CN113454253B - Copper alloy strip, method for producing same, resistance material for resistor using same, and resistor - Google Patents
Copper alloy strip, method for producing same, resistance material for resistor using same, and resistor Download PDFInfo
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- CN113454253B CN113454253B CN202080015486.XA CN202080015486A CN113454253B CN 113454253 B CN113454253 B CN 113454253B CN 202080015486 A CN202080015486 A CN 202080015486A CN 113454253 B CN113454253 B CN 113454253B
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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
- C22C9/02—Alloys based on copper with tin as the next major constituent
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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
- C22C9/04—Alloys based on copper with zinc as the next major constituent
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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
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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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
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- 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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- 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
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- 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
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Abstract
The copper alloy strip of the present invention has an alloy composition containing 3 to 20 mass% of manganese, the balance being copper and unavoidable impurities, and an average value of KAM measured by a back-scattered electron diffraction method is 1 DEG or more and less than 5 deg. The copper alloy strip of the present invention is suitable for manufacturing chips by performing press working, and the variation in resistance value between products and batches is small.
Description
Technical Field
The present invention relates to a copper alloy strip and a method for manufacturing the same, and a resistor material for a resistor and a resistor using the same, and more particularly, to a copper alloy strip which is suitable for manufacturing chips by performing press working and in which variation in the resistance value of the manufactured chips is small.
Background
For the metal material of the resistance member used in the resistor, the Temperature Coefficient of Resistance (TCR) as an index thereof is required to be small so that the resistance of the resistor is stable even if the environmental temperature changes. The temperature coefficient of resistance is a coefficient in which the magnitude of a change in resistance value caused by temperature is expressed in parts per million (ppm) per 1 ℃ and is represented by TCR (x 10- 6 /K)＝{(R-R 0 )/R 0 }×{1/(T-T 0 )}×10 6 The formula (c) is shown. Here, T in the formula represents a test temperature (. degree. C.), T 0 The reference temperature (. degree. C.), R the resistance value (. omega.) at the test temperature T, and R 0 Indicates the reference temperature T 0 Resistance value (Ω) at time. Since TCR of Cu-Mn-Ni alloy and Cu-Mn-Sn alloy is very small, they are widely used as alloy materials for forming resistive elements.
However, in a resistor manufactured by press-molding such an alloy material, there is a case where strain occurs in the alloy material during press-molding, and variation occurs in the resistance value, so that the resistor cannot be stably manufactured.
Patent document 1 discloses the following: by subjecting a copper alloy material to rolling treatment at a high pressure and then heating the copper alloy material in a non-oxidizing atmosphere of hydrogen, residual strain can be removed, and as a result, the temperature coefficient of resistance can be reduced. However, even in the alloy material manufactured as described above, the strain may remain unevenly, and the resistance value may vary.
Documents of the prior art
Patent document
Patent document 1: japanese laid-open patent publication No. 2016-69724
Disclosure of Invention
Problems to be solved by the invention
The present invention has been made in view of the above circumstances, and an object thereof is to provide a copper alloy strip which is suitable for manufacturing chips by performing press working and in which variations in resistance values occurring between products and batches are small, and a method for manufacturing the copper alloy strip.
Means for solving the problems
The inventors of the present application have made intensive studies and found that: in a copper alloy strip having an alloy composition containing 3 to 20 mass% of manganese and the balance comprising copper and unavoidable impurities, the average value of KAM measured by a back-scattered electron diffraction method is 1 DEG or more and less than 5 DEG, so that a chip produced by subjecting such a copper alloy strip to press working has little variation in resistance value between products and batches, and such a copper alloy strip can be produced by a production method comprising the steps of: a 1 st heat treatment step of heating a copper alloy material having an alloy composition substantially the same as that of the copper alloy strip in a high temperature range of 800 ℃ to 950 ℃; a hot working procedure; 1 or more sets of steps, when the 1 st cold working step of performing cold working at a high reduction ratio of 50% or more and the 2 nd heat treatment step of heating in an intermediate temperature region of 400 ℃ to 700 ℃ inclusive, are set as the 1 set of steps; a 2 nd cold rolling step of performing cold rolling at a low reduction ratio of 5% or more and less than 50%; and a 3 rd heat treatment step of maintaining the temperature of the steel sheet for 10 to 55 seconds after the temperature is increased to 200 ℃ or more and less than 400 ℃ at a temperature increase rate of 200 ℃/min or more, and then cooling the steel sheet to less than 50 ℃ at a cooling rate of 100 ℃/min or more, based on the above findings, the inventors of the present invention have completed the present invention.
