CN117157418A - Copper alloy material, resistor material for resistor using same, and resistor - Google Patents
Copper alloy material, resistor material for resistor using same, and resistor Download PDFInfo
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- CN117157418A CN117157418A CN202280026857.3A CN202280026857A CN117157418A CN 117157418 A CN117157418 A CN 117157418A CN 202280026857 A CN202280026857 A CN 202280026857A CN 117157418 A CN117157418 A CN 117157418A
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- 229910000881 Cu alloy Inorganic materials 0.000 title claims abstract description 121
- 239000000463 material Substances 0.000 title claims abstract description 89
- 239000010949 copper Substances 0.000 claims abstract description 68
- 239000000203 mixture Substances 0.000 claims abstract description 33
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- 239000013078 crystal Substances 0.000 claims description 32
- 229910045601 alloy Inorganic materials 0.000 claims description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 66
- 229910052802 copper Inorganic materials 0.000 abstract description 62
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 43
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- 238000005266 casting Methods 0.000 description 7
- 238000000265 homogenisation Methods 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000011651 chromium Substances 0.000 description 4
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
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- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000010622 cold drawing Methods 0.000 description 1
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Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C13/00—Resistors not provided for elsewhere
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C3/00—Non-adjustable metal resistors made of wire or ribbon, e.g. coiled, woven or formed as grids
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
Provided are a copper alloy material which has a sufficiently high volume resistivity as a resistive material and a small absolute value of copper thermal electromotive force, and which has a negative temperature coefficient of resistance and a small absolute value in a wide temperature range from normal temperature (for example, 20 ℃) to high temperature (for example, 150 ℃), a resistive material for a resistor and a resistor using the same. The copper alloy material has a composition containing Mn:20.0 mass% or more and 35.0 mass% or less, ni:5.0 mass% or more and 15.0 mass% or less and Fe:0.01 to 0.50 mass% inclusive, and Co is in the range of 0 to 1.50 mass% inclusive (inclusive of the case where the Co content is 0 mass%, and the total amount of Fe and Co is in the range of 0.10 to 2.00 mass%, with the balance being Cu and unavoidable impurities.
Description
Technical Field
The present invention relates to a copper alloy material, and a resistor material and a resistor using the same.
Background
The metal material of the resistive material used in the resistor is required to have a small absolute value of a Temperature Coefficient of Resistance (TCR) as an index thereof in order to stabilize the resistance of the resistor even when the ambient temperature changes. The temperature coefficient of resistance is a coefficient indicating the magnitude of a change in resistance value due to temperature in parts per million (ppm) per 1℃and TCR (. Times.10) -6 /℃)＝{(R-R 0 )/R 0 }×{1/(T-T 0 )}×10 6 Such a formula represents. Here, T in the formula represents a test temperature (. Degree. C.), T 0 The reference temperature (. Degree. C.) is represented by R, the resistance value (. OMEGA.) at the test temperature T is represented by R 0 Indicating a reference temperature T 0 Resistance value (Ω) at that time. In particular, cu—mn—ni alloys and cu—mn—sn alloys have a very small TCR, and thus are widely used as alloy materials constituting resistance materials.
However, for example, in a resistor designed to have a predetermined resistance value by forming a circuit (pattern) using a resistive material, when these cu—mn—ni alloy or cu—mn—sn alloy is used as the resistive material, it is necessary to reduce the volume resistivity to less than 50×10 -8 (Ω·m) to decrease the sectional area of the resistive material and increase the resistance value of the resistor. In such a resistor, when a large current temporarily flows through the circuit and when a large current is constantly flowing to some extent, joule heat generated in the resistive material having a small cross-sectional area is increased to generate heat, and as a result, the resistive material is likely to break (fuse) due to heat.
Therefore, in order to suppress the sectional area of the resistive material from becoming smaller, a resistive material having a larger volume resistivity is required.
For example, in patent document 1, In a copper alloy containing Mn in a range of 23 mass% to 28 mass%, and Ni in a range of 9 mass% to 13 mass%, 50X 10 can be obtained by configuring the mass fraction of Mn and the mass fraction of Ni so that the thermal electromotive force to copper is less than + -1 [ mu ] V/. Degree.C at 20 DEG C -8 [Ω·m]The above-mentioned high resistance (volume resistivity ρ) and a copper alloy having a low temperature coefficient of resistance and a high stability (time invariance) with respect to time of inherent resistance can be obtained.
In patent document 2, in a copper alloy containing Mn in a range of 21.0 mass% to 30.2 mass%, and Ni in a range of 8.2 mass% to 11.0 mass%, the value x [ ppm/°c ] of the TCR in a temperature range of 20 ℃ to 60 ℃ is set]X is-10-2 or 2-10, and the volume resistivity rho is 80X 10 -8 [Ω·m]115×10 above -8 [Ω·m]In the following, the reduction in the cross-sectional area of the circuit of the resistor such as the chip resistor using the resistive material can be suppressed, and the joule heating increase of the resistive material can be suppressed.
Prior art literature
Patent literature
Patent document 1: japanese patent application laid-open No. 2016-528376
Patent document 2: japanese patent laid-open No. 2017-053015
Disclosure of Invention
Problems to be solved by the invention
In recent years, in an electric system of an electric vehicle or the like, as a resistor such as a shunt resistor or a chip resistor, a resistor having a large volume resistivity ρ is required to have a high precision resistant to a use environment of a higher temperature, and as a copper alloy used for such a resistor, a copper alloy having a high precision resistant to a use environment of a higher temperature is required.
In contrast, in the copper alloy described in patent document 1, it is described that the thermal electromotive force (EMF) to copper at 20 ℃ is made to be less than ±1 μv/°c. Further, in the copper alloy described in patent document 1, as shown in fig. 3, it is known that the temperature dependence of the resistance becomes a large negative number in a temperature range of 20 ℃ to 150 ℃ including a higher temperature region, and therefore, an error is likely to occur in the resistance value in the high temperature region, but it is difficult to reduce the absolute value thereof.
In addition, in the copper alloy described in patent document 2, it is described that a copper thermal electromotive force (EMF) generated between a temperature environment of 20 ℃ and 100 ℃ is set to ±2 μv/c or less, and a Temperature Coefficient of Resistance (TCR) showing a temperature dependence of resistance is set to ±50x10 in a temperature range of 20 ℃ to 60 °c -6 [℃ -1 ]However, the following ranges are required to further reduce the absolute value of EMF and to control the Temperature Coefficient of Resistance (TCR) in a wide temperature range from normal temperature (e.g., 20 ℃) to high temperature (e.g., 150 ℃) to a negative number having a small absolute value.
As described above, the copper alloy described in patent documents 1 and 2 has room for improvement in terms of increasing the volume resistivity ρ and also considering the Temperature Coefficient of Resistance (TCR) and the thermal electromotive force (EMF) against copper in a wide temperature range from normal temperature to high temperature, and in terms of reducing the absolute value of the thermal electromotive force (EMF) against copper and setting the Temperature Coefficient of Resistance (TCR) in a wide temperature range from normal temperature (e.g., 20 ℃) to high temperature (e.g., 150 ℃) to a negative number having a small absolute value.
