WO2013031279A1 - Cu-ni-si alloy and method for manufacturing same - Google Patents
Cu-ni-si alloy and method for manufacturing same Download PDFInfo
- Publication number
- WO2013031279A1 WO2013031279A1 PCT/JP2012/059207 JP2012059207W WO2013031279A1 WO 2013031279 A1 WO2013031279 A1 WO 2013031279A1 JP 2012059207 W JP2012059207 W JP 2012059207W WO 2013031279 A1 WO2013031279 A1 WO 2013031279A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- orientation
- copper
- mass
- alloy
- cold rolling
- Prior art date
Links
Images
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
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
Definitions
- the present invention relates to a copper alloy having excellent strength and bending workability, which is suitable as a conductive spring material for connectors, terminals, relays, switches and the like, and a method for producing the same.
- the copper alloy used for these components is required to have good strength and electrical conductivity.
- the copper alloy used is required to have good strength and electrical conductivity.
- in-vehicle female terminals are often subjected to a notching process called notching on the inner surface of the bending before press bending. This is processing performed to improve the shape accuracy after press bending. With the miniaturization of products, notching processing tends to become deeper in order to further improve the shape accuracy of terminals. Therefore, a copper alloy used for a vehicle-mounted female terminal is required to have good bending workability in addition to good strength and electrical conductivity. Further, as the relay terminal is miniaturized, the material is required to have good bending workability because the material is subjected to tight bending to obtain a desired strength.
- precipitation strengthened copper alloys such as a Corson alloy having high strength and electrical conductivity are used, and the demand is increasing.
- Corson alloys Cu-Ni-Si alloys have both high strength and relatively high electrical conductivity.
- the strengthening mechanism is based on the precipitation of Ni-Si intermetallic particles in the Cu matrix.
- the conductivity is improved.
- strength and bending workability are contradictory properties, and it is desired to improve bending workability while maintaining high strength even in Cu—Ni—Si based alloys.
- Patent Document 1 As a method for improving the bending workability of the Cu—Ni—Si alloy, there is a method of controlling the crystal orientation as described in Patent Documents 1 to 3.
- the area ratio of ⁇ 001 ⁇ ⁇ 100> in the measurement result of EBSD analysis is set to 50% or more.
- Patent Document 2 the area ratio of ⁇ 001 ⁇ ⁇ 100> in the measurement result of EBSP analysis is 50%.
- the area ratio of ⁇ 110 ⁇ ⁇ 112> in the measurement result of EBSD analysis is 20% or less, and the area ratio of ⁇ 121 ⁇ ⁇ 111> is 20%.
- the bendability is improved by setting the area ratio of ⁇ 001 ⁇ ⁇ 100> to 5 to 60%.
- Patent Document 4 bending workability is improved by setting the work hardening index to 0.05 or more.
- the present inventors conducted a verification test on the effect of the preceding invention.
- a certain improvement effect was recognized, but the bending radius was 0.
- the present invention provides a Cu—Ni—Si alloy having excellent strength and bending workability, which is suitable as a conductive spring material for connectors, terminals, relays, switches and the like, and a method for producing the same.
- the conventional technology improves the bending workability of Cu-Ni-Si alloys by controlling the crystal orientation of the copper alloy, but not only controls the crystal orientation but also controls the work hardening index (n value). As a result, it was found that excellent bending workability can be obtained.
- the present invention completed on the basis of the above knowledge, in one aspect, contains 1.0 to 4.5 mass% Ni and 0.2 to 1.0 mass% Si, with the balance being copper and inevitable impurities.
- EBSD Electron Back-Scatter Diffraction: Electron Backscattering Diffraction
- the area ratio of the Cube orientation ⁇ 0 0 1 ⁇ ⁇ 1 0 0> is 5% or more
- the Brass orientation The area ratio of ⁇ 1 ⁇ 1 0 ⁇ ⁇ 1 1 ⁇ 2> is 20% or less
- the area ratio of Copper orientation ⁇ 1 1 2 ⁇ ⁇ 1 1 1> is 20% or less
- the work hardening index is 0.2 or less.
- the Cu—Ni—Si based alloy according to the present invention includes at least one of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and Ag in a total amount. 0.005 to 2.5 mass% is contained.
- an ingot containing 1.0 to 4.5 mass% Ni and 0.2 to 1.0 mass% Si, the balance being copper and inevitable impurities is produced.
- the ingot is hot-rolled, cold-rolled, heat-treated with a softening degree of 0.25 to 0.75, then cold-rolled with a working degree of 7 to 50%, and then solutionized.
- This is a method for producing a Cu—Ni—Si based alloy of the present invention, in which after the treatment, aging treatment and cold rolling at a strain rate of 1 ⁇ 10 ⁇ 4 (1 / second) or less are performed in an arbitrary order.
- the ingot is made of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr, and Ag. One or more of them are contained in a total amount of 0.005 to 2.5% by mass.
- the present invention is a copper-drawn product provided with the above copper alloy.
- the present invention is an electronic device component including the copper alloy.
- FIG. 4 is a graph showing the relationship between the annealing temperature and the tensile strength when the Cu—Ni—Si based alloy according to the present invention is annealed at various temperatures.
- Ni and Si concentration Ni and Si are precipitated as an intermetallic compound such as Ni 2 Si by aging treatment. This compound improves the strength, and by precipitation, Ni and Si dissolved in the Cu matrix are reduced, so that the conductivity is improved.
- the Ni concentration is less than 1.0% by mass or the Si concentration is less than 0.2% by mass, the desired strength cannot be obtained, and conversely, when the Ni concentration exceeds 4.5% by mass or the Si concentration is 1.
- the Ni concentration is controlled to 1.0 to 4.5 mass% and the Si concentration is controlled to 0.2 to 1.0 mass%.
- the Ni concentration is preferably 1.3 to 4.0% by mass
- the Si concentration is preferably 0.3 to 0.9% by mass.
- the Cu—Ni—Si based alloy according to the present invention preferably contains these elements in a total amount of 0.005 to 2.5% by mass, and preferably 0.1 to 2.0% by mass. More preferred.
- the Cube orientation is a state in which the (0 0 1) plane is oriented in the rolling surface normal direction (ND) and the (1 0 0) plane is oriented in the rolling direction (RD), and ⁇ 0 0 1 ⁇ It is indicated by an index of ⁇ 1 0 0>.
- the Brass orientation is a state in which the ND faces the (1 1 0) plane and the RD faces the (1 1 2) plane, and is indicated by an index of ⁇ 1 1 0 ⁇ ⁇ 1 1 2>.
- the Copper orientation is a state in which the ND faces the (1 1 2) plane and the RD faces the (1 1 1) plane, and is represented by an index of ⁇ 1 1 2 ⁇ ⁇ 1 1 1>.
- the area ratio of the Cube orientation is controlled to 5% or more. When the area ratio of the Cube orientation is less than 5%, the bending workability deteriorates rapidly.
- the upper limit of the area ratio of the Cube orientation is not restricted in terms of bendability, but in the case of the Cu—Ni—Si based alloy according to the present invention, the area ratio of the Cube orientation is not affected by any change in the manufacturing method. None exceed 80%.
- the area ratios of the Copper orientation and the Brass orientation are each controlled to 20% or less. If either the Copper azimuth area ratio or the Brass azimuth area ratio exceeds 20%, the bending workability deteriorates rapidly.
- the lower limits of the area ratio of the Copper orientation and the Brass orientation are not restricted in terms of bendability, but in the case of the Cu—Ni—Si based alloy according to the present invention, no matter how the production method is changed, the Copper orientation Either the area ratio or the area ratio of the Brass orientation is never less than 1%.
- n value is a value used as an index of this work hardening. A larger n value indicates that the metal has a greater increase in tensile strength due to work hardening.
- press bending In order to mold the material into an electronic component such as a connector, press bending must be performed. When press bending is performed, the material is work-hardened and its tensile strength increases. Generally, the tensile strength and bending workability of a material are in a trade-off relationship, and the higher the tensile strength, the worse the bending workability.
- the n value is controlled to 0.2 or less. n value becomes like this. Preferably it is 0.1 or less, More preferably, it is less than 0.05. When the n value exceeds 0.2, the bending workability deteriorates rapidly.
- the lower limit of the n value is not restricted in terms of bendability, but in the case of the Cu—Ni—Si alloy according to the present invention, the n value is less than 0.01 no matter how the manufacturing method is changed. There is nothing.
- strain relief annealing may be performed after the third cold rolling in order to recover the decrease in the spring limit value due to the third cold rolling.
- pre-annealing heat treatment
- second cold rolling with a relatively low workability are performed before the solution treatment.
- the preliminary annealing is performed under the condition that the softening degree S is 0.25 to 0.75.
- FIG. 1 illustrates the relationship between the annealing temperature and the tensile strength when the Cu—Ni—Si alloy according to the present invention is annealed at various temperatures.
- thermocouple A sample with a thermocouple attached is placed in a furnace heated to a specified temperature, and when the sample temperature measured by the thermocouple reaches the specified temperature, the sample is removed from the furnace and cooled with water, and the tensile strength is measured. It is a thing. Recrystallization progresses when the sample arrival temperature is 500 to 700 ° C., and the tensile strength is rapidly reduced. The gradual decrease in tensile strength on the high temperature side is due to the growth of recrystallized grains.
- the softening degree S in the pre-annealing is defined by the following equation.
- ⁇ 0 is the tensile strength before pre-annealing
- ⁇ and ⁇ 900 are the tensile strength after pre-annealing and after annealing at 900 ° C., respectively.
- the temperature of 900 ° C. is adopted as a reference temperature for knowing the tensile strength after recrystallization because the Cu—Ni—Si alloy according to the present invention is stably recrystallized when annealed at 900 ° C. Yes.
- S is less than 0.25, the area ratio of the Copper orientation increases to exceed 20%, and accordingly, the area ratio of the Cube orientation also decreases.
- the temperature, time and cooling rate of the pre-annealing are not particularly limited, and it is important to adjust S to the above range. Generally, when a continuous annealing furnace is used, the furnace temperature ranges from 400 to 700 ° C. for 5 seconds to 10 minutes, and when a batch annealing furnace is used, the furnace temperature ranges from 350 to 600 ° C. for 30 minutes to 20 hours. Done in The softening degree S can be adjusted to 0.25 to 0.75 by the following procedure. (1) Measure the tensile test strength ( ⁇ 0 ) of the material before pre-annealing.
- the material before preliminary annealing is annealed at 900 ° C. Specifically, the material to which the thermocouple is attached is inserted into a tubular furnace at 950 ° C., and when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and cooled with water. (3) Obtain the tensile strength ( ⁇ 900 ) of the material after annealing at 900 ° C. (4) For example, when ⁇ 0 is 800 MPa and ⁇ 900 is 300 MPa, the tensile strengths corresponding to the softening degrees of 0.25 and 0.75 are 675 MPa and 425 MPa, respectively.
- the annealing conditions are determined so that the tensile strength after annealing is 425 to 675 MPa.
- “when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and water-cooled” is specifically, for example, the sample is wired in the furnace. When suspended, the wire is cut when it reaches 900 ° C. and dropped into a water tank provided below, or immediately after the sample temperature reaches 900 ° C. by hand from inside the furnace. Take it out quickly by immersing it in a water tank.
- the strain rate of the present invention is specified as rolling speed / roll contact arc length, and in order to lower the strain rate, it is effective to slow the rolling speed, increase the number of rolling passes, and lengthen the roll contact arc length. Is.
- the lower limit of the strain rate is not limited from the point of the n value, but if rolling is performed below 1 ⁇ 10 ⁇ 5 (1 / second), the rolling time is long, which is not industrially preferable.
- the strain rate of rolling in a general industry is about 2 ⁇ 10 ⁇ 4 to 5 ⁇ 10 ⁇ 4 (1 / second).
- the working degree of cold rolling (3) is preferably 30 to 99%. In order to generate recrystallized grains partially by pre-annealing (4), it is necessary to introduce strain by cold rolling (3), and effective strain can be obtained at a workability of 30% or more.
- Cold rolling (7) and (9) is arbitrarily performed for increasing the strength and controlling the n value, and the strength increases with an increase in the rolling degree, but the bendability decreases.
- the effects of the present invention can be obtained regardless of the degree of cold rolling (7) and (9).
- the strain relief annealing (10) is optionally performed in order to recover the spring limit value and the like which are lowered by the cold rolling when the cold rolling (9) is performed.
- the effect of the present invention can be obtained regardless of the presence or absence of strain relief annealing (10).
- the strain relief annealing (10) may or may not be performed.
- general production conditions for the Cu—Ni—Si based alloy may be selected.
- the Cu—Ni—Si based alloy according to the present invention can be processed into various copper products, such as plates, strips and foils. Furthermore, the Cu—Ni—Si based alloy according to the present invention can be used for lead frames and connectors. It can be used for electronic parts such as pins, terminals, relays, switches, and foil materials for secondary batteries. Further, the final plate thickness (product plate thickness) of the Cu—Ni—Si alloy according to the present invention is not particularly limited, but is generally 0.05 to 1.0 mm in the case of the above product use.
- Example 1 An alloy containing Ni: 2.6% by mass, Si: 0.58% by mass, Sn: 0.5% by mass, and Zn: 0.4% by mass with the balance being copper and inevitable impurities is used as an experimental material. , Pre-annealing, workability of the second cold rolling and the relationship between the strain rate of the third cold rolling and the crystal orientation and n value, and the influence of the crystal orientation and n value on the bendability of the product .