That is, the gist of the present invention is as follows.
(1) A copper alloy strip having an alloy composition containing 3 to 20 mass% of manganese and the balance containing copper and unavoidable impurities, wherein the average value of KAM measured by a back-scattered electron diffraction method is 1 DEG or more and less than 5 deg.
(2) The copper alloy strip according to the above (1), wherein a ratio of an area in which the value of KAM is 1 ° or more and less than 4 ° is 50% or more with respect to the entire area of KAM measured by a back scattered electron diffraction method.
(3) The copper alloy strip according to the above (1) or (2), wherein a ratio of an area having a value of KAM of 6 ° or more and less than 15 ° to an entire area of KAM measured by a back scattered electron diffraction method is 3% or more and 25% or less.
(4) The copper alloy strip according to any one of the above (1) to (3), wherein the Vickers hardness is 150 or more and 200 or less.
(5) The copper alloy strip according to any one of the above (1) to (4), wherein the alloy composition further contains 1 or more elements selected from the group consisting of: 0.01 to 5 mass% of nickel, 0.01 to 5 mass% of tin, 0.01 to 5 mass% of zinc, 0.01 to 0.5 mass% of iron, 0.01 to 0.5 mass% of silicon, 0.01 to 0.5 mass% of chromium, 0.01 to 0.5 mass% of zirconium, 0.01 to 0.5 mass% of titanium, 0.01 to 0.5 mass% of silver, 0.01 to 0.5 mass% of magnesium, 0.01 to 0.5 mass% of cobalt, and 0.01 to 0.5 mass% of phosphorus.
(6) A method for producing a copper alloy strip according to any one of the above (1) to (5), comprising: a 1 st heat treatment step of heating a copper alloy material having an alloy composition substantially the same as that of the copper alloy strip in a high temperature range of 800 ℃ to 950 ℃; a hot working procedure; 1 or more sets of steps, when the 1 st cold working step of performing cold working at a high reduction ratio of 50% or more and the 2 nd heat treatment step of heating in an intermediate temperature region of 400 ℃ to 700 ℃ inclusive, are set as the 1 set of steps; a 2 nd cold working step of performing cold working at a low reduction ratio of 5% or more and less than 50%; and a 3 rd heat treatment step of maintaining the temperature of the steel sheet for 10 to 55 seconds after the temperature is increased to 200 ℃ or higher and lower than 400 ℃ at a temperature increase rate of 200 ℃/min or higher, and then cooling the steel sheet to less than 50 ℃ at a cooling rate of 100 ℃/min or higher.
(7) A resistor material for resistors, which comprises the copper alloy strip according to any one of the above (1) to (5).
(8) A resistor comprising the resistive material according to (7) above.
Effects of the invention
According to the present invention, it is possible to provide a copper alloy strip which is suitable for manufacturing chips by performing press working and in which variations in resistance values occurring between products and lots are small, and a method for manufacturing the copper alloy strip.
Detailed Description
(1) Copper alloy strip
Preferred embodiments of the copper alloy strip of the present invention will be described in detail below. The copper alloy strip according to the present invention has an alloy composition containing 3 to 20 mass% of manganese, and the balance being copper and unavoidable impurities, and is characterized in that the average value of KAM measured by a back-scattered electron diffraction method is 1 ° or more and less than 5 °.
In such a copper alloy strip, when Mn is contained in an amount of 3 mass% or more, an appropriate strain is generated in the copper alloy strip, and an appropriate KAM value is obtained. On the other hand, in the copper alloy strip, by setting the average value of KAM measured by the back scattered electron diffraction method to 1 ° or more and less than 5 °, the copper alloy strip has an extremely small strain, and the strain generated in the press working can be suppressed (offset) by using the strain, thereby suppressing variations in the resistance value between products and lots.
Composition of copper alloy strip
[ manganese: 3 to 20 mass%)
The copper alloy strip of the present invention contains 3 to 20 mass% of manganese. Manganese (Mn) is an essential component of the present invention. When the manganese content is in such a range, the temperature coefficient of resistance of the copper alloy material can be reduced. On the other hand, if the content of manganese is less than 3 mass%, the effect of reducing the temperature coefficient of resistance cannot be sufficiently obtained. When the manganese content is more than 20 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The manganese content is preferably 5 mass% or more from the viewpoint of the temperature coefficient of resistance.