Accordingly, an object of the present application is to provide a copper alloy material which has a sufficiently high volume resistivity as a resistive material and a small absolute value of a thermal electromotive force to copper and a negative temperature coefficient of resistance and a small absolute value in a wide temperature range from normal temperature (for example, 20 ℃) to high temperature (for example, 150 ℃), and a resistive material for a resistor and a resistor using the copper alloy material.
Means for solving the problems
The inventors of the present application have achieved the following findings. Namely: by having a composition containing Mn:20.0 mass% or more and 35.0 mass% or less, ni:5.0 mass% or more and 15.0 mass% or less and Fe: the alloy composition of 0.01 mass% or more and 0.50 mass% or less and Co is in the range of 0 mass% or more and 1.50 mass% or less (including the case where the content of Co is 0 mass%), and the total amount of Fe and Co is in the range of 0.10 mass% or more and 2.00 mass% or less, and the balance being Cu and unavoidable impurities, can give a copper alloy material which has a sufficiently high volume resistivity ρ as a resistive material, and has a small absolute value for copper thermal electromotive force (EMF), and has a negative resistance temperature coefficient and a small absolute value in a wide temperature range from normal temperature (e.g., 20 ℃) to high temperature (e.g., 150 ℃).
In order to achieve the above object, the present invention has the following main constitution.
(1) A copper alloy material having an alloy composition comprising: mn:20.0 mass% or more and 35.0 mass% or less, ni:5.0 mass% or more and 15.0 mass% or less, and Fe:0.01 to 0.50 mass%, and Co is in the range of 0 to 1.50 mass% (inclusive of the case where the Co content is 0 mass%), and the total amount of Fe and Co is in the range of 0.10 to 2.00 mass%, with the remainder being Cu and unavoidable impurities.
(2) The copper alloy material according to the above (1), wherein the alloy composition contains Mn:20.0 mass% or more and 30.0 mass% or less.
(3) The copper alloy material according to the above (1) or (2), wherein the alloy composition contains: fe:0.01 mass% to 0.30 mass%, and Co:0.01 to 1.50 mass%.
(4) The copper alloy material according to any one of the above (1) to (3), wherein w, x, y and z satisfy the following relationship of the formula (I) when the Mn content is w%, the Ni content is x%, the Fe content is y%, and the Co content is z%,
0.8w-10.5≤x+10y+5z≤0.8w-6.5(I)。
(5) The copper alloy material according to any one of the above (1) to (4), wherein the ratio of x to w is less than 0.40 when the content of Mn is w [ mass% ] and the content of Ni is x [ mass% ].
(6) The copper alloy material according to any one of the above (1) to (5), wherein the copper alloy material is a plate, a bar, a strip or a wire, and has an average crystal grain size of 60 μm or less.
(7) The copper alloy material according to any one of the above (1) to (6), wherein the alloy composition further contains a metal selected from the group consisting of Sn:0.01 mass% or more and 3.00 mass% or less, zn:0.01 mass% or more and 5.00 mass% or less, cr:0.01 mass% to 0.50 mass% and Ag:0.01 mass% or more and 0.50 mass% or less, al:0.01 mass% or more and 1.00 mass% or less, mg:0.01 mass% or more and 0.50 mass% or less, si:0.01 mass% or more and 0.50 mass% or less, and P:0.01 mass% or more and 0.50 mass% or less.
(8) A resistive material for a resistor, comprising the copper alloy material according to any one of the above (1) to (7).
(9) A resistor which is a shunt resistor or a chip resistor comprising the resistor material for a resistor according to (8) above.
Effects of the invention
According to the present invention, it is possible to provide a copper alloy material which has a sufficiently high volume resistivity as a resistive material and a small absolute value of a thermal electromotive force to copper and has a negative temperature coefficient of resistance and a small absolute value in a wide temperature range from normal temperature (for example, 20 ℃) to high temperature (for example, 150 ℃), and a resistive material for a resistor and a resistor using the same.
Drawings
Fig. 1 is a graph showing the relationship between w and (x+10y+5z) in the case where w represents w% by mass, x represents Ni represents x% by mass, y represents Fe represents y represents Co represents z represents Co represents w represents x+10y+5z, and the graph represents w represents the horizontal axis.
FIG. 2 is a schematic diagram for explaining a method of obtaining a thermal electromotive force (EMF) to copper for a sample material of examples of the present invention and comparative examples.
Detailed Description
Hereinafter, preferred embodiments of the copper alloy material of the present invention will be described in detail. In addition, in the composition of the alloy of the present invention, the term "mass%" may be simply expressed as "%".
The copper alloy material of the present invention has an alloy composition containing Mn:20.0 mass% or more and 35.0 mass% or less, ni:5.0 mass% or more and 15.0 mass% or less, and Fe:0.01 to 0.50 mass% inclusive, and Co is in the range of 0 to 1.50 mass% inclusive (inclusive of the case where the Co content is 0 mass%), and the total amount of Fe and Co is in the range of 0.10 to 2.00 mass% inclusive, with the balance being Cu and unavoidable impurities.
In this way, in the copper alloy material of the present invention, mn is contained in a range of 20.0 mass% or more and 35.0 mass% or less, ni is contained in a range of 5.0 mass% or more and 15.0 mass% or less, fe is contained in a range of 0.01 mass% or more and 0.50 mass% or less, and the content of Co is in a range of 0 mass% or more and 1.50 mass% or less (including the case where the content of Co is 0 mass%), whereby the absolute value of the p-copper thermal electromotive force (EMF) (hereinafter, sometimes simply referred to as "p-copper thermal electromotive force") generated between the temperature environments of 0 ℃ and 80 ℃ can be reduced, and the Temperature Coefficient of Resistance (TCR) (hereinafter, sometimes simply referred to as "temperature coefficient of resistance") in a temperature range of 20 ℃ or more and 150 ℃ becomes a negative number having a small absolute value, and therefore, the high precision of the resistor can be promoted even under a high temperature environment. Further, by containing Mn in a range of 20.0 mass% to 35.0 mass%, and Ni in a range of 5.0 mass% to 15.0 mass%, the volume resistivity ρ can be increased, the absolute value of the thermal electromotive force (EMF) to copper can be reduced, and the absolute value of the Temperature Coefficient of Resistance (TCR) in a temperature range of 20 ℃ to 150 ℃ can be made small negative. As a result, by using the copper alloy material of the present invention, a copper alloy material having a sufficiently high volume resistivity ρ as a resistive material and a small absolute value of copper thermal electromotive force (EMF) and a negative temperature coefficient of resistance and a small absolute value, and a resistive material for a resistor and a resistor using the same can be provided.