- a high-frequency melting furnace 2.5 kg of electrolytic copper was melted using a graphite crucible having an inner diameter of 60 mm and a depth of 200 mm in an argon atmosphere.
- Pre-annealing Insert a sample into an electric furnace adjusted to a predetermined temperature and hold it for a predetermined time, then place the sample in a water bath for cooling (water cooling), or leave the sample in the atmosphere for cooling (air cooling) 2 Cooled under street conditions.
- Second cold rolling Cold rolling was performed at various rolling degrees to a thickness of 0.18 mm.
- Solution treatment The sample was inserted into an electric furnace adjusted to 800 ° C. and held for 10 seconds, and then the sample was placed in a water bath and cooled.
- Aging treatment Heated in an Ar atmosphere at 450 ° C. for 5 hours using an electric furnace.
- a common rotation axis that can be expressed at the smallest angle is adopted.
- the deviation angle is calculated for all measurement points, and the first decimal place is an effective number.
- the area of crystal grains having an orientation within 10 ° from each of the Cube orientation, Copper orientation, and Brass orientation is the total measurement area. To obtain the area ratio.
- the information obtained in the azimuth analysis by EBSD includes azimuth information up to a depth of several tens of nanometers in which the electron beam penetrates the sample, but is described as an area ratio because it is sufficiently small with respect to the measured width. .
- Table 1 shows test conditions and evaluation results.
- the inventive examples were produced under the conditions specified by the present invention, the crystal orientation and the n value satisfied the specifications of the present invention, and MBR / t was 0.5 or less and good bending workability was obtained.
- Comparative Example 1 since the degree of softening in the pre-annealing was less than 0.25, the area ratio of Copper orientation exceeded 20%, and the area ratio of Cube orientation was less than 5%.
- Comparative Example 2 since the degree of softening in the preliminary annealing exceeded 0.75, the area ratio of the Brass orientation exceeded 20%, and the area ratio of the Cube orientation became less than 5%.
- Comparative Examples 3 and 4 the degree of workability of the second rolling deviated from the definition of the present invention, and the area ratio of the Cube orientation was less than 5%.
- Comparative Example 5 the strain rate of the third rolling deviated from the definition of the present invention, and the n value exceeded 0.2.
- MBR / t was 1, and bending workability was poor. Note that Comparative Example 5 was performed within the range of conditions recommended by Patent Document 3, and the crystal orientation satisfied the provisions of Patent Document 2.
- Example 2 It was examined whether the bendability improving effect shown in Example 1 could be obtained with Cu—Ni—Si based alloys having different components and production conditions. Casting, hot rolling and surface grinding were performed in the same manner as in Example 1 to obtain a 9 mm thick plate having the components shown in Table 2. The plate was subjected to rolling and heat treatment in the following process order to produce a product sample having a plate thickness of 0.15 mm.
- First cold rolling Cold rolling was performed to a predetermined thickness in accordance with the rolling degree of the second cold rolling.
- Pre-annealing Insert a sample into an electric furnace adjusted to a predetermined temperature and hold it for a predetermined time, then place the sample in a water bath for cooling (water cooling), or leave the sample in the atmosphere for cooling (air cooling) Cooling was performed under two conditions.
- Second cold rolling Cold rolling was performed at various rolling degrees to a thickness of 0.18 mm.
- Solution treatment The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was placed in a water bath and cooled. The temperature was selected so that the average diameter of the recrystallized grains was in the range of 5 to 25 ⁇ m.
- Aging treatment Heating was performed in an Ar atmosphere using an electric furnace at a predetermined temperature for 5 hours.
- the temperature was selected to maximize the tensile strength after aging.
- Third cold rolling Cold rolling was performed at various strain rates from 0.18 mm to 0.15 mm at a working degree of 17%.
- Strain relief annealing The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was left in the air and cooled.
- Example 2 Evaluation similar to Example 1 was performed about the sample after pre-annealing, and a product sample.
- Tables 2 and 3 show test conditions and evaluation results, respectively.
- “none” is written in the temperature column.
- the alloy of the present invention contains Ni and Si at the concentrations specified by the present invention, and is manufactured under the conditions specified by the present invention.
- the crystal orientation and the n value satisfy the specifications of the present invention, and MBR / t is 0. Bending workability as good as .5 or less was obtained.
- Comparative Example 6 since the strain rate of the third rolling deviated from the definition of the present invention, the n value exceeded 0.2 and the bending workability was poor.
- Comparative Examples 7, 8 and 9 the degree of softening in the pre-annealing was out of the definition of the present invention, and in Comparative Examples 10 and 11, the degree of work in the second rolling was out of the definition of the present invention. Beyond the provisions of the invention, the bending workability was poor. In Comparative Example 12, the Ni and Si concentrations were lower than those of the present invention, and the bending workability was good, but the 0.2% proof stress did not reach 500 MPa.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (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)
- Non-Insulated Conductors (AREA)
Abstract
Provided is a Cu-Ni-Si alloy and a method for manufacturing the Cu-Ni-Si alloy, the Cu-Ni-Si alloy being provided with exceptional strength and bendability, and being suitable as an electro-conductive spring material for a connector, terminal, relay, switch or other component. The Cu-Ni-Si alloy contains 1.0 to 4.5 wt% of Ni, 0.2 to 1.0 wt% of Si, and copper and inevitable impurities constituting the balance. Electron back-scatter diffraction (EBSD) measuring is performed. When the crystal orientation is analyzed the area of cube orientation {001} <100> constitutes 5% or more, the area of brass orientation {110} <112> constitutes 20% or less, and the area of copper orientation {112} <111> constitutes 20% or less. The work-hardening coefficient is 0.2 or less.
Description
本発明は、コネクタ、端子、リレー、スイッチ等の導電性ばね材として好適な、優れた強度、曲げ加工性を備えた銅合金及びその製造方法に関する。
The present invention relates to a copper alloy having excellent strength and bending workability, which is suitable as a conductive spring material for connectors, terminals, relays, switches and the like, and a method for producing the same.
近年、電子機器の小型化に伴い、電気・電子部品の小型化が進んでいる。そして、これら部品に使用される銅合金には良好な強度、導電率が要求される。
車載用端子においても小型化に伴い、使用される銅合金には良好な強度、導電率が要求される。さらに、車載用メス端子はプレス曲げ加工前に曲げ内面にノッチング加工と呼ばれる切り込み加工が施されることが多い。これはプレス曲げ加工後の形状精度を向上させるために行われる加工である。製品小型化に伴い、端子の形状精度をより向上させるためにノッチング加工は深くなる傾向にある。従って、車載用メス端子に使用される銅合金には良好な強度、導電率に加えて良好な曲げ加工性が要求される。さらに、リレー端子においても小型化に伴い、材料に所望の強度を得るために密着曲げが施されることから、材料には良好な曲げ加工性が要求される。 In recent years, with the miniaturization of electronic devices, the miniaturization of electrical and electronic components has been progressing. And the copper alloy used for these components is required to have good strength and electrical conductivity.
With the miniaturization of in-vehicle terminals, the copper alloy used is required to have good strength and electrical conductivity. Furthermore, in-vehicle female terminals are often subjected to a notching process called notching on the inner surface of the bending before press bending. This is processing performed to improve the shape accuracy after press bending. With the miniaturization of products, notching processing tends to become deeper in order to further improve the shape accuracy of terminals. Therefore, a copper alloy used for a vehicle-mounted female terminal is required to have good bending workability in addition to good strength and electrical conductivity. Further, as the relay terminal is miniaturized, the material is required to have good bending workability because the material is subjected to tight bending to obtain a desired strength.
車載用端子においても小型化に伴い、使用される銅合金には良好な強度、導電率が要求される。さらに、車載用メス端子はプレス曲げ加工前に曲げ内面にノッチング加工と呼ばれる切り込み加工が施されることが多い。これはプレス曲げ加工後の形状精度を向上させるために行われる加工である。製品小型化に伴い、端子の形状精度をより向上させるためにノッチング加工は深くなる傾向にある。従って、車載用メス端子に使用される銅合金には良好な強度、導電率に加えて良好な曲げ加工性が要求される。さらに、リレー端子においても小型化に伴い、材料に所望の強度を得るために密着曲げが施されることから、材料には良好な曲げ加工性が要求される。 In recent years, with the miniaturization of electronic devices, the miniaturization of electrical and electronic components has been progressing. And the copper alloy used for these components is required to have good strength and electrical conductivity.
With the miniaturization of in-vehicle terminals, the copper alloy used is required to have good strength and electrical conductivity. Furthermore, in-vehicle female terminals are often subjected to a notching process called notching on the inner surface of the bending before press bending. This is processing performed to improve the shape accuracy after press bending. With the miniaturization of products, notching processing tends to become deeper in order to further improve the shape accuracy of terminals. Therefore, a copper alloy used for a vehicle-mounted female terminal is required to have good bending workability in addition to good strength and electrical conductivity. Further, as the relay terminal is miniaturized, the material is required to have good bending workability because the material is subjected to tight bending to obtain a desired strength.
これらの要求に応じ、従来のりん青銅や黄銅といった固溶強化型銅合金に替わり、高い強度及び導電率を有するコルソン合金等の析出強化型銅合金が使用され、その需要は増加しつつある。コルソン合金の中でもCu-Ni-Si系合金は高強度と比較的高い導電率とを兼ね備えており、その強化機構は、Cuマトリックス中にNi-Si系の金属間化合物粒子が析出することにより強度及び導電率を向上させたものである。
一般に、強度と曲げ加工性とは相反する性質であり、Cu-Ni-Si系合金においても高強度を維持しつつ曲げ加工性の改善が望まれている。 In response to these demands, instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass, precipitation strengthened copper alloys such as a Corson alloy having high strength and electrical conductivity are used, and the demand is increasing. Among Corson alloys, Cu-Ni-Si alloys have both high strength and relatively high electrical conductivity. The strengthening mechanism is based on the precipitation of Ni-Si intermetallic particles in the Cu matrix. In addition, the conductivity is improved.
In general, strength and bending workability are contradictory properties, and it is desired to improve bending workability while maintaining high strength even in Cu—Ni—Si based alloys.
一般に、強度と曲げ加工性とは相反する性質であり、Cu-Ni-Si系合金においても高強度を維持しつつ曲げ加工性の改善が望まれている。 In response to these demands, instead of conventional solid solution strengthened copper alloys such as phosphor bronze and brass, precipitation strengthened copper alloys such as a Corson alloy having high strength and electrical conductivity are used, and the demand is increasing. Among Corson alloys, Cu-Ni-Si alloys have both high strength and relatively high electrical conductivity. The strengthening mechanism is based on the precipitation of Ni-Si intermetallic particles in the Cu matrix. In addition, the conductivity is improved.
In general, strength and bending workability are contradictory properties, and it is desired to improve bending workability while maintaining high strength even in Cu—Ni—Si based alloys.
Cu-Ni-Si系合金の曲げ加工性の改善方法として、特許文献1~3に記載されているように結晶方位を制御する方法がある。特許文献1ではEBSD分析の測定結果の{001}<100>の面積割合を50%以上とすることで、特許文献2ではEBSP分析の測定結果の{001}<100>の面積割合を50%以上とし、且つ、層状境界を有さないことで、特許文献3ではEBSD分析の測定結果の{110}<112>の面積割合を20%以下、{121}<111>の面積割合を20%以下、{001}<100>の面積割合を5~60%とすることで、それぞれ曲げ加工性を改善している。
また、特許文献4では加工硬化指数を0.05以上とすることで曲げ成形性を改善している。 As a method for improving the bending workability of the Cu—Ni—Si alloy, there is a method of controlling the crystal orientation as described in Patent Documents 1 to 3. In Patent Document 1, the area ratio of {001} <100> in the measurement result of EBSD analysis is set to 50% or more. In Patent Document 2, the area ratio of {001} <100> in the measurement result of EBSP analysis is 50%. With the above and no layered boundary, in Patent Document 3, the area ratio of {110} <112> in the measurement result of EBSD analysis is 20% or less, and the area ratio of {121} <111> is 20%. Hereinafter, the bendability is improved by setting the area ratio of {001} <100> to 5 to 60%.
Further, in Patent Document 4, bending workability is improved by setting the work hardening index to 0.05 or more.
また、特許文献4では加工硬化指数を0.05以上とすることで曲げ成形性を改善している。 As a method for improving the bending workability of the Cu—Ni—Si alloy, there is a method of controlling the crystal orientation as described in Patent Documents 1 to 3. In Patent Document 1, the area ratio of {001} <100> in the measurement result of EBSD analysis is set to 50% or more. In Patent Document 2, the area ratio of {001} <100> in the measurement result of EBSP analysis is 50%. With the above and no layered boundary, in Patent Document 3, the area ratio of {110} <112> in the measurement result of EBSD analysis is 20% or less, and the area ratio of {121} <111> is 20%. Hereinafter, the bendability is improved by setting the area ratio of {001} <100> to 5 to 60%.
Further, in Patent Document 4, bending workability is improved by setting the work hardening index to 0.05 or more.
