manganese-nickel alloys is the limitation to relatively low electrical resistivities of at most 0.5 (Ω · mm 2 ) / m.

Für größere spezifische elektrische Widerstände sind beispielsweise Nickel-Chrom-Legierungen bekannt, die jedoch ebenfalls verschiedene Nachteile aufweisen. Zum einen sind Nickel-Chrom-Legierungen meist wesentlich teurer als Kupfer-Mangan-Nickel-Legierungen. Zum anderen sind Nickel-Chrom-Legierungen fertigungstechnisch in vielerlei Hinsicht schwerer zu handhaben. Beispielsweise ist die Warmumformbarkeit von Nickel-Chrom-Legierungen relativ schlecht und zum Einstellen bestimmter elektrisch-physikalischer Werkstoffeigenschaften sind aufwändige Wärmebehandlungsprozesse notwendig. Außerdem sind die Arbeitstemperaturen im Schmelzprozess bei den Nickel-Chrom-Legierungen um 500K höher als bei den Kupfer-Mangan-Nickel-Legierungen, was zu höheren Energiekosten und Materialverschleiß der Arbeitsmittel führt. Darüber hinaus bereitet die ansonsten wünschenswerte gute Säurebeständigkeit von Nickel-Chrom-Legierungen große Probleme bei der ätztechnischen Herstellung von Widerstandsstrukturen und macht das Entfernen von wärmebehandlungsbedingten Oxiden durch Beizen zu einem aufwändigen und nicht gefährlichen Fertigungsschritt.For larger specific electrical resistances, for example, nickel-chromium alloys are known, which however also have various disadvantages. For one thing, nickel-chromium alloys are usually much more expensive than copper-manganese-nickel alloys. On the other hand, nickel-chromium alloys are difficult to handle in many respects in terms of production technology. For example, the hot workability of nickel-chromium alloys is relatively poor, and elaborate heat treatment processes are necessary for setting certain electrical-physical material properties. In addition, the working temperatures in the smelting process in the nickel-chromium alloys are 500K higher than in the copper-manganese-nickel alloys, which leads to higher energy costs and material wear of the work equipment. In addition, the otherwise desirable good acid resistance of nickel-chromium alloys poses major problems in the etch-making of resistor structures and makes the removal of heat-related oxides by pickling a costly and non-hazardous manufacturing step.

Ferner ist die Kupfer-Mangan-Nickel-Aluminium-Magnesium-Legierung 29-5-1 bekannt, die einen spezifischen elektrischen Widerstand von 1 (Ω·mm2)/m aufweist und dabei die Forderung nach einem niedrigen Temperaturkoeffizienten des spezifischen elektrischen Widerstandes erfüllt. Allerdings weist diese Widerstandslegierung eine hohe Thermokraft gegen Kupfer bei 20°C von +3 µV/K auf, woraus hohe Fehlerströme resultieren, welche diese Legierung für präzise messtechnische Anwendungen ungeeignet machen.Further, the copper-manganese-nickel-aluminum-magnesium alloy 29-5-1 is known which has a resistivity of 1 (Ω · mm 2 ) / m and thereby meets the demand for a low temperature coefficient of resistivity , However, this resistance alloy has a high thermo-power against copper at 20 ° C of +3 μV / K, resulting in high fault currents, which make this alloy unsuitable for precise metrological applications.

Ferner ist zum Stand der Technik hinzuweisen auf DE 1 092 218 B , US 3 985 589 , JP 62202038 A und EP 1 264 906 A1 .Furthermore, it should be noted on the prior art DE 1 092 218 B . US 3,985,589 . JP 62202038 A and EP 1 264 906 A1 ,

Schließlich offenbart DE 1 033 423 B eine gattungsgemäße Widerstandslegierung. Nachteilig an dieser bekannten Widerstandslegierung ist jedoch die betragsmäßig relativ große Thermokraft gegen Kupfer von -2µV/K.Finally revealed DE 1 033 423 B a generic resistance alloy. A disadvantage of this known resistance alloy, however, is the amount of relatively large thermoelectric force against copper of -2μV / K.