< optional composition of copper alloy strip >
In addition, the alloy strip of the present invention may further contain 1 or more elements selected from the group consisting of: 0.01 to 5 mass% of nickel, 0.01 to 5 mass% of tin, 0.01 to 5 mass% of zinc, 0.01 to 0.5 mass% of iron, 0.01 to 0.5 mass% of silicon, 0.01 to 0.5 mass% of chromium, 0.01 to 0.5 mass% of zirconium, 0.01 to 0.5 mass% of titanium, 0.01 to 0.5 mass% of silver, 0.01 to 0.5 mass% of magnesium, 0.01 to 0.5 mass% of cobalt, and 0.01 to 0.5 mass% of phosphorus. These elements are added to improve the temperature coefficient of resistance, to adjust the volume resistivity, and the like, but if they are added beyond the respective predetermined ranges, even if the use temperature is lower than 400 ℃, there is a possibility that the characteristics such as the resistance value change, and the raw material cost increases. Hereinafter, each metal element will be described.
[ nickel: 0.01 to 5 mass%)
The content of nickel (Ni) is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less. If the content of nickel is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of nickel exceeds 5 mass%, the amount of strain during processing increases, and it is difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of nickel may be, for example, 0 mass% or more (including the case where no nickel is contained), 0.001 mass% or more, or 0.005 mass% or more.
[ tin: 0.01 to 5 mass%)
The content of tin (Sn) is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less. If the tin content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the tin content exceeds 5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of tin may be, for example, 0 mass% or more (including the case where tin is not contained), 0.001 mass% or more, or 0.005 mass% or more.
[ iron: 0.01 to 0.5 mass%)
The content of iron (Fe) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less. If the content of iron is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of iron exceeds 0.5 mass%, the strain amount during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of iron may be, for example, 0 mass% or more (including the case where no iron is contained), 0.001 mass% or more, or 0.005 mass% or more.
[ zinc: 0.01 to 5 mass%)
The content of zinc (Zn) is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less. If the content of zinc is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of zinc exceeds 5 mass%, there is a possibility that variations in resistance value are caused by a dezincification phenomenon. The content of zinc may be, for example, 0 mass% or more (including the case of containing no zinc), 0.001 mass% or more, or 0.005 mass% or more.
[ silicon: 0.01 to 0.5 mass%)
The content of silicon (Si) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less. If the content of silicon is less than 0.01 mass%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of silicon exceeds 0.5 mass%, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of silicon may be, for example, 0 mass% or more (including the case where no silicon is contained), 0.001 mass% or more, or 0.005 mass% or more.
[ chromium: 0.01 to 0.5 mass%)
The content of chromium (Cr) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of chromium is less than 0.01 mass%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of chromium exceeds 0.5 mass%, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of chromium may be, for example, 0 mass% or more (including the case where chromium is not contained), 0.001 mass% or more, or 0.005 mass% or more.
[ zirconium: 0.01 to 0.5 mass%)
The content of zirconium (Zr) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of zirconium is less than 0.01 mass%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of zirconium exceeds 0.5 mass%, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of zirconium may be, for example, 0 mass% or more (including the case where zirconium is not contained), 0.001 mass% or more, or 0.005 mass% or more.
[ titanium: 0.01 to 0.5 mass%)
The content of titanium (Ti) is not particularly limited, and is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of titanium is less than 0.01 mass%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of titanium exceeds 0.5 mass%, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of titanium may be, for example, 0 mass% or more (including the case where no titanium is contained), 0.001 mass% or more, or 0.005 mass% or more.
[ silver: 0.01 to 0.5 mass%)
The content of silver (Ag) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the silver content is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of silver exceeds 0.5 mass%, the strain amount during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of silver may be, for example, 0 mass% or more (including the case where silver is not contained), 0.001 mass% or more, or 0.005 mass% or more.
[ magnesium: 0.01 to 0.5 mass%)
The content of magnesium (Mg) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the magnesium content is less than 0.01 mass%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of magnesium exceeds 0.5 mass%, the strain amount during processing increases, and it is difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of magnesium may be, for example, 0 mass% or more (including the case where no magnesium is contained), 0.001 mass% or more, or 0.005 mass% or more.