本発明者らは、前記先行発明の効果について検証試験を行った。その結果、特許文献3の技術ついて、曲げ加工性を曲げ半径0.15mm(曲げ半径/板厚=1)のW曲げで評価した場合に、一定の改善効果が認められたものの、曲げ半径0.075mm(曲げ半径/板厚=0.5)でW曲げ試験を行ったところ、割れが発生し、曲げ加工性の改善が不充分であることが分かった。そこで、本発明は、コネクタ、端子、リレー、スイッチ等の導電性ばね材として好適な、優れた強度、曲げ加工性を備えたCu-Ni-Si系合金及びその製造方法を提供することを課題とする。
The present inventors conducted a verification test on the effect of the preceding invention. As a result, when the bending workability was evaluated by W bending with a bending radius of 0.15 mm (bending radius / plate thickness = 1) with respect to the technique of Patent Document 3, a certain improvement effect was recognized, but the bending radius was 0. When a W bending test was performed at 0.075 mm (bending radius / plate thickness = 0.5), it was found that cracking occurred and the bending workability was insufficiently improved. Accordingly, the present invention provides a Cu—Ni—Si alloy having excellent strength and bending workability, which is suitable as a conductive spring material for connectors, terminals, relays, switches and the like, and a method for producing the same. And
従来技術では、銅合金の結晶方位を制御することにより、Cu-Ni-Si系合金の曲げ加工性を改善しているが、結晶方位制御だけでなく、さらに加工硬化指数(n値)を制御することにより、優れた曲げ加工性が得られることを見出した。
The conventional technology improves the bending workability of Cu-Ni-Si alloys by controlling the crystal orientation of the copper alloy, but not only controls the crystal orientation but also controls the work hardening index (n value). As a result, it was found that excellent bending workability can be obtained.
以上の知見を背景にして完成した本発明は一側面において、1.0~4.5質量%のNi及び0.2~1.0質量%のSiを含有し、残部が銅及び不可避的不純物からなり、EBSD(Electron Back-Scatter Diffraction:電子後方散乱回折)測定を行い、結晶方位を解析したときに、Cube方位{0 0 1}<1 0 0>の面積率が5%以上、Brass方位{1 1 0}<1 1 2>の面積率が20%以下、Copper方位{1 1 2}<1 1 1>の面積率が20%以下であり、加工硬化指数が0.2以下であるCu-Ni-Si系合金である。
The present invention completed on the basis of the above knowledge, in one aspect, contains 1.0 to 4.5 mass% Ni and 0.2 to 1.0 mass% Si, with the balance being copper and inevitable impurities. When the EBSD (Electron Back-Scatter Diffraction: Electron Backscattering Diffraction) measurement is performed and the crystal orientation is analyzed, the area ratio of the Cube orientation {0 0 1} <1 0 0> is 5% or more, and the Brass orientation The area ratio of {1} 1 0} <1 1 率 2> is 20% or less, the area ratio of Copper orientation {1 1 2} <1 1 1> is 20% or less, and the work hardening index is 0.2 or less. Cu—Ni—Si alloy.
本発明に係るCu-Ni-Si系合金は一実施形態において、Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgのうち1種以上を総量で0.005~2.5質量%含有する。
In one embodiment, the Cu—Ni—Si based alloy according to the present invention includes at least one of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and Ag in a total amount. 0.005 to 2.5 mass% is contained.
また、本発明は別の一側面において、1.0~4.5質量%のNi及び0.2~1.0質量%のSiを含有し、残部が銅及び不可避的不純物からなるインゴットを作製し、前記インゴットを熱間圧延した後、冷間圧延を行い、軟化度0.25~0.75の熱処理を行った後、加工度7~50%の冷間圧延を行い、次いで、溶体化処理を行った後、時効処理及び歪速度1×10-4(1/秒)以下の冷間圧延を任意の順で行う本発明のCu-Ni-Si系合金の製造方法である。
In another aspect of the present invention, an ingot containing 1.0 to 4.5 mass% Ni and 0.2 to 1.0 mass% Si, the balance being copper and inevitable impurities is produced. The ingot is hot-rolled, cold-rolled, heat-treated with a softening degree of 0.25 to 0.75, then cold-rolled with a working degree of 7 to 50%, and then solutionized. This is a method for producing a Cu—Ni—Si based alloy of the present invention, in which after the treatment, aging treatment and cold rolling at a strain rate of 1 × 10 −4 (1 / second) or less are performed in an arbitrary order.
本発明に係るCu-Ni-Si系合金の製造方法は一実施形態において、前記インゴットが、Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgのうち1種以上を総量で0.005~2.5質量%含有する。
In one embodiment of a method for producing a Cu—Ni—Si alloy according to the present invention, the ingot is made of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr, and Ag. One or more of them are contained in a total amount of 0.005 to 2.5% by mass.
本発明は更に別の一側面において、上記銅合金を備えた伸銅品である。
In yet another aspect, the present invention is a copper-drawn product provided with the above copper alloy.
本発明は更に別の一側面において、上記銅合金を備えた電子機器部品である。
In still another aspect, the present invention is an electronic device component including the copper alloy.
本発明によれば、コネクタ、端子、リレー、スイッチ等の導電性ばね材として好適な、優れた強度、曲げ加工性を備えたCu-Ni-Si系合金及びその製造方法を提供することができる。
According to the present invention, it is possible to provide a Cu—Ni—Si alloy having excellent strength and bending workability, which is suitable as a conductive spring material for connectors, terminals, relays, switches and the like, and a method for producing the same. .
(Ni及びSi濃度)
Ni及びSiは、時効処理を行うことにより、Ni2Si等の金属間化合物として析出する。この化合物は強度を向上させ、析出することによりCuマトリックス中に固溶したNi及びSiが減少するため導電率が向上する。しかしながら、Ni濃度が1.0質量%未満又はSi濃度が0.2質量%未満になると所望の強度が得られず、反対にNi濃度が4.5質量%を超えると又はSi濃度が1.0質量%を超えると熱間加工性が劣化する。このため、本発明に係るCu-Ni-Si系合金では、Ni濃度が1.0~4.5質量%、Si濃度が0.2~1.0質量%に制御されている。Ni濃度は1.3~4.0質量%が好ましく、Si濃度は0.3~0.9質量%が好ましい。 (Ni and Si concentration)
Ni and Si are precipitated as an intermetallic compound such as Ni 2 Si by aging treatment. This compound improves the strength, and by precipitation, Ni and Si dissolved in the Cu matrix are reduced, so that the conductivity is improved. However, when the Ni concentration is less than 1.0% by mass or the Si concentration is less than 0.2% by mass, the desired strength cannot be obtained, and conversely, when the Ni concentration exceeds 4.5% by mass or the Si concentration is 1. When it exceeds 0 mass%, hot workability will deteriorate. Therefore, in the Cu—Ni—Si based alloy according to the present invention, the Ni concentration is controlled to 1.0 to 4.5 mass% and the Si concentration is controlled to 0.2 to 1.0 mass%. The Ni concentration is preferably 1.3 to 4.0% by mass, and the Si concentration is preferably 0.3 to 0.9% by mass.
Ni及びSiは、時効処理を行うことにより、Ni2Si等の金属間化合物として析出する。この化合物は強度を向上させ、析出することによりCuマトリックス中に固溶したNi及びSiが減少するため導電率が向上する。しかしながら、Ni濃度が1.0質量%未満又はSi濃度が0.2質量%未満になると所望の強度が得られず、反対にNi濃度が4.5質量%を超えると又はSi濃度が1.0質量%を超えると熱間加工性が劣化する。このため、本発明に係るCu-Ni-Si系合金では、Ni濃度が1.0~4.5質量%、Si濃度が0.2~1.0質量%に制御されている。Ni濃度は1.3~4.0質量%が好ましく、Si濃度は0.3~0.9質量%が好ましい。 (Ni and Si concentration)
Ni and Si are precipitated as an intermetallic compound such as Ni 2 Si by aging treatment. This compound improves the strength, and by precipitation, Ni and Si dissolved in the Cu matrix are reduced, so that the conductivity is improved. However, when the Ni concentration is less than 1.0% by mass or the Si concentration is less than 0.2% by mass, the desired strength cannot be obtained, and conversely, when the Ni concentration exceeds 4.5% by mass or the Si concentration is 1. When it exceeds 0 mass%, hot workability will deteriorate. Therefore, in the Cu—Ni—Si based alloy according to the present invention, the Ni concentration is controlled to 1.0 to 4.5 mass% and the Si concentration is controlled to 0.2 to 1.0 mass%. The Ni concentration is preferably 1.3 to 4.0% by mass, and the Si concentration is preferably 0.3 to 0.9% by mass.
(その他の添加元素)
Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgの添加は強度上昇に寄与する。さらにZnはSnめっきの耐熱剥離性の向上に、Mgは応力緩和特性の向上に、Zr、Cr、Mnは熱間加工性の向上に効果がある。Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgの濃度が総量で0.005質量%未満であると上記の効果は得られず、反対に2.5質量%を超えると導電率が著しく低下して電気・電子部品材料として使用できない。このため、本発明に係るCu-Ni-Si系合金では、これらの元素を総量で0.005~2.5質量%含有することが好ましく、0.1~2.0質量%含有することがより好ましい。 (Other additive elements)
Addition of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr, and Ag contributes to an increase in strength. Furthermore, Zn is effective in improving the heat-resistant peelability of Sn plating, Mg is effective in improving stress relaxation characteristics, and Zr, Cr, and Mn are effective in improving hot workability. If the total concentration of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and Ag is less than 0.005% by mass, the above effect cannot be obtained. If it exceeds 5% by mass, the electrical conductivity is remarkably lowered and it cannot be used as an electric / electronic component material. Therefore, the Cu—Ni—Si based alloy according to the present invention preferably contains these elements in a total amount of 0.005 to 2.5% by mass, and preferably 0.1 to 2.0% by mass. More preferred.
Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgの添加は強度上昇に寄与する。さらにZnはSnめっきの耐熱剥離性の向上に、Mgは応力緩和特性の向上に、Zr、Cr、Mnは熱間加工性の向上に効果がある。Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgの濃度が総量で0.005質量%未満であると上記の効果は得られず、反対に2.5質量%を超えると導電率が著しく低下して電気・電子部品材料として使用できない。このため、本発明に係るCu-Ni-Si系合金では、これらの元素を総量で0.005~2.5質量%含有することが好ましく、0.1~2.0質量%含有することがより好ましい。 (Other additive elements)
Addition of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr, and Ag contributes to an increase in strength. Furthermore, Zn is effective in improving the heat-resistant peelability of Sn plating, Mg is effective in improving stress relaxation characteristics, and Zr, Cr, and Mn are effective in improving hot workability. If the total concentration of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and Ag is less than 0.005% by mass, the above effect cannot be obtained. If it exceeds 5% by mass, the electrical conductivity is remarkably lowered and it cannot be used as an electric / electronic component material. Therefore, the Cu—Ni—Si based alloy according to the present invention preferably contains these elements in a total amount of 0.005 to 2.5% by mass, and preferably 0.1 to 2.0% by mass. More preferred.
(結晶方位)
銅合金では、Cube方位が多くBrass方位及びCopper方位が少ない場合に、不均一な変形が抑制され、曲げ性が向上する。ここで、Cube方位とは、圧延面法線方向(ND)に(0 0 1)面を、圧延方向(RD)に(1 0 0)面を向いている状態であり、{0 0 1}<1 0 0>の指数で示される。Brass方位とは、NDに(1 1 0 )面を、RDに(1 1 2)面を向いている状態であり、{1 1 0}<1 1 2>の指数で示される。Copper方位とは、NDに(1 1 2 )面を、RDに(1 1 1)面を向いている状態であり、{1 1 2}<1 1 1>の指数で示される。
本発明に係るCu-Ni-Si系合金は、Cube方位の面積率が5%以上に制御されている。Cube方位の面積率が5%未満になると曲げ加工性が急激に悪化する。Cube方位の面積率の上限値は、曲げ性の点からは規制されないが、本発明に係るCu-Ni-Si系合金の場合、製造方法を如何に変化させても、Cube方位の面積率が80%を越えることは無い。
本発明に係るCu-Ni-Si系合金は、Copper方位及びBrass方位の面積率がそれぞれ20%以下に制御されている。Copper方位の面積率又はBrass方位の面積率のいずれかが20%を超えると曲げ加工性が急激に悪化する。Copper方位及びBrass方位の面積率の下限値は、曲げ性の点からは規制されないが、本発明に係るCu-Ni-Si系合金の場合、製造方法を如何に変化させても、Copper方位の面積率またはBrass方位の面積率のいずれかが1%未満になることは無い。 (Crystal orientation)
In the copper alloy, when the Cube orientation is large and the Brass orientation and the Copper orientation are small, non-uniform deformation is suppressed and bendability is improved. Here, the Cube orientation is a state in which the (0 0 1) plane is oriented in the rolling surface normal direction (ND) and the (1 0 0) plane is oriented in the rolling direction (RD), and {0 0 1} It is indicated by an index of <1 0 0>. The Brass orientation is a state in which the ND faces the (1 1 0) plane and the RD faces the (1 1 2) plane, and is indicated by an index of {1 1 0} <1 1 2>. The Copper orientation is a state in which the ND faces the (1 1 2) plane and the RD faces the (1 1 1) plane, and is represented by an index of {1 1 2} <1 1 1>.
In the Cu—Ni—Si alloy according to the present invention, the area ratio of the Cube orientation is controlled to 5% or more. When the area ratio of the Cube orientation is less than 5%, the bending workability deteriorates rapidly. The upper limit of the area ratio of the Cube orientation is not restricted in terms of bendability, but in the case of the Cu—Ni—Si based alloy according to the present invention, the area ratio of the Cube orientation is not affected by any change in the manufacturing method. Never exceed 80%.