Ferner umfasst der Stand der Technik auch Pashkov K E ET AL: "Special features of brazing oft he copper-manganese-nickel system with a powder brazing alloy", WELDING INTERNATIONAL, TAYLOR & FRANCIS, ABINGDON, GB, Bd. 24, Nr. 5, 1. Mai 2010 (2010-05-01), Seiten 385-389, XP001554242, ISSN: 0950-7116, DOI: 10.1080/09507110903399273 Tabelle 1, US 3 451 808 A , JP 2006-270078 A , JP 2009-242895 A , "Researches on Precision Resistance Materials" Author: Hiroyuki HIRAYAMA, JP H04-48041 , JP S62-202038 , KR 1999-0048844 und US 3 712 837 .Furthermore, the prior art also includes Pashkov KE ET AL: "Special features of brazing often copper-manganese-nickel system with a powder brazing alloy", WELDING INTERNATIONAL, TAYLOR & FRANCIS, ABINGDON, GB, Vol. 24, No. 5, May 1, 2010 (2010 -05-01), pages 385-389, XP001554242, ISSN: 0950-7116, DOI: 10.1080 / 09507110903399273 Table 1, US 3 451 808 A . JP 2006-270078 A . JP 2009-242895 A , "Research on Precision Resistance Materials" Author: Hiroyuki HIRAYAMA, JP H04-48041 . JP S62-202038 . KR 1999-0048844 and U.S. 3,712,837 ,

Aus JP 2011-249475 A ist ein Strommesswiderstand mit einem Widerstandselement aus einer Widerstandslegierung bekannt. In einem Ausführungsbeispiel besteht die Widerstandslegierung hierbei aus einer Kupfer-Mangan-Nickel-Legierung, insbesondere mit einem Kupfer-Anteil von 50-85 Gew.-%, einem Mangan-Anteil von 12-30 Gew.-% und einem Nickel-Anteil von 2-16 Gew.-%. Hierbei soll eine geringe Temperaturabhängigkeit des Widerstandswertes der Widerstandlegierung erreicht werden. Die vorstehend erwähnte Problematik der Thermokraft ist dagegen aus dieser Druckschrift nicht bekannt.Out JP 2011-249475 A For example, a current measuring resistor having a resistive element made of a resistance alloy is known. In one embodiment, the resistance alloy here consists of a copper-manganese-nickel alloy, in particular with a copper content of 50-85 wt .-%, a manganese content of 12-30 wt .-% and a nickel content of 2-16% by weight. In this case, a low temperature dependence of the resistance value of the resistance alloy should be achieved. The above-mentioned problem of thermoelectric power, however, is not known from this document.

Keine dieser Druckschriften offenbart jedoch eine gattungsgemäße Legierung mit einer niedrigen Thermokraft.However, none of these documents discloses a generic alloy with a low thermoelectric force.

Der Erfindung liegt deshalb die Aufgabe zugrunde, eine entsprechend verbesserte Widerstandslegierung auf Kupfer-Mangan-Nickel-Basis zu schaffen, die einen möglichst hohen spezifischen elektrischen Widerstand, eine niedrige Thermokraft gegen Kupfer, einen niedrigen Temperaturkoeffizienten des elektrischen Widerstands und eine hohe zeitliche Konstanz des spezifischen elektrischen Widerstands aufweist und diese Eigenschaften mit den eingangs beschriebenen guten technologischen Eigenschaften (z.B. Verarbeitbarkeit) der bekannten Kupfer-Mangan-Nickel-Legierungen kombiniert.The invention is therefore based on the object, a correspondingly improved resistance alloy based on copper-manganese-nickel to provide, which has the highest possible specific electrical resistance, a low thermal power to copper, a low temperature coefficient of electrical resistance and a high temporal constancy of electrical resistivity and these properties with the initially described good technological properties (eg processability) of the known copper Manganese nickel alloys combined.

Diese Aufgabe wird durch eine erfindungsgemäße Widerstandslegierung gemäß dem Unabhängigen Anspruch 1 gelöst.This object is achieved by a resistance alloy according to the invention according to the independent claim 1.