[ cobalt: 0.01 to 0.5 mass%)
The content of cobalt (Co) is not particularly limited, but is preferably 0.01 mass% or more and 0.5 mass% or less with respect to 100 mass% of the copper alloy strip. If the cobalt content is less than 0.01 mass%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of cobalt exceeds 0.5 mass%, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of cobalt may be, for example, 0 mass% or more (including the case where cobalt is not contained), 0.001 mass% or more, or 0.005 mass% or more.
[ phosphorus: 0.01 to 0.5 mass%)
The content of phosphorus (P) is not particularly limited, but is preferably 0.01 mass% or more and 5 mass% or less with respect to 100 mass% of the copper alloy strip. If the content of phosphorus is less than 0.01%, the effects of improving the temperature coefficient of resistance and adjusting the volume resistivity may not be sufficiently obtained. On the other hand, if the content of phosphorus exceeds 0.5 mass%, the amount of strain during processing increases, and it becomes difficult to obtain an appropriate strain distribution when heat treatment is performed in a low temperature region. The content of phosphorus may be, for example, 0 mass% or more (including the case where phosphorus is not contained), 0.001 mass% or more, or 0.005 mass% or more.
[ balance: copper and unavoidable impurities ]
The balance is Cu (copper) and inevitable impurities, in addition to the essential components and optional additional components. The "inevitable impurities" referred to herein mean: the components present in the raw materials of the copper-based product and the components inevitably mixed in the production process are not originally necessary components, but are trace and are impurities which are allowable without affecting the characteristics of the copper-based product. Examples of the components as inevitable impurities include non-metal elements such as sulfur (S) and oxygen (O), and metal elements such as aluminum (Al) and antimony (Sb). The upper limit of the content of these components may be 0.05 mass% for each of the above components and 0.20 mass% for the total amount of the above components.
< crystal structure of copper alloy strip >
The alloy strip of the present invention is characterized in that the average value of KAM measured by a back scattered electron diffraction method (EBSD method) is 1 DEG or more and less than 5 deg.
As described above, by setting the average value of KAM to 1 ° or more and less than 5 °, the copper alloy strip has extremely small strain, and the strain generated in the press working can be suppressed (offset) using the strain, thereby suppressing variations in the resistance value between products and batches. On the other hand, if the average value of KAM is less than 1 °, the copper alloy strip is in a state of little strain (a state after recrystallization), and strain is introduced by press working, resulting in variation in resistance value between products and batches. Further, if the average value of KAM is 5 ° or more, there is a possibility that: the resistance value changes due to the influence of heat generated during use, mounting, or the like, and variations occur in the resistance value between products and batches.
The proportion of the area having a value of KAM of 1 ° or more and less than 4 ° is preferably 50% or more with respect to the entire area of KAM measured by the back scattered electron diffraction method. By setting the proportion of the area having a KAM value of 1 ° or more and less than 4 ° to 50% or more of the entire area subjected to KAM measurement, variations in the resistance values between products and batches can be more effectively suppressed. The case where the proportion of the area having the KAM value of 1 ° or more and less than 4 ° is small means that the area less than 1 ° is large or the area more than 4 °, the case where the area less than 1 ° is large is in a state of less strain, and the case where the area more than 4 ° is large is in a high strain region, and for example, the resistance value is easily affected by heat at the time of mounting, and the resistance value is greatly affected by slight temperature fluctuation and time shortening, and the variation increases. The proportion of the area having a KAM value of 1 ° or more and less than 4 ° is preferably 50% or more, and more preferably 50% or more and less than 70%.
Further, the proportion of the area having a KAM value of 6 ° or more and less than 15 ° to the entire area of KAM measured by the back scattered electron diffraction method is preferably 3% or more and 25% or less. The percentage of the area having a KAM value of 6 ° or more and less than 15 ° to the area measured by KAM as a whole is 3% or more and 25% or less, indicating that there is a region having insufficient ductility, which becomes a starting point of fracture at the time of pressing, so that the pressing can be performed without increasing the amount of strain in the alloy, and the dimensional accuracy can be improved and the variation in the resistance value between products and batches can be more effectively suppressed. Further, the proportion of the area having a KAM value of 6 ° or more and less than 15 ° is more preferably 5% or more and 25% or less.