[1] Composition of copper alloy material
< essential component >
The alloy composition of the copper alloy material of the present invention is an alloy composition containing 20.0 mass% to 35.0 mass% of Mn, 5.0 mass% to 15.0 mass% of Ni, and 0.01 mass% to 0.50 mass% of Fe, and the content of Co is in the range of 0 mass% to 1.50 mass% (inclusive of the case where the content of Co is 0 mass%). That is, the alloy composition of the copper alloy material of the present invention contains Mn, ni, and Fe as essential containing components.
(Mn: 20.0 mass% or more and 35.0 mass% or less)
Mn (manganese) is an element that increases the volume resistivity ρ and adjusts the Temperature Coefficient of Resistance (TCR), which is a negative value, in a positive direction, thereby decreasing the absolute value of the Temperature Coefficient of Resistance (TCR). In order to exert this effect and obtain a homogeneous copper alloy material, mn is preferably contained in an amount of 20.0 mass% or more, more preferably 22.0 mass% or more, and even more preferably 24.0 mass% or more. Here, by increasing the Mn content to 22.0 mass% or more, 24.0 mass% or more, or 25.0 mass% or more, the volume resistivity ρ of the copper alloy material can be further increased. On the other hand, if the Mn content exceeds 35.0 mass%, the Temperature Coefficient of Resistance (TCR) tends to be positive, and the absolute value of the thermal electromotive force (EMF) to copper tends to be large. Therefore, the Mn content is preferably in the range of 20.0 mass% to 35.0 mass%. On the other hand, if the Mn content exceeds 30.0 mass%, after the copper alloy material is used for a long period of time as a resistance material or the like, the 2 nd phase different from the 1 st phase as the parent phase is liable to occur, and thus the electrical characteristics are liable to change with the passage of time. Therefore, from the viewpoint of improving the stability of the electrical characteristics against heat and the like, the Mn content is preferably 30.0 mass% or less.
(Ni: 5.0 mass% or more and 15.0 mass% or less)
Ni (nickel) is an element that reduces the absolute value of the thermal electromotive force (EMF) to copper. In order to exert this effect, ni is preferably contained in an amount of 5.0 mass% or more. On the other hand, when the Ni content is large, the absolute value of the Temperature Coefficient of Resistance (TCR) tends to increase in the negative direction. Therefore, the Ni content is preferably in the range of 5.0 mass% to 15.0 mass%. In particular, in the copper alloy material of the present invention, when the content of Mn is w% by mass and the content of Ni is x% by mass, the ratio of x to w is preferably less than 0.40. By reducing the ratio of x to w, the absolute value of the Temperature Coefficient of Resistance (TCR) can be further reduced. Therefore, the ratio of x to w is preferably less than 0.40, more preferably 0.35 or less. The Ni content in the copper alloy material may be in the range of 5.0 mass% to 15.0 mass%, may be in the range of 5.0 mass% to 12.0 mass%, or may be in the range of 5.0 mass% to 9.0 mass% from the standpoint of reducing the absolute value of the Temperature Coefficient of Resistance (TCR).
(Fe: 0.01 mass% or more and 0.50 mass% or less)
Fe (iron) is an element that reduces the absolute value of the copper thermal electromotive force (EMF) by adjusting the EMF in the positive direction. In particular, it is expected that the effect of Fe on the absolute value of the copper thermal electromotive force (EMF) is greater than that of Co described below, and that the raw material cost is also low, so that Fe is required to be contained in an amount of 0.01 mass% or more. On the other hand, fe is an element that is difficult to maintain in a solid solution state in the matrix (parent phase) and is easy to form the 2 nd phase. Particularly, when the Fe content exceeds 0.50 mass%, the absolute value of the Temperature Coefficient of Resistance (TCR) tends to be large due to the formation of crystals of the 2 nd phase, and the absolute value of the thermal electromotive force (EMF) to copper tends to be large. Therefore, the Fe content is preferably in the range of 0.01 mass% to 0.50 mass%. In particular, from the viewpoint of further improving the stability of the electrical characteristics against heat and the like, thereby further improving the reliability in long-term use as a resistive material and the like, the Fe content is more preferably 0.30 mass% or less, and still more preferably 0.20 mass% or less.
< 1 st optional additive component (Co) >)
( Co:0 mass% or more and 1.50 mass% or less (including the case of 0 mass%) )
The copper alloy material of the present invention may contain Co in addition to Mn, ni, and Fe as essential components. Co (cobalt) is an element that reduces the absolute value of the copper thermal electromotive force (EMF) by adjusting the EMF in the positive direction. Co is a component having a wide range of contents that can compensate for the shortage of Fe content and can obtain a uniform structure, and by using Co together with Fe, a desired thermal electromotive force (EMF) to copper can be easily obtained. The Co content may be 0 mass%, but from the viewpoint of exerting this effect, the Co content is preferably 0.01 mass% or more, more preferably 0.10 mass% or more. On the other hand, since Co is an expensive element, the Co content is preferably 1.50 mass% or less. Since Co is an element that is not likely to generate phase 2 unlike Fe, it is preferable to contain Co instead of Fe, and it is preferable to contain both Fe and Co. In particular, when the Co content is 0.01 mass% or more and the Fe content is 0.01 mass% or more and 0.30 mass% or less, even when the Mn content exceeds 30.0 mass%, the stability of the electric characteristics against heat and the like can be improved, and thus the reliability in long-term use as a resistance material and the like can be improved.
( Total of Fe and Co: 0.10 mass% or more and 2.00 mass% or less )
Fe and Co are elements that reduce the absolute value of the copper thermal electromotive force (EMF) by adjusting the EMF in the positive direction. In particular, from the viewpoint of easily obtaining a desired thermal electromotive force (EMF) to copper, by adding one or both of Fe and Co and containing them in a total of 0.10 mass% or more, the absolute value of the thermal electromotive force (EMF) to copper can be reduced even in the case of a trace amount of Fe of 0.01 mass% or no Co. On the other hand, if the total amount of Fe and Co exceeds 2.00 mass%, it is difficult to obtain a uniform structure, and thus the electric properties are liable to be deviated. Therefore, the total amount of Fe and Co is preferably in the range of 0.10 mass% to 2.00 mass%, more preferably in the range of 0.30 mass% to 1.65 mass%.
In the copper alloy material of the present invention, when the Mn content is w%, the Ni content is x%, the Fe content is y%, and the Co content is z%, w, x, y, and z preferably satisfy the relationship of the following formula (I).
0.8w-10.5≤x+10y+5z≤0.8w-6.5(I)
Wherein, by satisfying the relation of 0.8w-10.5 +.x+10y+5z, the copper thermal electromotive force (EMF) is not easy to take a larger value in the negative direction. On the other hand, by satisfying the relation that x+10y+5z is not more than 0.8w-6.5, the copper thermal electromotive force (EMF) is not easily set to a large value in the positive direction.