Die Massenanteile der verschiedenen Legierungsbestandteile sind hierbei so aufeinander abgestimmt, dass die erfindungsgemäße Widerstandslegierung eine niedrige Thermokraft gegenüber Kupfer aufweist, die bei 20°C kleiner ist als ±1 µV/K, ±0,5 µV/K oder sogar keiner als ±0,3 µV/K.The mass fractions of the various alloying constituents are matched to one another in such a way that the resistance alloy according to the invention has a low thermopower with respect to copper, which is less than ± 1 μV / K, ± 0.5 μV / K or even ± 0 at 20 ° C. 3 μV / K.

Ein bevorzugtes Ausführungsbeispiel einer erfindungsgemäßen Widerstandslegierung ist Cu65Ni10Mn25 mit einem Massenanteil von Kupfer von 65%, einem Massenanteil von Nickel von 10% und einem Massenanteil von Mangan von 25%.A preferred embodiment of a resistance alloy according to the invention is Cu 65 Ni 10 Mn 25 with a mass fraction of copper of 65%, a mass fraction of nickel of 10% and a mass fraction of manganese of 25%.

Ein anderes Ausführungsbeispiel einer erfindungsgemäßen Widerstandslegierung ist Cu64Ni10Mn25Sn1 mit einem Massenanteil von Kupfer von 64%, einem Massenanteil von Nickel von 10%, einem Massenanteil von Mangan von 25% und einem Massenanteil von Zinn von 1%.Another embodiment of a resistance alloy according to the invention is Cu 64 Ni 10 Mn 25 Sn 1 with a mass fraction of copper of 64%, a mass fraction of nickel of 10%, a mass fraction of manganese of 25% and a mass fraction of tin of 1%.

Ein weiteres Ausführungsbeispiel einer erfindungsgemäßen Widerstandslegierung ist Cu62Ni11Mn27 mit einem Massenanteil von Kupfer von 62%, einem Massenanteil von Nickel von 11% und einem Massenanteil von Mangan von 27%.Another embodiment of a resistance alloy according to the invention is Cu 62 Ni 11 Mn 27 with a mass fraction of copper of 62%, a mass fraction of nickel of 11% and a mass fraction of manganese of 27%.

Ein weiteres Ausführungsbeispiel einer erfindungsgemäßen Widerstandslegierung ist Cu61Ni11Mn27Sn1 mit einem Massenanteil von Kupfer von 61%, einem Massenanteil von Mangan von 27%, einem Massenanteil von Nickel von 11% und einem Massenanteil von Zinn von 1%.Another embodiment of a resistance alloy according to the invention is Cu 61 Ni 11 Mn 27 Sn 1 with a mass fraction of copper of 61%, a mass fraction of manganese of 27%, a mass fraction of nickel of 11% and a mass fraction of tin of 1%.

Bei der erfindungsgemäßen Widerstandslegierung liegt der spezifische elektrische Widerstand vorzugsweise im Bereich von 0,5 (Ω·mm2) /m bis 2 (Ω·mm2)/m.In the resistance alloy of the present invention, the specific electrical resistance is preferably in the range of 0.5 (Ω · mm 2 ) / m to 2 (Ω · mm 2 ) / m.

Weiterhin weist der spezifische elektrische Widerstand der erfindungsgemäßen Widerstandslegierung vorzugsweise eine hohe zeitliche Konstanz mit einer relativen Änderung von weniger als ±0,5% oder ±0,25% auf, insbesondere innerhalb eines Zeitraums von 3000 Stunden und einer Temperatur von mindestens +140°C, wobei die höhere Temperatur von mindestens +140°C den Alterungsprozess beschleunigt.Furthermore, the specific electrical resistance of the resistance alloy according to the invention preferably has a high temporal constancy with a relative change of less than ± 0.5% or ± 0.25%, in particular within a period of 3000 hours and a temperature of at least + 140 ° C. , where the higher temperature of at least + 140 ° C accelerates the aging process.