KAM was measured by a back-scattered electron diffraction method using JSM-7001FA manufactured by Japan Electron Ltd. The cross section of the copper alloy strip parallel to the rolling direction was mirror-polished by resin filling, electrolytic polishing, or the like, to prepare a measurement sample. For example, the surface of the sample can be mirror-polished by immersing the copper alloy strip in a phosphoric acid solution and applying an electric current for 60 seconds to perform electrolytic polishing. The measurement was performed in a step size of 0.05 μm with the visual field region of 100 μm × 100 μm at the center of the plate thickness in the cross-sectional sample as the measurement target. Using Analysis software OIM Analysis manufactured by TSL, the average value of KAM was calculated using the first adjacent measurement value whose boundary is the case where the crystal orientation difference is 15 ° or more for all points. In addition, in the visual field region, the range of 0 ° or more and less than 15 ° is divided into 15 parts to obtain the area ratio per 1 ° and the ratio of the area of 1 ° or more and less than 4 ° and the ratio of the area of 6 ° or more and less than 15 ° are obtained with respect to the area where KAM is measured and the area is measured as a whole. Such measurements were made at arbitrary 5 positions, and the average thereof was calculated.
< physical Properties of copper alloy strip >
The vickers hardness of the alloy strip of the present invention is not particularly limited, but is preferably 150 to 200, and more preferably 150 to 190. When the vickers hardness is within such a range, particularly, strain due to press working can be suppressed, and a change in characteristics such as an electrical resistance value due to heat can be suppressed.
The vickers hardness was measured from the surface of the copper alloy material according to the method specified in JIS Z2244 (2009). The load (test force) at this time was 2.9N, and the indenter depression time was 15 s.
The copper alloy strip of the present invention is useful as a resistance material for resistors such as shunt resistors and chip resistors.
(2) Method for manufacturing copper alloy strip
The method for manufacturing the copper alloy strip according to the embodiment of the present invention will be described in detail. The manufacturing method is characterized by comprising the following steps: a 1 st heat treatment step of heating a copper alloy material having an alloy composition substantially the same as that of the copper alloy strip in a high temperature region of 800 ℃ to 950 ℃; a hot working procedure; a step of setting a 1 st cold working step of performing cold working at a high reduction ratio of 50% or more and a 2 nd heat treatment step of heating in an intermediate temperature region of 400 ℃ to 700 ℃ as 1 or more of the 1 st step; a 2 nd cold rolling step of performing cold rolling at a low reduction ratio of 5% or more and less than 50%; and a 3 rd heat treatment step of maintaining the temperature of the steel sheet for 10 to 55 seconds after the temperature is increased to 200 ℃ or higher and lower than 400 ℃ at a temperature increase rate of 200 ℃/min or higher, and then cooling the steel sheet to less than 50 ℃ at a cooling rate of 100 ℃/min or higher. The respective steps are explained below.
< preparation of copper alloy raw Material >
The copper alloy raw material has an alloy composition substantially the same as that of the copper alloy strip. The copper alloy material is not particularly limited, and examples thereof include an ingot (ingot) produced by casting. The reason why the alloy composition of the copper alloy raw material is "substantially the same" as the alloy composition of the copper alloy strip is that the following cases are included: in each step of producing a copper alloy strip from a copper alloy material, when the copper alloy material contains a volatile (vaporized) component or the like, the copper alloy material is vaporized (evaporated) and disappears.
< 1 st Heat treatment Process >
The 1 st heat treatment step is a step of heating the copper alloy material in a high-temperature region of 800 ℃ to 950 ℃. By setting the heating temperature in the 1 st heat treatment step to a high temperature range of 800 ℃ to 950 ℃, solidification segregation, crystallized products, and precipitates generated during casting can be eliminated, and the raw material can be homogenized.
The heating time in the 1 st heat treatment step is not particularly limited, but is preferably 10 minutes to 10 hours.
< working procedure of thermal processing >
The hot working step is a step of performing working (e.g., rolling) at a temperature of, for example, about 800 to 950 ℃ to have a desired plate thickness. The hot working is not particularly limited, and may be any of rolling and extrusion.