Fig. 1 is a graph showing the relationship between x and (x+10y+5z) in the case where x represents the horizontal axis and (x+10y+5z) represents the vertical axis, where w represents the content of Mn, x represents the content of Ni, y represents the content of Fe, and z represents the content of Co, respectively, for a copper alloy material containing Mn, ni, and Fe and a copper alloy material containing Mn, ni, fe, and Co. In the graph of fig. 1, for a copper alloy material having an absolute value of 0.5 μv/deg.c or less for copper thermal electromotive force (EMF), o is plotted as a small absolute value of copper thermal electromotive force (EMF) and good as a resistive material. In addition, for a copper alloy material whose absolute value of the copper thermal electromotive force (EMF) exceeds 0.5 μv/°c, the absolute value of the copper thermal electromotive force (EMF) is large and plotted as a defective resistance material.
Here, for the copper alloy materials satisfying the above formula (I) in which the total amount of Fe and Co is 0.10 mass% or more, more specifically, the copper alloy materials of examples 1 to 20 of the present invention and comparative example 4 described later, the absolute value of the copper thermal electromotive force (EMF) is 0.5 μv/°c or less, and "o" is plotted in the graph of fig. 1. On the other hand, in the case of a copper alloy material containing Mn, ni, and Fe, or a copper alloy material containing Mn, ni, fe, and Co, and in which the total amount of Fe and Co that does not satisfy the formula (I) is 0.10 mass% or more, for example, in the case of copper alloy materials of comparative examples 3 and 5 described later, the absolute value of the copper thermal electromotive force (EMF) exceeds 0.5 μv/°c, and "x" is plotted in the graph of fig. 1.
Thus, by satisfying the relation of the above formula (I), a copper alloy material having a small absolute value of the copper thermal electromotive force (EMF) (for example, an absolute value of the EMF is 0.5 μv/c or less) can be easily obtained.
In fig. 1, as copper alloy materials in which the total amount of Fe and Co that do not satisfy the relation of the above formula (I) is 0.10 mass% or more, in addition to comparative examples 3 and 5, copper alloy materials containing Mn, ni, fe and Co and copper alloy materials containing Mn, ni, fe and Co are described, but the absolute values of the thermal electromotive force (EMF) for copper are all more than 0.5 μv/°c, and plotted "x" in the graph of fig. 1.
< 2 nd optional additional component (optional additional component other than Co) >)
The copper alloy material of the present invention may further contain, as an optional additive component, a material selected from the group consisting of Sn:0.01 mass% or more and 3.00 mass% or less, zn:0.01 mass% or more and 5.00 mass% or less, cr:0.01 mass% to 0.50 mass% and Ag:0.01 mass% or more and 0.50 mass% or less, al:0.01 mass% or more and 1.00 mass% or less, mg:0.01 mass% or more and 0.50 mass% or less, si:0.01 mass% or more and 0.50 mass% or less, and P:0.01 mass% or more and 0.50 mass% or less.
(Sn: 0.01 mass% or more and 3.00 mass% or less)
Sn (tin) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, sn is preferably contained in an amount of 0.01 mass% or more. On the other hand, when the Sn content is 3.00 mass% or less, the reduction in manufacturability due to embrittlement of the copper alloy material is less likely to occur.
(Zn: 0.01 mass% or more and 5.00 mass% or less)
Zn (zinc) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, zn is preferably contained in an amount of 0.01 mass% or more. On the other hand, the Zn content may adversely affect the volume resistivity ρ, the Temperature Coefficient of Resistance (TCR), and the stability of the electrical performance of the resistor such as copper thermal electromotive force (EMF), and is therefore preferably set to 5.00 mass% or less.
(Cr: 0.01 to 0.50 mass%)
Cr (chromium) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, cr is preferably contained in an amount of 0.01 mass% or more. On the other hand, the Cr content may adversely affect the volume resistivity ρ, the Temperature Coefficient of Resistance (TCR), and the stability of the electrical properties of the resistor such as copper thermoelectromotive force (EMF), and is therefore preferably 0.50 mass% or less.
(Ag: 0.01 to 0.50 mass%)
Silver (Ag) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, 0.01 mass% or more of Ag is preferably contained. On the other hand, the Ag content may adversely affect the stability of the electrical properties of the resistor such as the volume resistivity ρ, the Temperature Coefficient of Resistance (TCR), and the copper thermoelectromotive force (EMF), and is preferably 0.50 mass% or less.
(Al: 0.01 mass% or more and 1.00 mass% or less)
Al (aluminum) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, it is preferable to contain 0.01 mass% or more of Al. On the other hand, since the copper alloy material may be embrittled, the Al content is preferably 1.00 mass% or less.
(Mg: 0.01 mass% or more and 0.50 mass% or less)
Mg (magnesium) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, mg is preferably contained in an amount of 0.01 mass% or more. On the other hand, since embrittlement of the copper alloy material is likely, the Mg content is preferably 0.50 mass% or less.
(Si: 0.01 mass% or more and 0.50 mass% or less)
Si (silicon) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, si is preferably contained in an amount of 0.01 mass% or more. On the other hand, since the copper alloy material may be embrittled, the Si content is preferably 0.50 mass% or less.
(P: 0.01 to 0.50 mass%)
P (phosphorus) is a component that can be used to adjust the volume resistivity ρ. In order to exert this effect, it is preferable to contain 0.01 mass% or more of P. On the other hand, since the copper alloy material may be embrittled, the P content is preferably 0.50 mass% or less.
( Total amount of optional additional ingredients: 0.01 to 5.00 mass% )
In order to obtain the effect of the optional components, the optional components are preferably contained in a total amount of 0.01 mass% or more. On the other hand, if these optional additional components are contained in a large amount, compounds are easily formed between the components and the necessary components, and therefore, the total amount is preferably 5.00 mass% or less.
< balance: cu and unavoidable impurities
The balance being Cu (copper) and unavoidable impurities, in addition to the above-described essential and optional additional components. The "unavoidable impurities" described herein are impurities which are not essential in the copper-based product because they are substances which are substantially present in the raw material or substances which are inevitably mixed in the production process, but are allowable because they are trace amounts and do not affect the characteristics of the copper-based product. Examples of the unavoidable impurities include nonmetallic elements such as sulfur (S), carbon (C), and oxygen (O), and metallic elements such as antimony (Sb). The upper limit of the content of these components may be 0.05 mass% per the above components, and 0.20 mass% of the total amount of the above components.
[2] Shape and metallic structure of copper alloy material
The shape of the copper alloy material of the present invention is not particularly limited, and is preferably a plate, a bar, a strip or a wire from the viewpoint of facilitating hot or cold working steps described later. Among them, in a copper alloy material formed by rolling such as a plate material or a strip material, the rolling direction may be set to be the drawing direction. In addition, in a copper alloy material formed by drawing, pulling, and extruding such as a wire rod or bar material such as a flat wire rod or a round wire rod, any one of a drawing direction, a pulling direction, and an extruding direction may be used as a drawing direction.