In the Cu—Ni—Si alloy according to the present invention, the area ratios of the Copper orientation and the Brass orientation are each controlled to 20% or less. If either the Copper azimuth area ratio or the Brass azimuth area ratio exceeds 20%, the bending workability deteriorates rapidly. The lower limits of the area ratio of the Copper orientation and the Brass orientation are not restricted in terms of bendability, but in the case of the Cu—Ni—Si based alloy according to the present invention, no matter how the production method is changed, the Copper orientation Either the area ratio or the area ratio of the Brass orientation is never less than 1%.
銅合金では、Cube方位が多くBrass方位及びCopper方位が少ない場合に、不均一な変形が抑制され、曲げ性が向上する。ここで、Cube方位とは、圧延面法線方向(ND)に(0 0 1)面を、圧延方向(RD)に(1 0 0)面を向いている状態であり、{0 0 1}<1 0 0>の指数で示される。Brass方位とは、NDに(1 1 0 )面を、RDに(1 1 2)面を向いている状態であり、{1 1 0}<1 1 2>の指数で示される。Copper方位とは、NDに(1 1 2 )面を、RDに(1 1 1)面を向いている状態であり、{1 1 2}<1 1 1>の指数で示される。
本発明に係るCu-Ni-Si系合金は、Cube方位の面積率が5%以上に制御されている。Cube方位の面積率が5%未満になると曲げ加工性が急激に悪化する。Cube方位の面積率の上限値は、曲げ性の点からは規制されないが、本発明に係るCu-Ni-Si系合金の場合、製造方法を如何に変化させても、Cube方位の面積率が80%を越えることは無い。
本発明に係るCu-Ni-Si系合金は、Copper方位及びBrass方位の面積率がそれぞれ20%以下に制御されている。Copper方位の面積率又はBrass方位の面積率のいずれかが20%を超えると曲げ加工性が急激に悪化する。Copper方位及びBrass方位の面積率の下限値は、曲げ性の点からは規制されないが、本発明に係るCu-Ni-Si系合金の場合、製造方法を如何に変化させても、Copper方位の面積率またはBrass方位の面積率のいずれかが1%未満になることは無い。 (Crystal orientation)
In the copper alloy, when the Cube orientation is large and the Brass orientation and the Copper orientation are small, non-uniform deformation is suppressed and bendability is improved. Here, the Cube orientation is a state in which the (0 0 1) plane is oriented in the rolling surface normal direction (ND) and the (1 0 0) plane is oriented in the rolling direction (RD), and {0 0 1} It is indicated by an index of <1 0 0>. The Brass orientation is a state in which the ND faces the (1 1 0) plane and the RD faces the (1 1 2) plane, and is indicated by an index of {1 1 0} <1 1 2>. The Copper orientation is a state in which the ND faces the (1 1 2) plane and the RD faces the (1 1 1) plane, and is represented by an index of {1 1 2} <1 1 1>.
In the Cu—Ni—Si alloy according to the present invention, the area ratio of the Cube orientation is controlled to 5% or more. When the area ratio of the Cube orientation is less than 5%, the bending workability deteriorates rapidly. The upper limit of the area ratio of the Cube orientation is not restricted in terms of bendability, but in the case of the Cu—Ni—Si based alloy according to the present invention, the area ratio of the Cube orientation is not affected by any change in the manufacturing method. Never exceed 80%.
In the Cu—Ni—Si alloy according to the present invention, the area ratios of the Copper orientation and the Brass orientation are each controlled to 20% or less. If either the Copper azimuth area ratio or the Brass azimuth area ratio exceeds 20%, the bending workability deteriorates rapidly. The lower limits of the area ratio of the Copper orientation and the Brass orientation are not restricted in terms of bendability, but in the case of the Cu—Ni—Si based alloy according to the present invention, no matter how the production method is changed, the Copper orientation Either the area ratio or the area ratio of the Brass orientation is never less than 1%.
(加工硬化係数)
金属を塑性変形させると、歪が堆積し、加工硬化が起こり、金属の引張強さは上昇する。加工硬化係数(以下、n値)とはこの加工硬化の指標として用いられる値である。n値が大きいほど、その金属は加工硬化による引張強さの上昇が大きいことを示す。
材料をコネクタなどの電子部品に成型するためには、プレス曲げ加工を行わなければならない。プレス曲げ加工を行うと、材料は加工硬化し、その引張強さは上昇する。
一般的に材料の引張強さと曲げ加工性とはトレードオフの関係であり、引張強さが高いほど曲げ加工性は悪い。
従って、材料のプレス曲げ加工に起因した加工硬化による引張強さの上昇を抑制すればプレス曲げ加工時に割れが発生し難い。言い換えると、n値が小さいほど良好な曲げ加工性が得られる。
本発明に係るCu-Ni-Si系合金は、n値が0.2以下に制御されている。n値は、好ましくは0.1以下、さらに好ましくは0.05未満である。n値が0.2を超えると、曲げ加工性が急激に悪化する。n値の下限値は、曲げ性の点からは規制されないが、本発明に係るCu-Ni-Si系合金の場合、製造方法を如何に変化させても、n値が0.01未満になることは無い。 (Work hardening coefficient)
When a metal is plastically deformed, strain accumulates, work hardening occurs, and the tensile strength of the metal increases. The work hardening coefficient (hereinafter, n value) is a value used as an index of this work hardening. A larger n value indicates that the metal has a greater increase in tensile strength due to work hardening.
In order to mold the material into an electronic component such as a connector, press bending must be performed. When press bending is performed, the material is work-hardened and its tensile strength increases.
Generally, the tensile strength and bending workability of a material are in a trade-off relationship, and the higher the tensile strength, the worse the bending workability.
Therefore, if the increase in tensile strength due to work hardening caused by press bending of the material is suppressed, cracks are unlikely to occur during press bending. In other words, the smaller the n value, the better the bending workability can be obtained.
In the Cu—Ni—Si alloy according to the present invention, the n value is controlled to 0.2 or less. n value becomes like this. Preferably it is 0.1 or less, More preferably, it is less than 0.05. When the n value exceeds 0.2, the bending workability deteriorates rapidly. The lower limit of the n value is not restricted in terms of bendability, but in the case of the Cu—Ni—Si alloy according to the present invention, the n value is less than 0.01 no matter how the manufacturing method is changed. There is nothing.
金属を塑性変形させると、歪が堆積し、加工硬化が起こり、金属の引張強さは上昇する。加工硬化係数(以下、n値)とはこの加工硬化の指標として用いられる値である。n値が大きいほど、その金属は加工硬化による引張強さの上昇が大きいことを示す。
材料をコネクタなどの電子部品に成型するためには、プレス曲げ加工を行わなければならない。プレス曲げ加工を行うと、材料は加工硬化し、その引張強さは上昇する。
一般的に材料の引張強さと曲げ加工性とはトレードオフの関係であり、引張強さが高いほど曲げ加工性は悪い。
従って、材料のプレス曲げ加工に起因した加工硬化による引張強さの上昇を抑制すればプレス曲げ加工時に割れが発生し難い。言い換えると、n値が小さいほど良好な曲げ加工性が得られる。
本発明に係るCu-Ni-Si系合金は、n値が0.2以下に制御されている。n値は、好ましくは0.1以下、さらに好ましくは0.05未満である。n値が0.2を超えると、曲げ加工性が急激に悪化する。n値の下限値は、曲げ性の点からは規制されないが、本発明に係るCu-Ni-Si系合金の場合、製造方法を如何に変化させても、n値が0.01未満になることは無い。 (Work hardening coefficient)
When a metal is plastically deformed, strain accumulates, work hardening occurs, and the tensile strength of the metal increases. The work hardening coefficient (hereinafter, n value) is a value used as an index of this work hardening. A larger n value indicates that the metal has a greater increase in tensile strength due to work hardening.
In order to mold the material into an electronic component such as a connector, press bending must be performed. When press bending is performed, the material is work-hardened and its tensile strength increases.
Generally, the tensile strength and bending workability of a material are in a trade-off relationship, and the higher the tensile strength, the worse the bending workability.
Therefore, if the increase in tensile strength due to work hardening caused by press bending of the material is suppressed, cracks are unlikely to occur during press bending. In other words, the smaller the n value, the better the bending workability can be obtained.
In the Cu—Ni—Si alloy according to the present invention, the n value is controlled to 0.2 or less. n value becomes like this. Preferably it is 0.1 or less, More preferably, it is less than 0.05. When the n value exceeds 0.2, the bending workability deteriorates rapidly. The lower limit of the n value is not restricted in terms of bendability, but in the case of the Cu—Ni—Si alloy according to the present invention, the n value is less than 0.01 no matter how the manufacturing method is changed. There is nothing.
(製造方法)
本発明の製造方法としては、まず溶解炉で電気銅、Ni、Si等の原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。その後、熱間圧延、第一の冷間圧延、熱処理、第二の冷間圧延、溶体化処理、時効処理、第三の冷間圧延の順で所望の厚み及び特性を有する条や箔に仕上げる。熱処理、溶体化処理及び時効処理後には、加熱時に生成した表面酸化膜を除去するために、表面の酸洗や研磨等を行ってもよい。時効処理と第三の冷間圧延との順序を入れ替えてもよい。また、高強度化のために、溶体化処理と時効との間に冷間圧延を行ってもよい。さらに、第三の冷間圧延によるばね限界値の低下を回復させるために第三の冷間圧延後に歪取り焼鈍を行ってもよい。
本発明では、前記結晶方位を得るために、溶体化処理の前に、熱処理(以下、予備焼鈍)及び比較的低加工度の第二の冷間圧延を行う。予備焼鈍は、軟化度Sが0.25~0.75になる条件で行う。
図1に本発明に係るCu-Ni-Si系合金を種々の温度で焼鈍したときの焼鈍温度と引張強さとの関係を例示する。熱電対を取り付けた試料を所定の温度に加熱した炉に投入し、熱電対で測定される試料温度が所定の温度に到達したときに、試料を炉から取り出して水冷し、引張強さを測定したものである。試料到達温度が500~700℃の間で再結晶が進行し引張強さが急激に低下している。高温側での引張強さの緩やかな低下は、再結晶粒の成長によるものである。
予備焼鈍における軟化度Sを次式で定義する。
S=(σ0-σ)/(σ0-σ900)
ここで、σ0は予備焼鈍前の引張強さであり、σ及びσ900はそれぞれ予備焼鈍後及び900℃で焼鈍後の引張強さである。900℃という温度は、本発明に係るCu-Ni-Si系合金を900℃で焼鈍すると安定して完全再結晶することから、再結晶後の引張強さを知るための基準温度として採用している。
Sが0.25未満になると、Copper方位の面積率が増大して20%を超え、これに伴いCube方位の面積率の低下も生じる。
Sが0.75を越えると、Brass方位の面積率が増大して20%を超え、これに伴いCube方位の面積率の低下も生じる。
予備焼鈍の温度、時間及び冷却速度は特に制約されず、Sを上記範囲に調整することが肝要である。一般的には、連続焼鈍炉を用いる場合には炉温400~700℃で5秒間~10分間の範囲、バッチ焼鈍炉を用いる場合には炉温350~600℃で30分間~20時間の範囲で行われる。
なお、軟化度Sの0.25~0.75への調整は、次の手順により行うことができる。
(1)予備焼鈍前の材料の引張り試験強さ(σ0)を測定する。
(2)予備焼鈍前の材料を900℃で焼鈍する。具体的には、熱電対を取り付けた材料を950℃の管状炉に挿入し、熱電対で測定される試料温度が900℃に到達したときに、試料を炉から取り出して水冷する。
(3)上記900℃焼鈍後の材料の引張強さ(σ900)を求める。
(4)例えば、σ0が800MPa、σ900が300MPaの場合、軟化度0.25及び0.75に相当する引張強さは、それぞれ675MPa及び425MPaである。
(5)焼鈍後の引張強さが425~675MPaとなるように、焼鈍条件を決定する。
なお、上記工程(2)における「熱電対で測定される試料温度が900℃に到達したときに、試料を炉から取り出して水冷する」は、具体的には、例えば試料を炉内でワイヤーに吊しておき、900℃に到達した時点でワイヤーを切断して下方に設けておいた水槽内に落とすことで水冷するものや、試料温度が900℃に到達した直後に手作業により炉内から素早く取り出して水槽に漬けること等により行う。 (Production method)
In the production method of the present invention, first, raw materials such as electrolytic copper, Ni, and Si are melted in a melting furnace to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. Then, finish into a strip or foil having the desired thickness and characteristics in the order of hot rolling, first cold rolling, heat treatment, second cold rolling, solution treatment, aging treatment, and third cold rolling. . After heat treatment, solution treatment, and aging treatment, pickling or polishing of the surface may be performed in order to remove the surface oxide film generated during heating. The order of the aging treatment and the third cold rolling may be switched. In order to increase the strength, cold rolling may be performed between the solution treatment and aging. Furthermore, strain relief annealing may be performed after the third cold rolling in order to recover the decrease in the spring limit value due to the third cold rolling.
In the present invention, in order to obtain the crystal orientation, heat treatment (hereinafter, pre-annealing) and second cold rolling with a relatively low workability are performed before the solution treatment. The preliminary annealing is performed under the condition that the softening degree S is 0.25 to 0.75.