Darüber hinaus ist zu erwähnen, dass die erfindungsgemäße Widerstandslegierung vorzugsweise eine niedrige Thermokraft gegenüber Kupfer aufweist, die bei 20°C vorzugsweise kleiner ist als ±0,5 µV/K oder sogar keiner als ±0,3 µV/K. Weiterhin ist der spezifische elektrische Widerstand relativ temperaturkonstant mit einem niedrigen Temperaturkoeffizienten von vorzugsweise weniger als ±50·10-6 K-1, ±35·10-6 K-1, ±30·10-6 K-1 oder ±20·10-6 K-1, insbesondere in einem Temperaturbereich von +20°C bis +60°C.In addition, it should be mentioned that the resistance alloy according to the invention preferably has a low thermal power to copper, which at 20 ° C is preferably less than ± 0.5 μV / K or even none as ± 0.3 μV / K. Furthermore, the resistivity is relatively constant in temperature with a low temperature coefficient of preferably less than ± 50 · 10 -6 K -1 , ± 35 · 10 -6 K -1 , ± 30 · 10 -6 K -1 or ± 20 · 10 -6 K -1 , especially in a temperature range from + 20 ° C to + 60 ° C.

Zu den elektrischen Eigenschaften der erfindungsgemäßen Widerstandslegierung ist ferner zu erwähnen, dass die Widerstandslegierung eine Widerstands-Temperaturkurve aufweist, welche die relative Widerstandsänderung in Abhängigkeit von der Temperatur wiedergibt, wobei die Widerstands-Temperaturkurve einen zweiten Nulldurchgang aufweist, der vorzugsweise bei einer Temperatur von mehr als +20°C, +30°C oder +40°C und/oder bei einer Temperatur von weniger als +110°C, +100°C oder +90°C erfolgt.To the electrical properties of the resistance alloy according to the invention is also to be mentioned that the resistance alloy has a resistance-temperature curve representing the relative resistance change as a function of the temperature, wherein the resistance-temperature curve has a second zero crossing, preferably at a temperature of more than + 20 ° C, + 30 ° C or + 40 ° C and / or at a temperature of less than + 110 ° C, + 100 ° C or + 90 ° C.

Zu den mechanischen Eigenschaften der erfindungsgemäßen Widerstandslegierung ist eine mechanische Zugfestigkeit von mindestens 500 MPa, 550 MPa oder 580 MPa zu erwähnen. Darüber hinaus weist die erfindungsgemäße Widerstandslegierung vorzugsweise eine Streckgrenze von mindestens 150 MPa, 200 MPa oder 260 MPa auf, während die Bruchdehnung vorzugsweise größer ist als 30%, 35%, 40% oder sogar 45%.The mechanical properties of the resistance alloy according to the invention include a mechanical tensile strength of at least 500 MPa, 550 MPa or 580 MPa. Moreover, the resistance alloy according to the invention preferably has a yield strength of at least 150 MPa, 200 MPa or 260 MPa, while the elongation at break is preferably greater than 30%, 35%, 40% or even 45%.

Zu den technologischen Eigenschaften der erfindungsgemäßen Widerstandslegierung ist zu erwähnen, dass die Widerstandslegierung vorzugsweise weichlötfähig und/oder hartlötfähig ist. Darüber hinaus ist die erfindungsgemäße Widerstandslegierung vorzugsweise sehr gut umformbar, was sich beim Drahtziehen in einem logarithmischen Umformgrad von mindestens ϕ=-4,6 zeigt. Die erfindungsgemäße Widerstandslegierung kann in verschiedenen Lieferformen hergestellt werden, wie beispielsweise als Draht (z.B. Runddraht, Flachdraht), als Band, als Blech, als Stab, als Rohr oder als Folie. Die Erfindung ist jedoch hinsichtlich der Lieferformen nicht auf die vorstehend genannten Lieferformen beschränkt.It should be mentioned with regard to the technological properties of the resistance alloy according to the invention that the resistance alloy is preferably soft solderable and / or brazeable. In addition, the resistance alloy according to the invention is preferably very good formability, which shows in the wire drawing in a logarithmic degree of deformation of at least φ = -4.6. The resistance alloy according to the invention can be produced in various forms of delivery, for example as a wire (for example round wire, flat wire), as a band, as a sheet, as a rod, as a tube or as a foil. However, the invention is not limited in terms of forms of delivery to the above-mentioned forms of delivery.