The copper alloy material of the present invention is preferably a plate, a bar, a strip or a wire, and has an average crystal grain size of 60 μm or less. Here, by setting the average crystal grain size of the crystals to 60 μm or less, coarse grains are less likely to be formed on the copper alloy material, and therefore, the absolute value of the Temperature Coefficient of Resistance (TCR) and the absolute value of the thermal electromotive force (EMF) to copper can be reduced at the same time. In particular, in the copper alloy material of the present invention, such a copper alloy material having an average crystal grain size of 60 μm or less can be easily obtained. On the other hand, the lower limit of the average crystal grain size is not particularly limited, and may be 0.1 μm or more from the viewpoint of production. In the case where the average crystal grain size of the crystals is not equiaxed, and the crystal grain size is anisotropic by rolling in the stretching direction, drawing, or the like, the measurement is performed on a plane perpendicular to the stretching direction.
The average crystal grain size in the present specification can be measured according to the method for testing the crystal grain size of copper-extended product described in JIS H0501. More specifically, after a test material was prepared by embedding a copper alloy material in a resin so that the cross section thereof was exposed, the cross section orthogonal to the stretching direction was polished, wet etching was performed using an aqueous chromic acid solution, and the exposed crystal grains were observed by a Scanning Electron Microscope (SEM), whereby the crystal grain size (or crystal grain size) was measured. In particular, when the average crystal grain size on the surface perpendicular to the stretching direction is measured, the copper alloy material is embedded in the resin so that the cross section perpendicular to the stretching direction is exposed, and a test material is produced.
[3] One example of a method for producing a copper alloy material
The copper alloy material can be obtained by controlling the alloy composition and the manufacturing process in combination, and the manufacturing process is not particularly limited. Among them, the following methods are examples of the manufacturing process that can obtain the copper alloy material.
As an example of the method for producing a copper alloy material according to the present invention, at least a casting step [ step 1], a homogenizing heat treatment step [ step 2], a heat treatment step [ step 3], a cold working step [ step 4] and an annealing step [ step 5] are sequentially performed on a copper alloy raw material having an alloy composition substantially identical to the alloy composition of the copper alloy material. In the homogenization heat treatment step [ step 2], the heating temperature is set to be in the range of 750 ℃ to 900 ℃ and the holding time is set to be in the range of 10 minutes to 10 hours. In the cold working step [ step 4], the total working ratio is set to 50% or more. In the annealing step [ step 5], the heating temperature is set to a range of 600 ℃ to 800 ℃ and the holding time is set to a range of 1 minute to 2 hours.
(i) Casting procedure (procedure 1)
In the casting step [ step 1], a copper alloy raw material having the above alloy composition is melted and cast in an inert gas atmosphere or in vacuum by using a high-frequency melting furnace, thereby producing an ingot (cast ingot) having a predetermined shape (for example, 30mm in thickness, 50mm in width, and 300mm in length). The alloy composition of the copper alloy raw material does not necessarily completely match the alloy composition of the copper alloy material to be produced, but has substantially the same alloy composition as the alloy composition of the copper alloy material, although the alloy composition is adhered to a melting furnace or volatilized depending on the additive components in each step of production.
(ii) Homogenizing heat treatment Process (Process 2)
The homogenization heat treatment step [ step 2] is a step of performing a heat treatment for homogenization on the ingot after the casting step [ step 1 ]. Here, regarding the conditions of the heat treatment in the homogenizing heat treatment step [ step 2], it is preferable that the heating temperature is set to a range of 750 ℃ to 900 ℃ and the holding time at the heating temperature is set to a range of 10 minutes to 10 hours from the viewpoint of suppressing coarsening of crystal grains.
(iii) Thermal working procedure [ procedure 3]
The heat treatment step [ step 3] is a step of producing a heat-treated material by subjecting the homogenized ingot to rolling, drawing, or the like between heats until a predetermined thickness or dimension is reached. Here, the hot working step [ step 3] includes both a hot rolling step and a hot drawing (wire drawing) step. In addition, the processing temperature is preferably in the range of 750 ℃ to 900 ℃ in terms of the conditions of the heat processing step [ step 3], and may be the same as the heating temperature in the homogenizing heat treatment step [ step 2 ]. The processing rate in the hot working step [ step 3] is preferably 10% or more.
The "working ratio" is a value obtained by dividing the cross-sectional area before the working such as rolling and drawing by the cross-sectional area before the working by 100 and then multiplying the cross-sectional area by the percentage, and is expressed by the following formula.
[ working ratio ] = { ([ cross-sectional area before working ] - [ cross-sectional area after working ])/[ cross-sectional area before working ] } ×100% (v/v)
The hot-worked material after the hot working step [ step 3] is preferably cooled. The method for cooling the hot-working material is not particularly limited, and it is preferable to increase the cooling rate as much as possible, for example, to a cooling rate of 10 ℃/sec or more by a method such as water cooling, from the viewpoint that coarsening of crystal grains is less likely to occur.
Here, the cooled hot-work material may be subjected to surface cutting to remove the surface. By performing the surface cutting, the oxide film and defects on the surface generated in the hot working step [ step 3] can be removed. The conditions for the surface cutting are not particularly limited as long as they are generally performed. The amount of surface cutting from the surface of the hot-worked material by the surface cutting can be appropriately adjusted based on the conditions of the hot-working step [ step 3], and can be set to about 0.5 to 4mm from the surface of the hot-worked material, for example.
(v) Cold working procedure [ procedure 4]
The cold working step (step 4) is a step of subjecting the hot-worked material subjected to the hot working step (step 3) to working such as rolling and drawing at a predetermined working rate in a cold room, depending on the thickness of the product, the wire diameter and the size. Here, the cold working step [ step 4] includes both a cold rolling step and a cold drawing (wire drawing) step. In addition, the working conditions such as rolling and wire drawing in the cold working step [ step 4] may be set according to the size of the hot working material. In particular, in the annealing step [ step 5] described later, the total processing rate in the cold working step [ step 4] is preferably 50% or more from the viewpoint of promoting the formation of uniform crystal grains due to recrystallization.
(vi) Annealing Process [ Process 5]
The annealing step [ step 5] is a step of annealing the cold rolled material subjected to the cold working step [ step 4] by heat treatment to recrystallize the cold rolled material. Here, in the conditions of the heat treatment in the annealing step [ step 5], the heating temperature is in the range of 600 ℃ to 800 ℃ and the holding time at the heating temperature is in the range of 1 minute to 2 hours. On the other hand, when the heating temperature is lower than 600 ℃, and the holding time is lower than 1 minute, it is difficult to recrystallize the copper alloy material. In addition, when the heating temperature exceeds 800 ℃ and the holding time exceeds 2 hours, the absolute value of the Temperature Coefficient of Resistance (TCR) and the thermal electromotive force (EMF) to copper tends to be large due to coarsening of crystal grains. Further, from the viewpoint of stably producing a copper alloy material having a small absolute value of the Temperature Coefficient of Resistance (TCR) and a small absolute value of the thermal electromotive force (EMF) to copper by suppressing the formation of the 2 nd phase in the copper alloy material after the annealing step [ step 5], it is preferable to heat-treat the copper alloy material at a heating temperature of 600 ℃ or higher in the annealing step [ step 5], and then cool the copper alloy material to a temperature of 200 ℃ or lower within 20 seconds.