< No. 1 Cold working Process >
The 1 st cold working step is a step of performing cold working at a high reduction ratio of 50% or more. In the cold working step 1, cold working is appropriately performed according to a conventional method. By setting the reduction ratio in the 1 st cold working step to a high reduction ratio of 50% or more, the amount of strain serving as the driving force for recrystallization can be secured, and recrystallization in the next step can be facilitated.
< 2 nd Heat treatment Process >
The 2 nd heat treatment step is a step of heating in an intermediate temperature range of 400 ℃ to 700 ℃. By setting the heating temperature in the 2 nd heat treatment step to an intermediate temperature region of 400 ℃ to 700 ℃, recrystallization can be achieved, and a uniform structure with strain removed can be obtained. In the 2 nd heat treatment step, heat treatment is appropriately performed according to a conventional method.
The heating time in the 2 nd heat treatment is not particularly limited, but is preferably 10 seconds to 10 hours.
When the 2 steps of the 1 st cold working step and the 2 nd heat treatment step are set as 1 set of steps, only 1 set of steps may be performed, or 2 or more sets of steps may be repeatedly performed.
< 2 nd Cold Rolling Process >
The 2 nd cold rolling step is a step of performing cold working at a low reduction ratio of 5% or more and less than 50%. By performing cold working at a low reduction ratio in this manner, rolling can be performed while suppressing strain unevenness in the alloy material. On the other hand, if the reduction ratio in the 2 nd cold rolling step is 50% or more, even if heating is performed in the 3 rd heat treatment step in the subsequent stage, it is possible to suppress the strain generated at this time from being maintained in a non-uniform state, and to suppress variations in the resistance value between products and lots produced by press molding. Further, by setting the KAM value to 20% or more and less than 50%, the proportion of the area having the KAM value of 6 ° or more and less than 15 ° to the entire area subjected to KAM measurement can be set within an appropriate range.
< 3 rd Heat treatment Process >
The 3 rd heat treatment step is a step of holding the substrate at 200 ℃ or higher and lower than 400 ℃ at a temperature rise rate of 200 ℃/min or higher for 10 to 55 seconds, and then cooling the substrate at a cooling rate of 100 ℃/min or higher to lower than 50 ℃, and the heating step is a step of heating the substrate in the 3 rd heat treatment step. By heating in the low temperature region in this manner, the crystal grains are not recrystallized, and the strain in the crystal can be suppressed and adjusted so that the average value of KAM measured by the back scattered electron diffraction method is 1 ° or more and less than 5 °. Further, by setting the temperature to 250 ℃ or higher, the ratio of the area having a KAM value of 6 ° or more and less than 15 ° to the entire area subjected to KAM measurement and the ratio of the area having a KAM value of 1 ° or more and less than 4 ° to the entire area subjected to KAM measurement can be set to appropriate ranges.
In the method for manufacturing the copper alloy strip, a step other than the above-described steps may be provided. Examples thereof include: a surface cutting step of removing the thick oxide film formed after the hot working step by mechanical polishing; a degreasing step for removing rolling oil; a polishing step of mechanically or chemically removing the thin oxide film formed by the heat treatment; a rust prevention step for preventing discoloration; and so on.
The embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments, and various modifications can be made within the scope of the present invention, including all the aspects included in the concept of the present invention and the claims.
Examples
Next, examples of the present invention and comparative examples will be described in order to make the effects of the present invention more clear, but the present invention is not limited to these examples.
(inventive examples 1 to 15 and comparative examples 1 to 5)
Ingots (10kg) having the alloy compositions described in the column "alloy compositions" in table 1 were produced by casting. The ingot was subjected to a first heat treatment step 1 at a heating temperature of 800 ℃ to 950 ℃ and a heating time of 10 minutes to 10 hours to homogenize the alloy components, and then subjected to a hot working step at a working ratio of more than 70% to form a plate (dimension: length 500mm, width 100mm, thickness 10mm) and water-cooling to obtain a plate-like article.
Next, a 1 st cold working step of performing a high reduction ratio of 90% or more and a 2 nd heat treatment step of heating at an intermediate temperature range of 400 ℃ to 700 ℃ are performed. In inventive examples 1 to 5, 7, 8, 10 to 15 and comparative examples 1 to 5, the 1 st cold working step and the 2 nd heat treatment step were each performed 1 time (1 set). In addition, in inventive examples 6 and 9, the processing rate and the heating condition were changed in the 1 st and 2 nd steps, and the treatment was performed 2 times (2 sets) respectively.