FIG. 1 illustrates the relationship between the annealing temperature and the tensile strength when the Cu—Ni—Si alloy according to the present invention is annealed at various temperatures. A sample with a thermocouple attached is placed in a furnace heated to a specified temperature, and when the sample temperature measured by the thermocouple reaches the specified temperature, the sample is removed from the furnace and cooled with water, and the tensile strength is measured. It is a thing. Recrystallization progresses when the sample arrival temperature is 500 to 700 ° C., and the tensile strength is rapidly reduced. The gradual decrease in tensile strength on the high temperature side is due to the growth of recrystallized grains.
The softening degree S in the pre-annealing is defined by the following equation.
S = (σ 0 −σ) / (σ 0 −σ 900 )
Here, σ 0 is the tensile strength before pre-annealing, and σ and σ 900 are the tensile strength after pre-annealing and after annealing at 900 ° C., respectively. The temperature of 900 ° C. is adopted as a reference temperature for knowing the tensile strength after recrystallization because the Cu—Ni—Si alloy according to the present invention is stably recrystallized when annealed at 900 ° C. Yes.
When S is less than 0.25, the area ratio of the Copper orientation increases to exceed 20%, and accordingly, the area ratio of the Cube orientation also decreases.
When S exceeds 0.75, the area ratio of the Brass orientation increases and exceeds 20%, and accordingly, the area ratio of the Cube orientation also decreases.
The temperature, time and cooling rate of the pre-annealing are not particularly limited, and it is important to adjust S to the above range. Generally, when a continuous annealing furnace is used, the furnace temperature ranges from 400 to 700 ° C. for 5 seconds to 10 minutes, and when a batch annealing furnace is used, the furnace temperature ranges from 350 to 600 ° C. for 30 minutes to 20 hours. Done in
The softening degree S can be adjusted to 0.25 to 0.75 by the following procedure.
(1) Measure the tensile test strength (σ 0 ) of the material before pre-annealing.
(2) The material before preliminary annealing is annealed at 900 ° C. Specifically, the material to which the thermocouple is attached is inserted into a tubular furnace at 950 ° C., and when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and cooled with water.
(3) Obtain the tensile strength (σ 900 ) of the material after annealing at 900 ° C.
(4) For example, when σ 0 is 800 MPa and σ 900 is 300 MPa, the tensile strengths corresponding to the softening degrees of 0.25 and 0.75 are 675 MPa and 425 MPa, respectively.
(5) The annealing conditions are determined so that the tensile strength after annealing is 425 to 675 MPa.
In the above step (2), “when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and water-cooled” is specifically, for example, the sample is wired in the furnace. When suspended, the wire is cut when it reaches 900 ° C. and dropped into a water tank provided below, or immediately after the sample temperature reaches 900 ° C. by hand from inside the furnace. Take it out quickly by immersing it in a water tank.
本発明の製造方法としては、まず溶解炉で電気銅、Ni、Si等の原料を溶解し、所望の組成の溶湯を得る。そして、この溶湯をインゴットに鋳造する。その後、熱間圧延、第一の冷間圧延、熱処理、第二の冷間圧延、溶体化処理、時効処理、第三の冷間圧延の順で所望の厚み及び特性を有する条や箔に仕上げる。熱処理、溶体化処理及び時効処理後には、加熱時に生成した表面酸化膜を除去するために、表面の酸洗や研磨等を行ってもよい。時効処理と第三の冷間圧延との順序を入れ替えてもよい。また、高強度化のために、溶体化処理と時効との間に冷間圧延を行ってもよい。さらに、第三の冷間圧延によるばね限界値の低下を回復させるために第三の冷間圧延後に歪取り焼鈍を行ってもよい。
本発明では、前記結晶方位を得るために、溶体化処理の前に、熱処理(以下、予備焼鈍)及び比較的低加工度の第二の冷間圧延を行う。予備焼鈍は、軟化度Sが0.25~0.75になる条件で行う。
図1に本発明に係るCu-Ni-Si系合金を種々の温度で焼鈍したときの焼鈍温度と引張強さとの関係を例示する。熱電対を取り付けた試料を所定の温度に加熱した炉に投入し、熱電対で測定される試料温度が所定の温度に到達したときに、試料を炉から取り出して水冷し、引張強さを測定したものである。試料到達温度が500~700℃の間で再結晶が進行し引張強さが急激に低下している。高温側での引張強さの緩やかな低下は、再結晶粒の成長によるものである。
予備焼鈍における軟化度Sを次式で定義する。
S=(σ0-σ)/(σ0-σ900)
ここで、σ0は予備焼鈍前の引張強さであり、σ及びσ900はそれぞれ予備焼鈍後及び900℃で焼鈍後の引張強さである。900℃という温度は、本発明に係るCu-Ni-Si系合金を900℃で焼鈍すると安定して完全再結晶することから、再結晶後の引張強さを知るための基準温度として採用している。
Sが0.25未満になると、Copper方位の面積率が増大して20%を超え、これに伴いCube方位の面積率の低下も生じる。
Sが0.75を越えると、Brass方位の面積率が増大して20%を超え、これに伴いCube方位の面積率の低下も生じる。
予備焼鈍の温度、時間及び冷却速度は特に制約されず、Sを上記範囲に調整することが肝要である。一般的には、連続焼鈍炉を用いる場合には炉温400~700℃で5秒間~10分間の範囲、バッチ焼鈍炉を用いる場合には炉温350~600℃で30分間~20時間の範囲で行われる。
なお、軟化度Sの0.25~0.75への調整は、次の手順により行うことができる。
(1)予備焼鈍前の材料の引張り試験強さ(σ0)を測定する。
(2)予備焼鈍前の材料を900℃で焼鈍する。具体的には、熱電対を取り付けた材料を950℃の管状炉に挿入し、熱電対で測定される試料温度が900℃に到達したときに、試料を炉から取り出して水冷する。
(3)上記900℃焼鈍後の材料の引張強さ(σ900)を求める。
(4)例えば、σ0が800MPa、σ900が300MPaの場合、軟化度0.25及び0.75に相当する引張強さは、それぞれ675MPa及び425MPaである。
(5)焼鈍後の引張強さが425~675MPaとなるように、焼鈍条件を決定する。
なお、上記工程(2)における「熱電対で測定される試料温度が900℃に到達したときに、試料を炉から取り出して水冷する」は、具体的には、例えば試料を炉内でワイヤーに吊しておき、900℃に到達した時点でワイヤーを切断して下方に設けておいた水槽内に落とすことで水冷するものや、試料温度が900℃に到達した直後に手作業により炉内から素早く取り出して水槽に漬けること等により行う。 (Production method)
In the production method of the present invention, first, raw materials such as electrolytic copper, Ni, and Si are melted in a melting furnace to obtain a molten metal having a desired composition. Then, this molten metal is cast into an ingot. Then, finish into a strip or foil having the desired thickness and characteristics in the order of hot rolling, first cold rolling, heat treatment, second cold rolling, solution treatment, aging treatment, and third cold rolling. . After heat treatment, solution treatment, and aging treatment, pickling or polishing of the surface may be performed in order to remove the surface oxide film generated during heating. The order of the aging treatment and the third cold rolling may be switched. In order to increase the strength, cold rolling may be performed between the solution treatment and aging. Furthermore, strain relief annealing may be performed after the third cold rolling in order to recover the decrease in the spring limit value due to the third cold rolling.
In the present invention, in order to obtain the crystal orientation, heat treatment (hereinafter, pre-annealing) and second cold rolling with a relatively low workability are performed before the solution treatment. The preliminary annealing is performed under the condition that the softening degree S is 0.25 to 0.75.
FIG. 1 illustrates the relationship between the annealing temperature and the tensile strength when the Cu—Ni—Si alloy according to the present invention is annealed at various temperatures. A sample with a thermocouple attached is placed in a furnace heated to a specified temperature, and when the sample temperature measured by the thermocouple reaches the specified temperature, the sample is removed from the furnace and cooled with water, and the tensile strength is measured. It is a thing. Recrystallization progresses when the sample arrival temperature is 500 to 700 ° C., and the tensile strength is rapidly reduced. The gradual decrease in tensile strength on the high temperature side is due to the growth of recrystallized grains.
The softening degree S in the pre-annealing is defined by the following equation.
S = (σ 0 −σ) / (σ 0 −σ 900 )
Here, σ 0 is the tensile strength before pre-annealing, and σ and σ 900 are the tensile strength after pre-annealing and after annealing at 900 ° C., respectively. The temperature of 900 ° C. is adopted as a reference temperature for knowing the tensile strength after recrystallization because the Cu—Ni—Si alloy according to the present invention is stably recrystallized when annealed at 900 ° C. Yes.
When S is less than 0.25, the area ratio of the Copper orientation increases to exceed 20%, and accordingly, the area ratio of the Cube orientation also decreases.
When S exceeds 0.75, the area ratio of the Brass orientation increases and exceeds 20%, and accordingly, the area ratio of the Cube orientation also decreases.
The temperature, time and cooling rate of the pre-annealing are not particularly limited, and it is important to adjust S to the above range. Generally, when a continuous annealing furnace is used, the furnace temperature ranges from 400 to 700 ° C. for 5 seconds to 10 minutes, and when a batch annealing furnace is used, the furnace temperature ranges from 350 to 600 ° C. for 30 minutes to 20 hours. Done in
The softening degree S can be adjusted to 0.25 to 0.75 by the following procedure.
(1) Measure the tensile test strength (σ 0 ) of the material before pre-annealing.
(2) The material before preliminary annealing is annealed at 900 ° C. Specifically, the material to which the thermocouple is attached is inserted into a tubular furnace at 950 ° C., and when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and cooled with water.
(3) Obtain the tensile strength (σ 900 ) of the material after annealing at 900 ° C.
(4) For example, when σ 0 is 800 MPa and σ 900 is 300 MPa, the tensile strengths corresponding to the softening degrees of 0.25 and 0.75 are 675 MPa and 425 MPa, respectively.
(5) The annealing conditions are determined so that the tensile strength after annealing is 425 to 675 MPa.
In the above step (2), “when the sample temperature measured by the thermocouple reaches 900 ° C., the sample is taken out of the furnace and water-cooled” is specifically, for example, the sample is wired in the furnace. When suspended, the wire is cut when it reaches 900 ° C. and dropped into a water tank provided below, or immediately after the sample temperature reaches 900 ° C. by hand from inside the furnace. Take it out quickly by immersing it in a water tank.
上記焼鈍の後、溶体化処理に先立ち、加工度Rを7~50%とする第二の冷間圧延を行う。加工度R(%)は、
R=(t0-t)/t0×100
(t0:圧延前の板厚、t:圧延後の板厚)
で定義する。
加工度Rがこの範囲から外れるとCube方位の面積率が5%未満になる。
さらに、n値を0.2以下に制御するために第三の冷間圧延の歪速度を1×10-4(1/秒)以下に制御する。本発明の歪速度とは、圧延速度/ロール接触弧長として特定され、歪速度を低下させるためには、圧延速度を遅くする、圧延のパス回数を増やしロール接触弧長を長くする等が効果的である。歪速度の下限値は、n値の点からは制限されないが、1×10-5(1/秒)を下回るような圧延を行うと、その圧延時間が長く工業的には好ましくない。一般的な工業における圧延の歪速度は2×10-4~5×10-4(1/秒)程度である。 After the annealing, prior to the solution treatment, a second cold rolling with a working degree R of 7 to 50% is performed. Degree of processing R (%)
R = (t 0 −t) / t 0 × 100
(T 0 : thickness before rolling, t: thickness after rolling)
Define in.
When the processing degree R is out of this range, the area ratio of the Cube orientation becomes less than 5%.
Further, in order to control the n value to 0.2 or less, the strain rate of the third cold rolling is controlled to 1 × 10 −4 (1 / second) or less. The strain rate of the present invention is specified as rolling speed / roll contact arc length, and in order to lower the strain rate, it is effective to slow the rolling speed, increase the number of rolling passes, and lengthen the roll contact arc length. Is. The lower limit of the strain rate is not limited from the point of the n value, but if rolling is performed below 1 × 10 −5 (1 / second), the rolling time is long, which is not industrially preferable. The strain rate of rolling in a general industry is about 2 × 10 −4 to 5 × 10 −4 (1 / second).
R=(t0-t)/t0×100
(t0:圧延前の板厚、t:圧延後の板厚)
で定義する。
加工度Rがこの範囲から外れるとCube方位の面積率が5%未満になる。
さらに、n値を0.2以下に制御するために第三の冷間圧延の歪速度を1×10-4(1/秒)以下に制御する。本発明の歪速度とは、圧延速度/ロール接触弧長として特定され、歪速度を低下させるためには、圧延速度を遅くする、圧延のパス回数を増やしロール接触弧長を長くする等が効果的である。歪速度の下限値は、n値の点からは制限されないが、1×10-5(1/秒)を下回るような圧延を行うと、その圧延時間が長く工業的には好ましくない。一般的な工業における圧延の歪速度は2×10-4~5×10-4(1/秒)程度である。 After the annealing, prior to the solution treatment, a second cold rolling with a working degree R of 7 to 50% is performed. Degree of processing R (%)
R = (t 0 −t) / t 0 × 100
(T 0 : thickness before rolling, t: thickness after rolling)
Define in.