Darüber hinaus umfasst die Erfindung auch ein elektrisches bzw. elektronisches Bauelement mit einem Widerstandselement aus der erfindungsgemäßen Widerstandslegierung. Beispielsweise kann es sich hierbei um einen Widerstand handeln, insbesondere um einen niederohmigen Strommesswiderstand, wie er an sich beispielsweise aus EP 0 605 800 A1 bekannt ist. Schließlich umfasst die Erfindung auch ein entsprechendes Herstellungsverfahren gemäss dem Unabhängigen Anspruch 7 wie es sich bereits aus der vorstehenden Beschreibung der erfindungsgemäßen Widerstandslegierung ergibt.In addition, the invention also includes an electrical or electronic component with a resistance element of the resistance alloy according to the invention. For example, this may be a resistor, in particular a low-impedance current measuring resistor, as it itself, for example EP 0 605 800 A1 is known. Finally, the invention also includes a corresponding manufacturing method according to the independent claim 7 as it is already known from the above Description of the resistance alloy according to the invention results.

Im Rahmen des erfindungsgemäßen Herstellungsverfahrens kann die Widerstandslegierung einem künstlichen thermischen Alterungsprozess unterworfen werden, wobei die Widerstandslegierung von einer Ausgangstemperatur auf eine Alterungstemperatur erwärmt wird. Dieser Prozess kann im Rahmen des Alterungsprozesses mehrfach wiederholt werden, wobei die Widerstandslegierung mehrfach periodisch auf die Alterungstemperatur erwärmt und wieder auf die Ausgangstemperatur abgekühlt wird. Die Alterungstemperatur kann beispielsweise im Bereich von +80°C bis +300°C liegen, während die Ausgangstemperatur vorzugsweise kleiner ist als +30°C oder +20°C.In the context of the manufacturing method according to the invention, the resistance alloy can be subjected to an artificial thermal aging process, wherein the resistance alloy is heated from an initial temperature to an aging temperature. This process can be repeated several times as part of the aging process, wherein the resistance alloy is repeatedly heated periodically to the aging temperature and cooled back to the starting temperature. The aging temperature may be, for example, in the range of + 80 ° C to + 300 ° C, while the starting temperature is preferably less than + 30 ° C or + 20 ° C.

Andere vorteilhafte Weiterbildungen der Erfindung sind in den Unteransprüchen gekennzeichnet oder werden nachstehend zusammen mit der Beschreibung der bevorzugten Ausführungsbeispiele der Erfindung anhand der Figuren näher erläutert. Es zeigen:

Figur 1:
ein Phasendiagramm für eine Kupfer-Mangan-Nickel-Legierung, wobei der erfindungsgemäße Bereich in dem Phasendiagramm eingetragen ist,
Figur 2:
eine exemplarische Bauform eines erfindungsgemäßen Strommesswiderstands mit einem Widerstandselement aus der erfindungsgemäßen Widerstandslegierung,
Figur 3:
ein Diagramm zur Verdeutlichung der Temperaturabhängigkeit des spezifischen elektrischen Widerstands bei verschiedenen Ausführungsbeispielen der erfindungsgemäßen Widerstandslegierung sowie
Figur 4:
ein Diagramm zur Verdeutlichung der Langzeitstabilität der erfindungsgemäßen Widerstandslegierung.
Other advantageous developments of the invention are characterized in the subclaims or are explained in more detail below together with the description of the preferred embodiments of the invention with reference to FIGS. Show it:
FIG. 1:
a phase diagram for a copper-manganese-nickel alloy, wherein the area according to the invention is registered in the phase diagram,
FIG. 2:
an exemplary design of a current measuring resistor according to the invention with a resistor element of the resistance alloy according to the invention,
FIG. 3:
a diagram illustrating the temperature dependence of the resistivity in various embodiments of the resistance alloy according to the invention and
FIG. 4:
a diagram illustrating the long-term stability of the resistance alloy according to the invention.

Figur 1 zeigt ein Phasendiagramm einer Kupfer-Mangan-Nickel-Legierung, wobei der Massenanteil von Kupfer auf der Achse links oben angegeben ist, während der Massenanteil von Nickel auf der Achse rechts oben wiedergegeben ist. Der Massenanteil von Mangan findet sich dagegen auf der unteren Achse. FIG. 1 shows a phase diagram of a copper-manganese-nickel alloy, wherein the mass fraction of copper is indicated on the axis top left, while the mass fraction of nickel is reproduced on the axis top right. The mass fraction of manganese, however, is found on the lower axis.