Here, the cold working step [ step 4] and the annealing step [ step 5] may be repeated for the cold rolled material after the annealing step [ step 5]. Accordingly, the copper alloy material is a plate, a rod, a bar, or a wire having a desired shape, and coarse crystal grains are not easily formed, so that a copper alloy material exhibiting desired characteristics in terms of volume resistivity, temperature coefficient of resistance, and thermal electromotive force to copper can be obtained.
[4] Use of copper alloy material
The copper alloy material of the present invention may be in the form of a strip such as a strip, a flat wire, a round wire, or the like, in addition to a plate or a bar, and is extremely useful as a resistor material for resistors such as shunt resistors and chip resistors. That is, the resistor material preferably includes the copper alloy material. The resistor such as the shunt resistor or the chip resistor preferably has a resistor material for a resistor including the copper alloy material.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various modifications are possible within the scope of the present invention, including the concept of the present invention and all aspects contained in the claims.
Examples
Next, the present invention and comparative examples will be described in order to further clarify the effects of the present invention, but the present invention is not limited to these examples.
(inventive examples 1 to 15 and comparative examples 1 to 5)
A casting step of melting a copper alloy raw material having an alloy composition shown in table 1, and cooling the melted copper alloy raw material from the melt to cast the copper alloy raw material was performed [ step 1], to obtain an ingot. The alloy composition of comparative example 1 has the same alloy composition as the copper alloy described in patent document 1.
The ingot was subjected to a homogenization heat treatment step [ step 2] of heat-treating at a heating temperature of 800 ℃ and a holding time of 5 hours, and then, a heat treatment step [ step 3] of stretching in the longitudinal direction was performed at a working temperature of 800 ℃ so that the total working rate became 67% (the thickness before working was 30mm, and the thickness after working was 10 mm), to obtain a heat-treated material. Then, the surface was cooled to room temperature by water cooling, and surface cutting was performed to remove the oxide film formed on the surface.
The hot work material after the hot working step [ step 3] was subjected to a cold working step [ step 4] of rolling in the longitudinal direction at a total working ratio of 88% (thickness before working: 8mm, thickness after working: 1 mm). An annealing step (step 5) of subjecting the rolled material after the cold working step (step 4) to a heat treatment at a heating temperature in the range of 600 ℃ to 800 ℃ for a holding time of 1 minute to 2 hours.
Further, the hot work material after the annealing step [ step 5] was subjected to the 2 nd cold working step [ step 4] of rolling at a total working ratio of 70% (thickness before working: 1mm, thickness after working: 0.3 mm) along the longitudinal direction. And a 2 nd annealing step [ step 5] of performing heat treatment at a heating temperature in a range of 600 ℃ to 800 ℃ for a holding time of 1 minute to 2 hours on the cold rolled material after the 2 nd cold working step [ step 4]. In this way, copper alloy sheets of examples 1 to 15 of the present invention and comparative examples 1 to 5 in which the crystal grain size was adjusted were produced.
In table 1, a horizontal line "-" is shown in a column of a component not contained in the alloy composition of the copper alloy raw material, and it is clear that the component is not contained or is lower than the detection threshold value even if the component is contained.
Examples 16 to 18 of the present invention
A casting step [ step 1] of melting a copper alloy material having the alloy composition shown in Table 1, cooling the molten copper material to 300℃and casting the molten copper material was performed to obtain an ingot having a diameter of 30 mm. The ingot was subjected to a homogenization heat treatment step [ step 2] of heat-treating at a heating temperature of 800 ℃ and a holding time of 5 hours, and then subjected to a heat treatment step [ step 3] of stretching in the longitudinal direction in 1 pass of rolling at a working temperature of 800 ℃ so that the total working rate became 11%, to obtain a bar as a heat-treated material (the diameter of the ingot before working was 30mm, and the diameter of the bar after working was 10 mm). Then, the surface was cooled to room temperature by water cooling, and surface cutting was performed to remove the oxide film formed on the surface.
The rod material after the hot working step [ step 3] was subjected to a cold working step [ step 4], namely, drawn with a round die so as to have a total working rate of 96% (the diameter of the rod material before working was 10mm, and the diameter of the round wire rod after working was 1.95 mm). An annealing step (step 5) of heat-treating the cold-rolled material after the cold-working step (step 4) at a heating temperature in the range of 600 ℃ to 800 ℃ for a holding time of 1 minute to 2 hours. Thus, copper alloy wires of examples 16 to 18 of the present invention, in which the crystal grain size was adjusted, were produced.
Examples 19 to 22 of the present invention
The bar obtained after the hot working step [ step 3] in the same manner as in examples 16 to 18 was subjected to the cold working step [ step 4], namely, drawing was performed with a flat die having four corners with a radius of curvature of 0.1mm, whereby drawing was performed so as to achieve a total working ratio of 99% (the diameter of the bar before working was 10mm, and the thickness of the flat wire after working was 1mm and the width was 3 mm). An annealing step (step 5) of heat-treating the cold-rolled material after the cold-working step (step 4) at a heating temperature in the range of 600 ℃ to 800 ℃ for a holding time of 1 minute to 2 hours.
Further, the hot work material after the annealing step [ step 5] was subjected to the 2 nd cold working step [ step 4] of rolling at a total working ratio of 70% (thickness before working: 1mm, thickness after working: 0.3 mm) along the longitudinal direction. And a 2 nd annealing step [ step 5] of performing heat treatment at a heating temperature in a range of 600 ℃ to 800 ℃ for a holding time of 1 minute to 2 hours on the cold rolled material after the 2 nd cold working step [ step 4]. Thus, copper alloy wires of examples 19 to 22 of the present invention, in which the crystal grain size was adjusted, were produced.
[ various measurement and evaluation methods ]
The following characteristic evaluation was performed using the copper alloy materials (copper alloy sheet material, copper alloy wire rod) according to the above-described invention examples and comparative examples. Evaluation conditions of the respective characteristics are as follows.
[1] Determination of average Crystal particle size
The copper alloy material thus produced was buried in a resin so that a cross section perpendicular to the drawing direction of the copper alloy material was exposed, and after producing a test material, the cross section perpendicular to the drawing direction was polished. Next, after wet etching was performed on the polished test material using an aqueous chromic acid solution, 3 fields of view were observed at a magnification of 50 to 2000 times based on the average crystal grain size using a Scanning Electron Microscope (SEM) (model: SSX-550, manufactured by shimadzu corporation) for the exposed crystal grains, and the crystal grain size was measured by a cutting method in the copper-extended product crystal grain size test method described in JIS H0501, and the average crystal grain size was calculated as an average value of the crystal grain sizes in 3 fields of view. The results are shown in Table 2.