When the processing degree R is out of this range, the area ratio of the Cube orientation becomes less than 5%.
Further, in order to control the n value to 0.2 or less, the strain rate of the third cold rolling is controlled to 1 × 10 −4 (1 / second) or less. The strain rate of the present invention is specified as rolling speed / roll contact arc length, and in order to lower the strain rate, it is effective to slow the rolling speed, increase the number of rolling passes, and lengthen the roll contact arc length. Is. The lower limit of the strain rate is not limited from the point of the n value, but if rolling is performed below 1 × 10 −5 (1 / second), the rolling time is long, which is not industrially preferable. The strain rate of rolling in a general industry is about 2 × 10 −4 to 5 × 10 −4 (1 / second).
本発明に係る合金の製造方法を工程順に列記すると次のようになる。
(1)インゴットの鋳造
(2)熱間圧延(温度800~1000℃、厚み5~20mm程度まで)
(3)冷間圧延(加工度30~99%)
(4)予備焼鈍(軟化度S=0.25~0.75)
(5)軽圧延(加工度7~50%)
(6)溶体化処理(700~900℃で5~300秒間)
(7)冷間圧延(加工度1~60%、歪速度1×10-4(1/秒)以下)
(8)時効処理(350~550℃で2~20時間)
(9)冷間圧延(加工度1~50%、歪速度1×10-4(1/秒)以下)
(10)歪取り焼鈍(300~700℃で5秒~10時間)
ここで、冷間圧延(3)の加工度は30~99%とすることが好ましい。予備焼鈍(4)で部分的に再結晶粒を生成させるためには、冷間圧延(3)で歪を導入しておく必要があり、30%以上の加工度で有効な歪が得られる。一方、加工度が99%を超えると、圧延材のエッジ等に割れが発生し、圧延中の材料が破断することがある。
冷間圧延(7)及び(9)は高強度化ならびにn値の制御のために任意に行うものであり、圧延加工度の増加とともに強度が増加する反面、曲げ性が低下する。冷間圧延(7)及び(9)の加工度によらず、本発明の効果は得られる。ただし、冷間圧延(7)及び(9)におけるそれぞれの加工度が上記上限値を超えることは曲げ性の点から好ましくなく、それぞれの加工度が上記下限値を下回ることは高強度化の効果の点から好ましくない。また、n値を制御するため、冷間圧延(7)または冷間圧延(9)の少なくともいずれか一方の冷間圧延を行う必要が有る。
歪取り焼鈍(10)は、冷間圧延(9)を行う場合にこの冷間圧延で低下するばね限界値等を回復させるために任意に行うものである。歪取り焼鈍(10)の有無に関わらず、本発明の効果は得られる。歪取り焼鈍(10)は行ってもよいし行わなくてもよい。
なお、工程(2)、(6)及び(8)については、Cu-Ni-Si系合金の一般的な製造条件を選択すればよい。 It is as follows when the manufacturing method of the alloy which concerns on this invention is listed in process order.
(1) Ingot casting (2) Hot rolling (temperature 800-1000 ° C, thickness 5-20mm)
(3) Cold rolling (working degree 30-99%)
(4) Pre-annealing (softening degree S = 0.25 to 0.75)
(5) Light rolling (working degree 7-50%)
(6) Solution treatment (700 to 900 ° C. for 5 to 300 seconds)
(7) Cold rolling (working degree 1-60%, strain rate 1 × 10 -4 (1 / second) or less)
(8) Aging treatment (350 to 550 ° C for 2 to 20 hours)
(9) Cold rolling (working degree 1-50%, strain rate 1 × 10 -4 (1 / second) or less)
(10) Strain relief annealing (300 to 700 ° C for 5 seconds to 10 hours)
Here, the working degree of cold rolling (3) is preferably 30 to 99%. In order to generate recrystallized grains partially by pre-annealing (4), it is necessary to introduce strain by cold rolling (3), and effective strain can be obtained at a workability of 30% or more. On the other hand, if the degree of work exceeds 99%, cracks may occur at the edges of the rolled material and the material being rolled may break.
Cold rolling (7) and (9) is arbitrarily performed for increasing the strength and controlling the n value, and the strength increases with an increase in the rolling degree, but the bendability decreases. The effects of the present invention can be obtained regardless of the degree of cold rolling (7) and (9). However, it is not preferable from the viewpoint of bendability that the respective working degrees in the cold rolling (7) and (9) exceed the above upper limit value, and the fact that each working degree is below the above lower limit effect of increasing the strength. From the point of view, it is not preferable. Further, in order to control the n value, it is necessary to perform at least one of cold rolling (7) and cold rolling (9).
The strain relief annealing (10) is optionally performed in order to recover the spring limit value and the like which are lowered by the cold rolling when the cold rolling (9) is performed. The effect of the present invention can be obtained regardless of the presence or absence of strain relief annealing (10). The strain relief annealing (10) may or may not be performed.
For the steps (2), (6) and (8), general production conditions for the Cu—Ni—Si based alloy may be selected.
(1)インゴットの鋳造
(2)熱間圧延(温度800~1000℃、厚み5~20mm程度まで)
(3)冷間圧延(加工度30~99%)
(4)予備焼鈍(軟化度S=0.25~0.75)
(5)軽圧延(加工度7~50%)
(6)溶体化処理(700~900℃で5~300秒間)
(7)冷間圧延(加工度1~60%、歪速度1×10-4(1/秒)以下)
(8)時効処理(350~550℃で2~20時間)
(9)冷間圧延(加工度1~50%、歪速度1×10-4(1/秒)以下)
(10)歪取り焼鈍(300~700℃で5秒~10時間)
ここで、冷間圧延(3)の加工度は30~99%とすることが好ましい。予備焼鈍(4)で部分的に再結晶粒を生成させるためには、冷間圧延(3)で歪を導入しておく必要があり、30%以上の加工度で有効な歪が得られる。一方、加工度が99%を超えると、圧延材のエッジ等に割れが発生し、圧延中の材料が破断することがある。
冷間圧延(7)及び(9)は高強度化ならびにn値の制御のために任意に行うものであり、圧延加工度の増加とともに強度が増加する反面、曲げ性が低下する。冷間圧延(7)及び(9)の加工度によらず、本発明の効果は得られる。ただし、冷間圧延(7)及び(9)におけるそれぞれの加工度が上記上限値を超えることは曲げ性の点から好ましくなく、それぞれの加工度が上記下限値を下回ることは高強度化の効果の点から好ましくない。また、n値を制御するため、冷間圧延(7)または冷間圧延(9)の少なくともいずれか一方の冷間圧延を行う必要が有る。
歪取り焼鈍(10)は、冷間圧延(9)を行う場合にこの冷間圧延で低下するばね限界値等を回復させるために任意に行うものである。歪取り焼鈍(10)の有無に関わらず、本発明の効果は得られる。歪取り焼鈍(10)は行ってもよいし行わなくてもよい。
なお、工程(2)、(6)及び(8)については、Cu-Ni-Si系合金の一般的な製造条件を選択すればよい。 It is as follows when the manufacturing method of the alloy which concerns on this invention is listed in process order.
(1) Ingot casting (2) Hot rolling (temperature 800-1000 ° C, thickness 5-20mm)
(3) Cold rolling (working degree 30-99%)
(4) Pre-annealing (softening degree S = 0.25 to 0.75)
(5) Light rolling (working degree 7-50%)
(6) Solution treatment (700 to 900 ° C. for 5 to 300 seconds)
(7) Cold rolling (working degree 1-60%, strain rate 1 × 10 -4 (1 / second) or less)
(8) Aging treatment (350 to 550 ° C for 2 to 20 hours)
(9) Cold rolling (working degree 1-50%, strain rate 1 × 10 -4 (1 / second) or less)
(10) Strain relief annealing (300 to 700 ° C for 5 seconds to 10 hours)
Here, the working degree of cold rolling (3) is preferably 30 to 99%. In order to generate recrystallized grains partially by pre-annealing (4), it is necessary to introduce strain by cold rolling (3), and effective strain can be obtained at a workability of 30% or more. On the other hand, if the degree of work exceeds 99%, cracks may occur at the edges of the rolled material and the material being rolled may break.
Cold rolling (7) and (9) is arbitrarily performed for increasing the strength and controlling the n value, and the strength increases with an increase in the rolling degree, but the bendability decreases. The effects of the present invention can be obtained regardless of the degree of cold rolling (7) and (9). However, it is not preferable from the viewpoint of bendability that the respective working degrees in the cold rolling (7) and (9) exceed the above upper limit value, and the fact that each working degree is below the above lower limit effect of increasing the strength. From the point of view, it is not preferable. Further, in order to control the n value, it is necessary to perform at least one of cold rolling (7) and cold rolling (9).
The strain relief annealing (10) is optionally performed in order to recover the spring limit value and the like which are lowered by the cold rolling when the cold rolling (9) is performed. The effect of the present invention can be obtained regardless of the presence or absence of strain relief annealing (10). The strain relief annealing (10) may or may not be performed.
For the steps (2), (6) and (8), general production conditions for the Cu—Ni—Si based alloy may be selected.
本発明に係るCu-Ni-Si系合金は種々の伸銅品、例えば板、条及び箔に加工することができ、更に、本発明に係るCu-Ni-Si系合金は、リードフレーム、コネクタ、ピン、端子、リレー、スイッチ、二次電池用箔材等の電子機器部品等に使用することができる。
また、本発明に係るCu-Ni-Si系合金の最終板厚(製品板厚)は特に限定されないが、一般的に上記製品用途の場合、0.05~1.0mmである。 The Cu—Ni—Si based alloy according to the present invention can be processed into various copper products, such as plates, strips and foils. Furthermore, the Cu—Ni—Si based alloy according to the present invention can be used for lead frames and connectors. It can be used for electronic parts such as pins, terminals, relays, switches, and foil materials for secondary batteries.
Further, the final plate thickness (product plate thickness) of the Cu—Ni—Si alloy according to the present invention is not particularly limited, but is generally 0.05 to 1.0 mm in the case of the above product use.
また、本発明に係るCu-Ni-Si系合金の最終板厚(製品板厚)は特に限定されないが、一般的に上記製品用途の場合、0.05~1.0mmである。 The Cu—Ni—Si based alloy according to the present invention can be processed into various copper products, such as plates, strips and foils. Furthermore, the Cu—Ni—Si based alloy according to the present invention can be used for lead frames and connectors. It can be used for electronic parts such as pins, terminals, relays, switches, and foil materials for secondary batteries.
Further, the final plate thickness (product plate thickness) of the Cu—Ni—Si alloy according to the present invention is not particularly limited, but is generally 0.05 to 1.0 mm in the case of the above product use.
以下に本発明の実施例を比較例と共に示すが、これらの実施例は本発明及びその利点をよりよく理解するために提供するものであり、発明が限定されることを意図するものではない。
EXAMPLES Examples of the present invention will be described below together with comparative examples, but these examples are provided for better understanding of the present invention and its advantages, and are not intended to limit the invention.
(実施例1)
Ni:2.6質量%、Si:0.58質量%、Sn:0.5質量%、及び、Zn:0.4質量%を含有し残部が銅及び不可避的不純物からなる合金を実験材料とし、予備焼鈍、第二の冷間圧延の加工度及び第三の冷間圧延の歪速度と結晶方位及びn値との関係、さらに結晶方位及びn値が製品の曲げ性に及ぼす影響を検討した。
高周波溶解炉にてアルゴン雰囲気中で内径60mm、深さ200mmの黒鉛るつぼを用い、電気銅2.5kgを溶解した。上記合金組成が得られるよう合金元素を添加し、溶湯温度を1300℃に調整した後、鋳鉄製の鋳型に鋳込み、厚さ30mm、幅60mm、長さ120mmのインゴットを製造した。このインゴットを950℃で3時間加熱し、厚さ10mmまで熱間圧延した。熱間圧延板表面の酸化スケールをグラインダーで研削し除去した。研削後の厚みは9mmであった。その後、次の工程順で圧延及び熱処理を施し、板厚0.15mmの製品試料を作製した。
(1)第一の冷間圧延:第二の冷間圧延の圧延加工度に応じ、所定の厚みまで冷間圧延した。
(2)予備焼鈍:所定温度に調整した電気炉に試料を挿入し、所定時間保持した後、試料を水槽に入れ冷却(水冷)、又は、試料を大気中に放置し冷却(空冷)の2通りの条件で冷却した。
(3)第二の冷間圧延:種々の圧延加工度で、厚み0.18mmまで冷間圧延を行った。
(4)溶体化処理:800℃に調整した電気炉に試料を挿入し、10秒間保持した後、試料を水槽に入れ冷却した。
(5)時効処理:電気炉を用い450℃で5時間、Ar雰囲気中で加熱した。
(6)第三の冷間圧延:種々の歪速度で、0.18mmから0.15mmまで加工度17%で冷間圧延した。
(7)歪取り焼鈍:400℃に調整した電気炉に試料を挿入し、10秒間保持した後、試料を大気中に放置し冷却した。
予備焼鈍後の試料及び製品試料(この場合は歪取り焼鈍上がり)について、次の評価を行った。 (Example 1)
An alloy containing Ni: 2.6% by mass, Si: 0.58% by mass, Sn: 0.5% by mass, and Zn: 0.4% by mass with the balance being copper and inevitable impurities is used as an experimental material. , Pre-annealing, workability of the second cold rolling and the relationship between the strain rate of the third cold rolling and the crystal orientation and n value, and the influence of the crystal orientation and n value on the bendability of the product .