Zum einen zeigt das Phasendiagramm in schraffierter Form ein Gebiet 1, in dem die Widerstandslegierung zu Aushärtungen neigt.On the one hand the phase diagram shows in hatched form a region 1 in which the resistance alloy tends to harden.

Zum anderen zeigt das Phasendiagramm eine Linie 2, die mit α=0 bezeichnet ist, wobei der Temperaturkoeffizient der Widerstandslegierung auf dieser Linie gleich Null ist, d.h. die Widerstandslegierung weist auf dieser Linie einen spezifischen elektrischen Widerstand auf, der unabhängig von der Temperatur ist.On the other hand, the phase diagram shows a line 2 labeled α = 0, where the temperature coefficient of the resistance alloy on that line is zero, i. The resistance alloy has a specific electrical resistance in this line, which is independent of the temperature.

Schließlich zeigt das Phasendiagramm noch einen Bereich 3, der die erfindungsgemäße Widerstandslegierung kennzeichnet, wobei der Massenanteil von Mangan in dem Bereich 3 zwischen 23% und 28% liegt, während der Massenanteil von Nickel im Bereich 3 zwischen 9% und 13% liegt.Finally, the phase diagram also shows a region 3, which characterizes the resistance alloy according to the invention, wherein the mass fraction of manganese in the region 3 is between 23% and 28%, while the mass fraction of nickel in the region 3 is between 9% and 13%.

Figur 2 zeigt eine vereinfachte perspektivische Ansicht eines erfindungsgemäßen Strommesswiderstands 4, wie er an sich bereits aus EP 0 605 800 A1 bekannt ist, so dass zur Vermeidung von Wiederholungen auf diese Patentanmeldung verwiesen wird, deren Inhalt der vorliegenden Beschreibung in vollem Umfang zuzurechnen ist. FIG. 2 shows a simplified perspective view of a current sense resistor 4 according to the invention, as it itself already out EP 0 605 800 A1 is known, so that reference is made to avoid repetition of this patent application, the content of which is attributable to the present description in its entirety.

Der Strommesswiderstand 4 besteht im Wesentlichen aus zwei plattenförmigen Anschlussteilen 5, 6 aus Kupfer und einem dazwischen angeordneten Widerstandselement 7 aus der erfindungsgemäßen Widerstandslegierung, wobei es sich beispielsweise um Cu65Ni10Mn25 handeln kann.The current measuring resistor 4 essentially consists of two plate-shaped connection parts 5, 6 made of copper and a resistance element 7 arranged therebetween of the resistance alloy according to the invention, which may be, for example, Cu 65 Ni 10 Mn 25 .

Figur 3 zeigt den temperaturabhängigen Verlauf der relativen Widerstandsänderung DR/R20 in Abhängigkeit von der Temperatur. Daraus ist auch ersichtlich, dass die verschiedenen beispielhaften Widerstandslegierungen jeweils einen zweiten Nulldurchgang 8, 9 bzw. 10 aufweisen, wobei der Nulldurchgang 8 ungefähr bei einer Temperatur TNULL1=43°C erfolgt, während der Nulldurchgang 9 ungefähr bei einer Temperatur TNULL2=75°C erfolgt. Der Nulldurchgang 10 erfolgt dagegen ungefähr bei einer Temperatur von TNULL3=82°C. FIG. 3 shows the temperature-dependent course of the relative resistance change DR / R20 as a function of the temperature. It can also be seen that the various exemplary resistance alloys each have a second zero crossing 8, 9 and 10, respectively, where the zero crossing 8 occurs approximately at a temperature T NULL1 = 43 ° C, while the zero crossing 9 occurs approximately at a temperature T NULL2 = 75 ° C takes place. By contrast, the zero crossing 10 takes place approximately at a temperature of T NULL3 = 82 ° C.

Schließlich zeigt Figur 4 die Langzeitstabilität der erfindungsgemäßen Widerstandslegierung. Daraus ist ersichtlich, dass die relative Widerstandsänderung dR über einen Zeitraum von 3000 Stunden wesentlich kleiner ist als 0,25%.Finally shows FIG. 4 the long-term stability of the resistance alloy according to the invention. It can be seen that the relative change in resistance dR over a period of 3000 hours is substantially less than 0.25%.