And then, performing a 2 nd cold working step and a 3 rd heat treatment step, wherein the 2 nd cold working step is performed at a low working ratio of 5% or more and less than 50%, and in the 3 rd heat treatment step, the temperature is raised to 200 ℃ or more and less than 400 ℃ at a temperature raising rate of 200 ℃/min or more, then the temperature is maintained for 10 to 55 seconds, and then the steel is cooled to less than 50 ℃ at a cooling rate of 100 ℃/min or more. In comparative example 1, the 2 nd cold working step and the 3 rd heat treatment step were not performed, and in comparative example 4, the 3 rd heat treatment step was not performed, and therefore, the column of the non-performed steps is represented as "-" in table 1.
[ composition of copper alloy strip ]
The chemical composition of the copper alloy strip was measured by ICP analysis and is shown in table 1 below.
[ Electron Back-scattered diffraction ]
KAM was measured by a back-scattered electron diffraction method using JSM-7001FA manufactured by Japan Electron Ltd. The cross section of the copper alloy strip parallel to the rolling direction was mirror-polished by resin filling, electrolytic polishing, or the like, to prepare a measurement sample. The measurement was performed in a step size of 0.05 μm with a field of view of 100. mu. m.times.100 μm at the center of the plate thickness in the cross-sectional sample as the measurement target. The average value of KAM was calculated using Analysis software OIM Analysis manufactured by TSL corporation with the crystal orientation difference of 15 ° or more as a boundary. In this field of view, the range of 0 ° or more and less than 15 ° is divided into 15 parts (0 ° or more and less than 1 °, 1 ° or more and less than 2 °, 2 ° or more and less than 3 °, … … 14 ° or more and less than 15 °), and the area ratio per 1 ° is determined, thereby determining the ratio of the area of KAM having 1 ° or more and less than 4 ° and the ratio of the area of KAM having 6 ° or more and less than 15 ° in the 100 μm × 100 μm field of view as the measurement object. Such measurements were made at arbitrary 5 positions, and the average thereof was calculated.
[ Vickers hardness ]
Vickers hardness was measured from the surface of the copper alloy material according to the method prescribed in JIS Z2244 (2009). The load (test force) at this time was 2.9N, and the indenter depression time was 15 s.
[ deviation of resistance value ]
A chip having a thickness of 0.2mm, a width of 2mm and a length of 60mm was press-molded, heat-treated at 260 ℃ for 30 minutes in an argon atmosphere in consideration of the influence of heat at the time of mounting, and then the resistance value was measured by a four-terminal method in which the distance between voltage terminals was 30 mm. The measurement was performed with n being 500, and the standard deviation and the average value were obtained from the results. The variation in the resistance value was evaluated as "a" for a test piece (copper alloy strip) having a value of 0.50% or less, which was obtained using the formula (standard deviation/average value × 100), as "B" for a test piece having a value of more than 0.50% and 0.55% or less, as "C" for a test piece having a value of more than 0.55% and 0.60% or less, and as "D" for a test piece having a value of more than 0.60%. When the value obtained by using the formula (standard deviation/average value × 100) is 0.60% or less (i.e., a to C evaluation), the deviation of the resistance value is evaluated as an acceptable level.
[ Table 1]
As is clear from table 1, the copper alloy strips of inventive examples 1 to 15 have a composition containing 3 to 20 mass% of manganese, and the average value of KAM measured by the back scattered electron diffraction method is 1 ° or more and less than 5 °, which is within the appropriate range of the present invention, so that the variation in the resistance value is small even after heat treatment at 260 ℃ for 30 minutes after press molding.
On the other hand, it is understood that the test piece (copper alloy strip) of comparative example 1 has a composition containing 12 mass% of manganese, but the average value of KAM measured by the back scattered electron diffraction method is 0.5 ° which is smaller than the appropriate range of the present invention, and therefore, the variation in the resistance value after heat treatment at 260 ℃ for 30 minutes after press molding is large.
It is also understood that the test piece (copper alloy strip) of comparative example 2 has a composition containing 12 mass% of manganese, but the average value of KAM measured by the back scattered electron diffraction method is 12.1 °, which is larger than the appropriate range of the present invention, and therefore, the variation in the resistance value after heat treatment at 260 ℃ for 30 minutes after press molding is large.