In a high-frequency melting furnace, 2.5 kg of electrolytic copper was melted using a graphite crucible having an inner diameter of 60 mm and a depth of 200 mm in an argon atmosphere. Alloy elements were added to obtain the above alloy composition, the melt temperature was adjusted to 1300 ° C., and then cast into a cast iron mold to produce an ingot having a thickness of 30 mm, a width of 60 mm, and a length of 120 mm. This ingot was heated at 950 ° C. for 3 hours and hot-rolled to a thickness of 10 mm. The oxidized scale on the surface of the hot rolled plate was removed by grinding with a grinder. The thickness after grinding was 9 mm. Thereafter, rolling and heat treatment were performed in the following order of steps to produce a product sample having a thickness of 0.15 mm.
(1) First cold rolling: Cold rolling was performed to a predetermined thickness in accordance with the rolling degree of the second cold rolling.
(2) Pre-annealing: Insert a sample into an electric furnace adjusted to a predetermined temperature and hold it for a predetermined time, then place the sample in a water bath for cooling (water cooling), or leave the sample in the atmosphere for cooling (air cooling) 2 Cooled under street conditions.
(3) Second cold rolling: Cold rolling was performed at various rolling degrees to a thickness of 0.18 mm.
(4) Solution treatment: The sample was inserted into an electric furnace adjusted to 800 ° C. and held for 10 seconds, and then the sample was placed in a water bath and cooled.
(5) Aging treatment: Heated in an Ar atmosphere at 450 ° C. for 5 hours using an electric furnace.
(6) Third cold rolling: Cold rolling was performed at various strain rates from 0.18 mm to 0.15 mm at a working degree of 17%.
(7) Strain relief annealing: The sample was inserted into an electric furnace adjusted to 400 ° C. and held for 10 seconds, and then the sample was left in the air and cooled.
The following evaluation was performed on the sample after the preliminary annealing and the product sample (in this case, the strain relief annealing was completed).
Ni:2.6質量%、Si:0.58質量%、Sn:0.5質量%、及び、Zn:0.4質量%を含有し残部が銅及び不可避的不純物からなる合金を実験材料とし、予備焼鈍、第二の冷間圧延の加工度及び第三の冷間圧延の歪速度と結晶方位及びn値との関係、さらに結晶方位及びn値が製品の曲げ性に及ぼす影響を検討した。
高周波溶解炉にてアルゴン雰囲気中で内径60mm、深さ200mmの黒鉛るつぼを用い、電気銅2.5kgを溶解した。上記合金組成が得られるよう合金元素を添加し、溶湯温度を1300℃に調整した後、鋳鉄製の鋳型に鋳込み、厚さ30mm、幅60mm、長さ120mmのインゴットを製造した。このインゴットを950℃で3時間加熱し、厚さ10mmまで熱間圧延した。熱間圧延板表面の酸化スケールをグラインダーで研削し除去した。研削後の厚みは9mmであった。その後、次の工程順で圧延及び熱処理を施し、板厚0.15mmの製品試料を作製した。
(1)第一の冷間圧延:第二の冷間圧延の圧延加工度に応じ、所定の厚みまで冷間圧延した。
(2)予備焼鈍:所定温度に調整した電気炉に試料を挿入し、所定時間保持した後、試料を水槽に入れ冷却(水冷)、又は、試料を大気中に放置し冷却(空冷)の2通りの条件で冷却した。
(3)第二の冷間圧延:種々の圧延加工度で、厚み0.18mmまで冷間圧延を行った。
(4)溶体化処理:800℃に調整した電気炉に試料を挿入し、10秒間保持した後、試料を水槽に入れ冷却した。
(5)時効処理:電気炉を用い450℃で5時間、Ar雰囲気中で加熱した。
(6)第三の冷間圧延:種々の歪速度で、0.18mmから0.15mmまで加工度17%で冷間圧延した。
(7)歪取り焼鈍:400℃に調整した電気炉に試料を挿入し、10秒間保持した後、試料を大気中に放置し冷却した。
予備焼鈍後の試料及び製品試料(この場合は歪取り焼鈍上がり)について、次の評価を行った。 (Example 1)
An alloy containing Ni: 2.6% by mass, Si: 0.58% by mass, Sn: 0.5% by mass, and Zn: 0.4% by mass with the balance being copper and inevitable impurities is used as an experimental material. , Pre-annealing, workability of the second cold rolling and the relationship between the strain rate of the third cold rolling and the crystal orientation and n value, and the influence of the crystal orientation and n value on the bendability of the product .
In a high-frequency melting furnace, 2.5 kg of electrolytic copper was melted using a graphite crucible having an inner diameter of 60 mm and a depth of 200 mm in an argon atmosphere. Alloy elements were added to obtain the above alloy composition, the melt temperature was adjusted to 1300 ° C., and then cast into a cast iron mold to produce an ingot having a thickness of 30 mm, a width of 60 mm, and a length of 120 mm. This ingot was heated at 950 ° C. for 3 hours and hot-rolled to a thickness of 10 mm. The oxidized scale on the surface of the hot rolled plate was removed by grinding with a grinder. The thickness after grinding was 9 mm. Thereafter, rolling and heat treatment were performed in the following order of steps to produce a product sample having a thickness of 0.15 mm.
(1) First cold rolling: Cold rolling was performed to a predetermined thickness in accordance with the rolling degree of the second cold rolling.
(2) Pre-annealing: Insert a sample into an electric furnace adjusted to a predetermined temperature and hold it for a predetermined time, then place the sample in a water bath for cooling (water cooling), or leave the sample in the atmosphere for cooling (air cooling) 2 Cooled under street conditions.
(3) Second cold rolling: Cold rolling was performed at various rolling degrees to a thickness of 0.18 mm.
(4) Solution treatment: The sample was inserted into an electric furnace adjusted to 800 ° C. and held for 10 seconds, and then the sample was placed in a water bath and cooled.
(5) Aging treatment: Heated in an Ar atmosphere at 450 ° C. for 5 hours using an electric furnace.
(6) Third cold rolling: Cold rolling was performed at various strain rates from 0.18 mm to 0.15 mm at a working degree of 17%.
(7) Strain relief annealing: The sample was inserted into an electric furnace adjusted to 400 ° C. and held for 10 seconds, and then the sample was left in the air and cooled.
The following evaluation was performed on the sample after the preliminary annealing and the product sample (in this case, the strain relief annealing was completed).
(予備焼鈍での軟化度評価)
予備焼鈍前及び予備焼鈍後の試料につき、引張試験機を用いてJIS Z 2241に準拠して圧延方向と平行に引張強さを測定し、それぞれの値をσ0及びσとした。また、900℃焼鈍試料を前記手順(950℃の炉に挿入し試料が900℃に到達したときに水冷)で作製し、圧延方向と平行に引張強さを同様に測定してσ900を求めた。σ0、σ、σ900から、次式により軟化度Sを求めた。
S=(σ0-σ)/(σ0-σ900) (Evaluation of softening degree in preliminary annealing)
About the sample before pre-annealing and after pre-annealing, the tensile strength was measured in parallel with the rolling direction using a tensile tester according to JIS Z 2241, and the respective values were taken as σ 0 and σ. In addition, a 900 ° C. annealed sample was prepared by the above procedure (water cooling when the sample reached 900 ° C. when inserted in a furnace at 950 ° C.), and the tensile strength was measured in parallel with the rolling direction to obtain σ 900 . It was. From σ 0 , σ, and σ 900 , the degree of softening S was determined by the following equation.
S = (σ 0 −σ) / (σ 0 −σ 900 )
予備焼鈍前及び予備焼鈍後の試料につき、引張試験機を用いてJIS Z 2241に準拠して圧延方向と平行に引張強さを測定し、それぞれの値をσ0及びσとした。また、900℃焼鈍試料を前記手順(950℃の炉に挿入し試料が900℃に到達したときに水冷)で作製し、圧延方向と平行に引張強さを同様に測定してσ900を求めた。σ0、σ、σ900から、次式により軟化度Sを求めた。
S=(σ0-σ)/(σ0-σ900) (Evaluation of softening degree in preliminary annealing)
About the sample before pre-annealing and after pre-annealing, the tensile strength was measured in parallel with the rolling direction using a tensile tester according to JIS Z 2241, and the respective values were taken as σ 0 and σ. In addition, a 900 ° C. annealed sample was prepared by the above procedure (water cooling when the sample reached 900 ° C. when inserted in a furnace at 950 ° C.), and the tensile strength was measured in parallel with the rolling direction to obtain σ 900 . It was. From σ 0 , σ, and σ 900 , the degree of softening S was determined by the following equation.
S = (σ 0 −σ) / (σ 0 −σ 900 )
(製品の結晶方位測定)
Cube方位、Copper方位及びBrass方位の面積率をEBSD(Electron Back-Scatter Diffraction:電子後方散乱回折)により測定した。
EBSD測定では、結晶粒を200個以上含む、500μm四方の試料面積に対し、0.5μmのステップでスキャンし、方位を解析した。理想方位からのずれ角度については、共通の回転軸を中心に回転角を計算し、ずれ角度とした。例えば、S方位(2 3 1)[6 -4 3]に対して、(1 2 1)[1 -1 1]は(20 10 17)方向を回転軸にして、19.4°回転した関係になっており、この角度をずれ角度とした。共通の回転軸は最も小さいずれ角度で表現できるものを採用した。全ての測定点に対してこのずれ角度を計算して小数第一位までを有効数字とし、Cube方位、Copper方位、Brass方位のそれぞれから10°以内の方位を持つ結晶粒の面積を全測定面積で除し、面積率とした。EBSDによる方位解析において得られる情報は、電子線が試料に侵入する数10nmの深さまでの方位情報を含んでいるが、測定している広さに対して充分に小さいため、面積率として記載した。 (Measurement of crystal orientation of products)
The area ratios of Cube orientation, Copper orientation, and Brass orientation were measured by EBSD (Electron Back-Scatter Diffraction).
In the EBSD measurement, a sample area of 500 μm square containing 200 or more crystal grains was scanned in 0.5 μm steps, and the orientation was analyzed. Regarding the deviation angle from the ideal orientation, the rotation angle was calculated around the common rotation axis, and was taken as the deviation angle. For example, with respect to the S orientation (2 3 1) [6 -4 3], (1 2 1) [1 -1 1] is rotated by 19.4 ° with the (20 10 17) direction as the rotation axis. This angle was taken as the deviation angle. A common rotation axis that can be expressed at the smallest angle is adopted. The deviation angle is calculated for all measurement points, and the first decimal place is an effective number. The area of crystal grains having an orientation within 10 ° from each of the Cube orientation, Copper orientation, and Brass orientation is the total measurement area. To obtain the area ratio. The information obtained in the azimuth analysis by EBSD includes azimuth information up to a depth of several tens of nanometers in which the electron beam penetrates the sample, but is described as an area ratio because it is sufficiently small with respect to the measured width. .
Cube方位、Copper方位及びBrass方位の面積率をEBSD(Electron Back-Scatter Diffraction:電子後方散乱回折)により測定した。
EBSD測定では、結晶粒を200個以上含む、500μm四方の試料面積に対し、0.5μmのステップでスキャンし、方位を解析した。理想方位からのずれ角度については、共通の回転軸を中心に回転角を計算し、ずれ角度とした。例えば、S方位(2 3 1)[6 -4 3]に対して、(1 2 1)[1 -1 1]は(20 10 17)方向を回転軸にして、19.4°回転した関係になっており、この角度をずれ角度とした。共通の回転軸は最も小さいずれ角度で表現できるものを採用した。全ての測定点に対してこのずれ角度を計算して小数第一位までを有効数字とし、Cube方位、Copper方位、Brass方位のそれぞれから10°以内の方位を持つ結晶粒の面積を全測定面積で除し、面積率とした。EBSDによる方位解析において得られる情報は、電子線が試料に侵入する数10nmの深さまでの方位情報を含んでいるが、測定している広さに対して充分に小さいため、面積率として記載した。 (Measurement of crystal orientation of products)
The area ratios of Cube orientation, Copper orientation, and Brass orientation were measured by EBSD (Electron Back-Scatter Diffraction).
In the EBSD measurement, a sample area of 500 μm square containing 200 or more crystal grains was scanned in 0.5 μm steps, and the orientation was analyzed. Regarding the deviation angle from the ideal orientation, the rotation angle was calculated around the common rotation axis, and was taken as the deviation angle. For example, with respect to the S orientation (2 3 1) [6 -4 3], (1 2 1) [1 -1 1] is rotated by 19.4 ° with the (20 10 17) direction as the rotation axis. This angle was taken as the deviation angle. A common rotation axis that can be expressed at the smallest angle is adopted. The deviation angle is calculated for all measurement points, and the first decimal place is an effective number. The area of crystal grains having an orientation within 10 ° from each of the Cube orientation, Copper orientation, and Brass orientation is the total measurement area. To obtain the area ratio. The information obtained in the azimuth analysis by EBSD includes azimuth information up to a depth of several tens of nanometers in which the electron beam penetrates the sample, but is described as an area ratio because it is sufficiently small with respect to the measured width. .