[2] Determination of volume resistivity
For the present invention examples 1 to 15 and comparative examples 1 to 5, which obtained plates, the obtained plates having a thickness of 0.3mm were cut into plates having a width of 10mm and a length of 300mm, and test materials were produced. Further, in examples 16 to 22 of the present invention, in which round wires or flat wires were obtained, the round wires or flat wires obtained were cut into pieces with a length of 300mm, and test materials were produced.
In the measurement of the volume resistivity ρ, the voltage was measured at room temperature of 20℃by the four terminal method based on the method specified in JIS C2525, with the distance between voltage terminals set at 200mm and the measurement current set at 100mA, and the volume resistivity ρ [ μΩ·cm ] was obtained from the obtained values.
Regarding the measured volume resistivity ρ, the case of 80 μΩ·cm or more was evaluated as sufficiently large, and excellent as a resistive material and evaluated as "good". The volume resistivity ρ was set to 70 μΩ·cm or more and less than 80 μΩ·cm, and was evaluated as "o" when the volume resistivity ρ was large and the resistance material was good. On the other hand, when the volume resistivity ρ was smaller than 70 μΩ·cm, it was evaluated as "x" when the volume resistivity ρ was small and the resistance material was poor. In this example, "verygood" and "≡" were evaluated as acceptable levels. The results are shown in Table 2.
[3] Method for measuring copper thermal electromotive force (EMF)
For the present invention examples 1 to 15 and comparative examples 1 to 5, which obtained plates, the obtained plates having a thickness of 0.3mm were cut into plates having a width of 10mm and a length of 1000mm, and test materials were produced. Further, in examples 16 to 22 of the present invention, in which round wires or flat wires were obtained, the round wires or flat wires obtained were cut into pieces having a length of 1000mm, and test materials were produced.
The measurement of the copper thermal electromotive force (EMF) of the test material was performed in accordance with JIS C2527. More specifically, as shown in FIG. 2, in the measurement of the copper thermal electromotive force (EMF) of the test material 1, a fully annealed pure copper wire having a diameter of 1mm was used as the standard copper wire 2, and a temperature measuring contact P connecting one end of the test material 1 and the standard copper wire 2 was used 1 Immersing in warm water kept in a constant temperature bath 41 at 80 ℃ and connecting the other ends of the test material 1 and the standard copper wire 2 with the reference contacts P of the copper wires 31 and 32 21 、P 22 Immersed in ice water at 0℃which is kept cold by the freezing point device 42, and the electromotive force at this time is measured by the voltage measuring device 43. The resulting electromotive force was divided by 80 [. Degree.C.as a temperature difference]The thermal electromotive force EMF (μV/. Degree.C.) for copper was obtained.
The absolute value of the measured copper thermal electromotive force (EMF) was evaluated as "excellent" when the absolute value of the measured copper thermal electromotive force (EMF) was small and the measured copper thermal electromotive force (EMF) was excellent as a resistive material. On the other hand, the absolute value of the copper thermal electromotive force (EMF) was evaluated as "x" when the absolute value of the EMF was greater than 0.5 μv/°c, and the EMF was evaluated as a resistive material defect. The results are shown in Table 2.
[4] Method for measuring Temperature Coefficient of Resistance (TCR)
For the present invention examples 1 to 15 and comparative examples 1 to 5, which obtained plates, the obtained plates having a thickness of 0.3mm were cut into plates having a width of 10mm and a length of 300mm, and test materials were produced. Further, in examples 16 to 22 of the present invention, in which round wires or flat wires were obtained, the round wires or flat wires obtained were cut into pieces with a length of 300mm, and test materials were produced.
In the measurement of the Temperature Coefficient of Resistance (TCR), the voltage at 150℃was measured by the four-terminal method based on the method defined in JIS C2526, with the distance between voltage terminals set at 200mm and the measurement current set at 100mA, and the resistance R at 150℃was obtained from the obtained value 150℃ [mΩ]. Then, the voltage at which the temperature of the material to be tested was cooled to 20℃was measured, and the resistance value R at 20℃was obtained from the obtained value 20℃ [mΩ]. Then, based on the obtained resistance value, i.e., R 150℃ R is R 20℃ By tcr= { (R) 150℃ [mΩ]-R 20℃ [mΩ])/R 20℃ [mΩ]}×{1/(150[℃]-20[℃])}×10 6 The Temperature Coefficient of Resistance (TCR) (ppm/. Degree. C.) was calculated.
The measured Temperature Coefficient of Resistance (TCR) was evaluated as "", as excellent in that the Temperature Coefficient of Resistance (TCR) was negative and the absolute value was small, with the Temperature Coefficient of Resistance (TCR) being from-50 ppm/. Degree.C.to 0 ppm/. Degree.C.. The Temperature Coefficient of Resistance (TCR) was evaluated as "O" when the Temperature Coefficient of Resistance (TCR) was negative and the absolute value was small, and the temperature coefficient of resistance was not less than-60 ppm/. Degree.C and less than-50 ppm/. Degree.C. On the other hand, the Temperature Coefficient of Resistance (TCR) was evaluated as "X" when it was less than-60 ppm/. Degree.C.as negative but not excellent because of its large absolute value. In addition, even when the Temperature Coefficient of Resistance (TCR) exceeded 0ppm/°c, the Temperature Coefficient of Resistance (TCR) was evaluated as "x" because it was not excellent due to a positive value. The results are shown in Table 2.
[5] Evaluation of reliability
In addition, in order to examine the reliability of the copper alloy material used as a resistive material or the like for a long period of time, particularly the stability of the electrical characteristics against heat or the like, examples 1 to 22 and comparative examples 1 to 5 of the present invention were conducted, and the test material having the volume resistivity measured in the measurement of the volume resistivity of [2] was heated at 400℃for 2 hours, whereby the stability of the electrical characteristics against heat was accelerated. After the acceleration test by heating, the volume resistivity of the test material was measured by the same method as in the measurement of the volume resistivity of [2], and the difference between the volume resistivity before heating and the volume resistivity after heating was obtained. Here, the difference between the volume resistivity before heating and the volume resistivity after heating was 1.0 μΩ·cm or less, which was evaluated as "excellent" because the decrease in volume resistivity due to heating was sufficiently small and the reliability was excellent. The difference between the volume resistivity before and after the heating was more than 1.0 μΩ·cm and 2.0 μΩ·cm or less was evaluated as "o" as the decrease in volume resistivity due to the heating was small and the reliability was good. Further, when the difference between the volume resistivity before heating and the volume resistivity after heating exceeds 2.0 μΩ·cm, the decrease in volume resistivity due to heating was regarded as large, and it was relatively poor from the viewpoint of reliability, and was evaluated as "Δ″. The results are shown in Table 2.