Bezugszeichenliste:LIST OF REFERENCE NUMBERS

11
Gebiet der AushärtungArea of curing
22
Linie mit α=0 (Temperaturkonstanz)Line with α = 0 (temperature constancy)
33
Erfindungsgemäßer LegierungsbereichInventive alloy range
44
StrommesswiderstandCurrent sense resistor
55
Anschlussteilconnector
66
Anschlussteilconnector
77
Widerstandselementresistive element
88th
Zweiter NulldurchgangSecond zero crossing
99
Zweiter NulldurchgangSecond zero crossing
1010
Zweiter NulldurchgangSecond zero crossing

Claims (7)

  1. Resistance alloy (3) having a low thermo-electrive force with regard to copper at 20°C of less than ±1 µV/K, for a low-resistance current sense resistor (4), with the following mass proportions of the constituents:
    a) copper component: 65%, nickel component: 10% and manganese component: 25%; or
    b) nickel component: 10%, manganese component: 25%, tin component: 1%, copper component: remainder, or
    c) copper component: 62%, nickel component: 11%, manganese component: 27%, or
    d) nickel component: 11%, manganese component: 27%, tin component: up to 1%, copper component: remainder.
  2. Resistance alloy (3) according to claim 1,
    characterized by
    a) a resistivity greater than 0.5 (Ω·mm2) /m, 0.6 (Ω·mm2) /m, 0.7 (Ω·mm2) /m or 0.8 (Ω·mm2) /m and/or less than 2.0 (Ω·mm2) /m, 1.5 (Ω·mm2) /m, 1.2 (Ω·mm2) /m or 1 (Ω·mm2) /m; and/or
    b) a resistivity with a high temporal constancy with a relative change of less than ±0,5% or ±0,25%; and/or
    c) a low thermo-electric force at 20°C of less than ±0,5µV/K or ±0,3µV/K relative to copper; and/or
    d) a resistivity with a low temperature coefficient of less than ±50·10-6 K-1, ±35·10-6 K-1, ±30·10-6 K-1 or ±20·10-6 K-1; and/or
    e) a resistance-temperature curve representing the relative resistance change (DR/R20) as a function of temperature, said resistance-temperature curve having a second zero crossing (8, 9, 10) occurring at a temperature greater than +20°C, +30°C or +40°C and/or less than +110°C, +100°C or +90°C.
  3. Resistance alloy (3) according to one of the preceding claims, characterized by
    a) a mechanical tensile strength of at least 500 MPa, 550 MPa or 580 MPa; and/or
    b) a yield strength of at least 150 MPa, 200 MPa or 260 MPa; and/or
    c) an elongation at break of at least 30%, 35%, 40% or 45%.
  4. Resistance alloy (3) according to one of the preceding claims, characterized in that
    a) the resistance alloy (3) is solderable and/or brazeable, and/or
    b) in that the resistance alloy (3) can be deformed so well that it achieves a logarithmic degree of deformation of at least ϕ=-4.6 during wire drawing.
  5. Resistance alloy (3) according to one of the preceding claims, characterized by one of the following delivery forms:
    a) as wire,
    b) as a band,
    c) as sheet metal,
    d) as a bar,
    e) as a tube; or
    f) as film.
  6. Low-resistance current sense resistor (4) with a resistor element made of a resistance alloy (3) according to one of the preceding claims.
  7. Manufacturing method for manufacturing a resistor according to one of the preceding claims, wherein
    a) the resistance alloy (3) is subjected to an artificial thermal ageing process, the resistance alloy (3) being heated from an initial temperature to an ageing temperature, and/or
    b) the resistance alloy (3) is periodically heated to the ageing temperature several times during the ageing process and cooled down again to the initial temperature, and/or
    c) the ageing temperature is greater than +80°C, +100°C, +120°C, and/or less than +300°C, +200°C or +150°C; and/or
    d) the initial temperature is less than +30°C or +20°C.
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DE102013010301A1 (en) 2014-12-24
CN105308204A (en) 2016-02-03

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