It is also understood that the test piece (copper alloy strip) of comparative example 3 has a composition containing 7 mass% of manganese, but the average value of KAM measured by the back scattered electron diffraction method when heated at 700 ℃ as the 3 rd heat treatment is 0.6 °, which is smaller than the appropriate range of the present invention, and the variation in the resistance value when heat-treated at 260 ℃ for 30 minutes after press molding is large.
It is understood that the test piece (copper alloy strip) of comparative example 4 has a composition containing 10 mass% of manganese, but the average value of KAM measured by the back scattered electron diffraction method is 13.8 °, which is larger than the appropriate range of the present invention, and therefore, the variation in the resistance value after heat treatment at 260 ℃ for 30 minutes after press molding is large.
It is understood that the test piece (copper alloy strip) of comparative example 5 has a composition containing 5 mass% of manganese, but the average value of KAM measured by the back scattered electron diffraction method is 0.9 ° which is larger than the appropriate range of the present invention, and therefore, the variation in the resistance value after heat treatment at 260 ℃ for 30 minutes after press molding is large.
Claims (7)
1. A copper alloy strip having an alloy composition containing 3 to 20 mass% of manganese and the balance including copper and unavoidable impurities,
an average value of KAM measured by back scattered electron diffraction method is 1 DEG or more and less than 5 DEG,
the copper alloy strip has a Vickers hardness of 150 to 200 inclusive.
2. The copper alloy strip according to claim 1, wherein a ratio of an area having a value of KAM of 1 ° or more and less than 4 ° to an entire area of KAM measured by a back scattered electron diffraction method is 50% or more.
3. The copper alloy strip according to claim 1 or 2, wherein a ratio of an area having a value of KAM of 6 ° or more and less than 15 ° to the entire area of KAM measured by a back-scattered electron diffraction method is 3% or more and 25% or less.
4. The copper alloy strip according to claim 1 or 2, wherein the alloy composition further contains 1 or more elements selected from the group consisting of:
0.01 to 5 mass% of nickel,
0.01 to 5 mass% of tin,
0.01 to 5 mass% of zinc,
0.01 to 0.5 mass% of iron,
0.01 to 0.5 mass% of silicon,
0.01 to 0.5 mass% of chromium,
0.01 to 0.5 mass% of zirconium,
0.01 to 0.5 mass% of titanium,
0.01 to 0.5 mass% of silver,
0.01 to 0.5 mass% of magnesium,
0.01 to 0.5 mass% of cobalt, and
0.01 to 0.5 mass% of phosphorus.
5. A method for producing a copper alloy strip according to any one of claims 1 to 4, comprising:
a first heat treatment step of heating a copper alloy material having an alloy composition substantially the same as that of the copper alloy strip in a high-temperature region of 800 ℃ to 950 ℃;
a hot working procedure;
1 or more sets of steps, when the 1 st cold working step of performing cold working at a high reduction ratio of 50% or more and the 2 nd heat treatment step of heating in an intermediate temperature region of 400 ℃ to 700 ℃ inclusive, are set as the 1 or more sets of steps;
a 2 nd cold working step of performing cold working at a low reduction ratio of 5% or more and less than 50%; and
and a 3 rd heat treatment step of maintaining the temperature of the substrate at 200 ℃ or higher and lower than 400 ℃ at a temperature rise rate of 200 ℃/min or higher for 10 to 55 seconds, and then cooling the substrate at a cooling rate of 100 ℃/min or higher to less than 50 ℃.
6. A resistor material for resistors, which comprises the copper alloy strip according to any one of claims 1 to 4.
7. A resistor having the resistive material of claim 6.
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| JP6961861B1 (en) * | 2020-05-29 | 2021-11-05 | 古河電気工業株式会社 | Copper alloy strips and their manufacturing methods, resistor materials for resistors using them, and resistors |
| WO2023276906A1 (en) * | 2021-06-28 | 2023-01-05 | 古河電気工業株式会社 | Copper alloy material, resistive material for resistor using same, and resistor |
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| US9845521B2 (en) * | 2010-12-13 | 2017-12-19 | Kobe Steel, Ltd. | Copper alloy |
| KR20140025607A (en) * | 2011-08-04 | 2014-03-04 | 가부시키가이샤 고베 세이코쇼 | Copper alloy |
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