[6] Comprehensive evaluation
Among these evaluation results, 3 were evaluated as "excellent" for all of the 3 evaluation results concerning the volume resistivity ρ, the copper thermal electromotive force (EMF) and the Temperature Coefficient of Resistance (TCR), and were evaluated as "excellent" for all of the 3 as excellent. In addition, when 1 or 2 of the 3 evaluation results were evaluated as "verygood", and the rest were evaluated as "o", the volume resistivity ρ, the characteristics of copper thermal electromotive force (EMF) and Temperature Coefficient of Resistance (TCR) were good, and were evaluated as "o". On the other hand, when any one of the 3 evaluation results concerning the volume resistivity ρ, the copper thermal electromotive force (EMF), and the Temperature Coefficient of Resistance (TCR) was "x", the characteristic of the volume resistivity ρ, the copper thermal electromotive force (EMF), and the Temperature Coefficient of Resistance (TCR) was insufficient, and was evaluated as "x". The results are shown in Table 2.
TABLE 1
TABLE 2
As is clear from the results of tables 1 and 2, the alloy compositions of the copper alloy materials of examples 1 to 22 of the present invention were within the appropriate range of the present invention, and all of the 3 evaluation results concerning the volume resistivity ρ, the thermal electromotive force (EMF) of copper, and the Temperature Coefficient of Resistance (TCR) were evaluated as "excellent" or "o", and were also evaluated as "excellent" or "o" in the overall evaluation.
Therefore, the copper alloy materials of examples 1 to 22 of the present invention were evaluated as "excellent" or "o" in the overall evaluation, and therefore had a sufficiently high volume resistivity as a resistive material, and had a small absolute value for the copper thermoelectromotive force, and the temperature coefficient of resistance in a wide temperature range from normal temperature (e.g., 20 ℃) to high temperature (e.g., 150 ℃) was negative and had a small absolute value.
On the other hand, the alloy compositions of the copper alloy materials of comparative examples 1 to 5 were all outside the appropriate range of the present invention. Therefore, the copper alloy materials of comparative examples 1 to 5 were evaluated as "x" in terms of at least one of the volume resistivity ρ, the thermal electromotive force (EMF) and the Temperature Coefficient of Resistance (TCR) of copper.
It is also clear that in the case where the Mn content exceeds 30.0 mass%, in the present invention example 5, the Fe content is set to 0.30 mass% or less, and thus the stability of the electric characteristics against heat and the like is improved as compared with the present invention examples 2 and 4 in which the Fe content is 0.40 mass% or more and the reliability evaluation result is evaluated as "Δ", and thus the reliability evaluation result is evaluated as "o".
It is also clear that in the present invention examples 1, 3, 6, 7, 10 to 15, 17 to 19, 21, and 22, the content of Fe was 0.20 mass% or less, and thus, the stability of the electric characteristics against heat and the like was improved as compared with the present invention examples 2, 4, 5, 8, 9, 16, and 20 in which the content of Fe was 0.25 mass% or more and the reliability evaluation result was evaluated as "o" or "Δ", and therefore, the reliability evaluation result was evaluated as "excellent".
Description of the reference numerals
1 test material
2 standard copper wire
31. 32 copper wire
41 constant temperature bath
42 freezing point device
43 voltage measuring device
P1 temperature measurement contact
P 21 、P 22 Reference contact
Claims (9)
1. A copper alloy material having an alloy composition comprising:
mn:20.0 to 35.0 mass%,
Ni:5.0 to 15.0 mass%, and
fe:0.01 to 0.50 mass%, and
co is in the range of 0 mass% to 1.50 mass% (inclusive of the case where the content of Co is 0 mass%) and
the total amount of Fe and Co is in the range of 0.10 to 2.00 mass%, with the balance being Cu and unavoidable impurities.
2. The copper alloy material according to claim 1, wherein the alloy composition contains Mn:20.0 mass% or more and 30.0 mass% or less.
3. The copper alloy material according to claim 1, wherein the alloy composition contains:
fe:0.01 to 0.30 mass%, and
co:0.01 to 1.50 mass%.
4. The copper alloy material according to claim 1, wherein w, x, y and z satisfy the relationship of the following formula (I) when the Mn content is w%, the Ni content is x%, the Fe content is y%, and the Co content is z%,
0.8w-10.5≤x+10y+5z≤0.8w-6.5(I)。
5. The copper alloy material according to claim 1, wherein when the content of Mn is set to w [ mass% ] and the content of Ni is set to x [ mass% ], the ratio of x to w is less than 0.40.
6. The copper alloy material according to claim 1, wherein the copper alloy material is a plate, a bar, a strip or a wire, and has an average crystal grain size of 60 μm or less.
7. The copper alloy material according to claim 1, wherein the alloy composition further contains a material selected from the group consisting of
Sn:0.01 to 3.00 mass%,
Zn:0.01 to 5.00 mass%,
Cr:0.01 to 0.50 mass%,
Ag:0.01 to 0.50 mass%,
Al:0.01 to 1.00 mass%,
Mg:0.01 to 0.50 mass%,
Si:0.01 to 0.50 mass%, and
p:0.01 mass% or more and 0.50 mass% or less.
8. A resistive material for a resistor, comprising the copper alloy material according to any one of claims 1 to 7.
9. A resistor which is a shunt resistor or a chip resistor having the resistive material for resistor according to claim 8.
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| JP2021107028 | 2021-06-28 | ||
| JP2021-107028 | 2021-06-28 | ||
| PCT/JP2022/025406 WO2023276904A1 (en) | 2021-06-28 | 2022-06-24 | Copper alloy material, and resistive material for resistor and resistor using same |
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| JP (1) | JP7214930B1 (en) |
| KR (1) | KR20240026276A (en) |
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| US3091527A (en) * | 1961-01-27 | 1963-05-28 | Leeds & Northrup Co | Copper base alloys particularly suited for precision resistance |
| JPS5641096A (en) * | 1979-09-10 | 1981-04-17 | Mitsubishi Metal Corp | Low melting point cu-mn system soldering material having excellent wetting property and fluidity |
| CN100584975C (en) * | 2006-11-23 | 2010-01-27 | 北京有色金属研究总院 | Copper-base alloy and preparation method thereof |
| CN102337425B (en) * | 2011-10-29 | 2013-07-24 | 重庆川仪自动化股份有限公司 | Ni-Al exothermic resistance alloy material |
| DE102013010301A1 (en) * | 2013-06-19 | 2014-12-24 | Isabellenhütte Heusler Gmbh & Co. Kg | Resistance alloy, component manufactured therefrom and manufacturing method therefor |
| JP2017053015A (en) | 2015-09-11 | 2017-03-16 | 日立金属株式会社 | Resistive material |
| JP7194145B2 (en) * | 2020-04-01 | 2022-12-21 | Koa株式会社 | Alloys for resistors and use of alloys for resistors in resistors |
| CN112375938B (en) * | 2020-10-26 | 2022-03-22 | 有研工程技术研究院有限公司 | High-temperature-resistant ultrahigh-strength high-elasticity stress relaxation-resistant copper alloy and preparation method and application thereof |
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