(製品の引張試験)
引張試験機を用いてJIS Z 2241に準拠し圧延方向と平行に引張試験を行い、応力-歪曲線を得た。この曲線より引張強さ及び0.2%耐力を求めた。さらに、応力-歪曲線を真応力-真歪曲線に変換し、n値を読み取った。 (Product tensile test)
Using a tensile tester, a tensile test was performed in parallel with the rolling direction in accordance with JIS Z 2241 to obtain a stress-strain curve. Tensile strength and 0.2% yield strength were determined from this curve. Further, the stress-strain curve was converted to a true stress-true strain curve, and the n value was read.
引張試験機を用いてJIS Z 2241に準拠し圧延方向と平行に引張試験を行い、応力-歪曲線を得た。この曲線より引張強さ及び0.2%耐力を求めた。さらに、応力-歪曲線を真応力-真歪曲線に変換し、n値を読み取った。 (Product tensile test)
Using a tensile tester, a tensile test was performed in parallel with the rolling direction in accordance with JIS Z 2241 to obtain a stress-strain curve. Tensile strength and 0.2% yield strength were determined from this curve. Further, the stress-strain curve was converted to a true stress-true strain curve, and the n value was read.
(製品の曲げ試験)
圧延方向に対して平行方向にJIS H 3130に記載されたW曲げ試験を行った際、割れの生じない最小曲げ半径(MBR、単位:mm)を求め、板厚(t、単位:mm)との比(MBR/t)を測定した。 (Product bending test)
When the W bending test described in JIS H 3130 was performed in a direction parallel to the rolling direction, the minimum bending radius (MBR, unit: mm) without cracking was obtained, and the plate thickness (t, unit: mm) and The ratio (MBR / t) was measured.
圧延方向に対して平行方向にJIS H 3130に記載されたW曲げ試験を行った際、割れの生じない最小曲げ半径(MBR、単位:mm)を求め、板厚(t、単位:mm)との比(MBR/t)を測定した。 (Product bending test)
When the W bending test described in JIS H 3130 was performed in a direction parallel to the rolling direction, the minimum bending radius (MBR, unit: mm) without cracking was obtained, and the plate thickness (t, unit: mm) and The ratio (MBR / t) was measured.
表1に試験条件及び評価結果を示す。発明例は、本発明が規定する条件で製造したものであり、結晶方位及びn値が本発明の規定を満たし、MBR/tが0.5以下と良好な曲げ加工性が得られた。
比較例1は、予備焼鈍での軟化度が0.25未満になったため、Copper方位の面積率が20%を超え、Cube方位の面積率が5%未満になった。比較例2は、予備焼鈍での軟化度が0.75を超えたため、Brass方位の面積率が20%を超え、Cube方位の面積率が5%未満になった。比較例3及び4は、第二圧延の加工度が本発明の規定から外れたものであり、Cube方位の面積率が5%未満になった。比較例5は、第三圧延の歪速度が本発明の規定から外れたものであり、n値が0.2を超えた。以上の比較例では、MBR/tが1となり、曲げ加工性が悪かった。
なお、比較例5は特許文献3が推奨する条件の範囲で行われたものであり、その結晶方位は特許文献2の規定を満足するものであった。 Table 1 shows test conditions and evaluation results. The inventive examples were produced under the conditions specified by the present invention, the crystal orientation and the n value satisfied the specifications of the present invention, and MBR / t was 0.5 or less and good bending workability was obtained.
In Comparative Example 1, since the degree of softening in the pre-annealing was less than 0.25, the area ratio of Copper orientation exceeded 20%, and the area ratio of Cube orientation was less than 5%. In Comparative Example 2, since the degree of softening in the preliminary annealing exceeded 0.75, the area ratio of the Brass orientation exceeded 20%, and the area ratio of the Cube orientation became less than 5%. In Comparative Examples 3 and 4, the degree of workability of the second rolling deviated from the definition of the present invention, and the area ratio of the Cube orientation was less than 5%. In Comparative Example 5, the strain rate of the third rolling deviated from the definition of the present invention, and the n value exceeded 0.2. In the above comparative examples, MBR / t was 1, and bending workability was poor.
Note that Comparative Example 5 was performed within the range of conditions recommended by Patent Document 3, and the crystal orientation satisfied the provisions of Patent Document 2.
比較例1は、予備焼鈍での軟化度が0.25未満になったため、Copper方位の面積率が20%を超え、Cube方位の面積率が5%未満になった。比較例2は、予備焼鈍での軟化度が0.75を超えたため、Brass方位の面積率が20%を超え、Cube方位の面積率が5%未満になった。比較例3及び4は、第二圧延の加工度が本発明の規定から外れたものであり、Cube方位の面積率が5%未満になった。比較例5は、第三圧延の歪速度が本発明の規定から外れたものであり、n値が0.2を超えた。以上の比較例では、MBR/tが1となり、曲げ加工性が悪かった。
なお、比較例5は特許文献3が推奨する条件の範囲で行われたものであり、その結晶方位は特許文献2の規定を満足するものであった。 Table 1 shows test conditions and evaluation results. The inventive examples were produced under the conditions specified by the present invention, the crystal orientation and the n value satisfied the specifications of the present invention, and MBR / t was 0.5 or less and good bending workability was obtained.
In Comparative Example 1, since the degree of softening in the pre-annealing was less than 0.25, the area ratio of Copper orientation exceeded 20%, and the area ratio of Cube orientation was less than 5%. In Comparative Example 2, since the degree of softening in the preliminary annealing exceeded 0.75, the area ratio of the Brass orientation exceeded 20%, and the area ratio of the Cube orientation became less than 5%. In Comparative Examples 3 and 4, the degree of workability of the second rolling deviated from the definition of the present invention, and the area ratio of the Cube orientation was less than 5%. In Comparative Example 5, the strain rate of the third rolling deviated from the definition of the present invention, and the n value exceeded 0.2. In the above comparative examples, MBR / t was 1, and bending workability was poor.
Note that Comparative Example 5 was performed within the range of conditions recommended by Patent Document 3, and the crystal orientation satisfied the provisions of Patent Document 2.
(実施例2)
実施例1で示した曲げ性の改善効果が、異なる成分及び製造条件のCu-Ni-Si系合金でも得られるかについての検討を行った。
実施例1と同様の方法で鋳造、熱間圧延及び表面研削を行い、表2の成分を有する厚み9mmの板を得た。この板に対し次の工程順で圧延及び熱処理を施し、板厚0.15mmの製品試料を作製した。
(1)第一の冷間圧延:第二の冷間圧延の圧延加工度に応じ、所定の厚みまで冷間圧延した。
(2)予備焼鈍:所定温度に調整した電気炉に、試料を挿入し、所定時間保持した後、試料を水槽に入れ冷却(水冷)、又は、試料を大気中に放置し冷却(空冷)の2通りの条件で冷却した。
(3)第二の冷間圧延:種々の圧延加工度で、厚み0.18mmまで冷間圧延を行った。
(4)溶体化処理:所定温度に調整した電気炉に試料を挿入し、10秒間保持した後、試料を水槽に入れ冷却した。該温度は再結晶粒の平均直径が5~25μmの範囲になる範囲で選択した。
(5)時効処理:電気炉を用い所定温度で5時間、Ar雰囲気中で加熱した。該温度は時効後の引張強さが最大になるように選択した。
(6)第三の冷間圧延:種々の歪速度で、0.18mmから0.15mmまで加工度17%で冷間圧延した。
(7)歪取り焼鈍:所定温度に調整した電気炉に試料を挿入し、10秒間保持した後、試料を大気中に放置し冷却した。 (Example 2)
It was examined whether the bendability improving effect shown in Example 1 could be obtained with Cu—Ni—Si based alloys having different components and production conditions.
Casting, hot rolling and surface grinding were performed in the same manner as in Example 1 to obtain a 9 mm thick plate having the components shown in Table 2. The plate was subjected to rolling and heat treatment in the following process order to produce a product sample having a plate thickness of 0.15 mm.
(1) First cold rolling: Cold rolling was performed to a predetermined thickness in accordance with the rolling degree of the second cold rolling.
(2) Pre-annealing: Insert a sample into an electric furnace adjusted to a predetermined temperature and hold it for a predetermined time, then place the sample in a water bath for cooling (water cooling), or leave the sample in the atmosphere for cooling (air cooling) Cooling was performed under two conditions.
(3) Second cold rolling: Cold rolling was performed at various rolling degrees to a thickness of 0.18 mm.
(4) Solution treatment: The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was placed in a water bath and cooled. The temperature was selected so that the average diameter of the recrystallized grains was in the range of 5 to 25 μm.
(5) Aging treatment: Heating was performed in an Ar atmosphere using an electric furnace at a predetermined temperature for 5 hours. The temperature was selected to maximize the tensile strength after aging.
(6) Third cold rolling: Cold rolling was performed at various strain rates from 0.18 mm to 0.15 mm at a working degree of 17%.
(7) Strain relief annealing: The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was left in the air and cooled.
実施例1で示した曲げ性の改善効果が、異なる成分及び製造条件のCu-Ni-Si系合金でも得られるかについての検討を行った。
実施例1と同様の方法で鋳造、熱間圧延及び表面研削を行い、表2の成分を有する厚み9mmの板を得た。この板に対し次の工程順で圧延及び熱処理を施し、板厚0.15mmの製品試料を作製した。
(1)第一の冷間圧延:第二の冷間圧延の圧延加工度に応じ、所定の厚みまで冷間圧延した。
(2)予備焼鈍:所定温度に調整した電気炉に、試料を挿入し、所定時間保持した後、試料を水槽に入れ冷却(水冷)、又は、試料を大気中に放置し冷却(空冷)の2通りの条件で冷却した。
(3)第二の冷間圧延:種々の圧延加工度で、厚み0.18mmまで冷間圧延を行った。
(4)溶体化処理:所定温度に調整した電気炉に試料を挿入し、10秒間保持した後、試料を水槽に入れ冷却した。該温度は再結晶粒の平均直径が5~25μmの範囲になる範囲で選択した。
(5)時効処理:電気炉を用い所定温度で5時間、Ar雰囲気中で加熱した。該温度は時効後の引張強さが最大になるように選択した。
(6)第三の冷間圧延:種々の歪速度で、0.18mmから0.15mmまで加工度17%で冷間圧延した。
(7)歪取り焼鈍:所定温度に調整した電気炉に試料を挿入し、10秒間保持した後、試料を大気中に放置し冷却した。 (Example 2)
It was examined whether the bendability improving effect shown in Example 1 could be obtained with Cu—Ni—Si based alloys having different components and production conditions.
Casting, hot rolling and surface grinding were performed in the same manner as in Example 1 to obtain a 9 mm thick plate having the components shown in Table 2. The plate was subjected to rolling and heat treatment in the following process order to produce a product sample having a plate thickness of 0.15 mm.
(1) First cold rolling: Cold rolling was performed to a predetermined thickness in accordance with the rolling degree of the second cold rolling.
(2) Pre-annealing: Insert a sample into an electric furnace adjusted to a predetermined temperature and hold it for a predetermined time, then place the sample in a water bath for cooling (water cooling), or leave the sample in the atmosphere for cooling (air cooling) Cooling was performed under two conditions.
(3) Second cold rolling: Cold rolling was performed at various rolling degrees to a thickness of 0.18 mm.
(4) Solution treatment: The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was placed in a water bath and cooled. The temperature was selected so that the average diameter of the recrystallized grains was in the range of 5 to 25 μm.
(5) Aging treatment: Heating was performed in an Ar atmosphere using an electric furnace at a predetermined temperature for 5 hours. The temperature was selected to maximize the tensile strength after aging.
(6) Third cold rolling: Cold rolling was performed at various strain rates from 0.18 mm to 0.15 mm at a working degree of 17%.
(7) Strain relief annealing: The sample was inserted into an electric furnace adjusted to a predetermined temperature and held for 10 seconds, and then the sample was left in the air and cooled.
予備焼鈍後の試料及び製品試料について、実施例1と同様の評価を行った。表2及び3に、それぞれ試験条件及び評価結果を示す。歪取り焼鈍を行わなかった場合は、その温度の欄に「なし」と表記している。
本発明合金は、本発明が規定する濃度のNi及びSiを含有し、本発明が規定する条件で製造したものであり、結晶方位及びn値が本発明の規定を満たし、MBR/tが0.5以下と良好な曲げ加工性が得られた。
一方、比較例6は、第三圧延の歪速度が本発明の規定から外れたため、n値が0.2を超え、その曲げ加工性は悪かった。比較例7、8及び9は、予備焼鈍での軟化度が本発明の規定から外れたため、比較例10及び11は第二圧延の加工度が本発明の規定から外れたため、その結晶方位が本発明の規定から外れ、曲げ加工性は悪かった。比較例12は、Ni及びSi濃度が本発明の規定を下回ったものであり、その曲げ加工性は良好であったが、0.2%耐力が500MPaにも達しなかった。 Evaluation similar to Example 1 was performed about the sample after pre-annealing, and a product sample. Tables 2 and 3 show test conditions and evaluation results, respectively. When the strain relief annealing is not performed, “none” is written in the temperature column.
The alloy of the present invention contains Ni and Si at the concentrations specified by the present invention, and is manufactured under the conditions specified by the present invention. The crystal orientation and the n value satisfy the specifications of the present invention, and MBR / t is 0. Bending workability as good as .5 or less was obtained.
On the other hand, in Comparative Example 6, since the strain rate of the third rolling deviated from the definition of the present invention, the n value exceeded 0.2 and the bending workability was poor. In Comparative Examples 7, 8 and 9, the degree of softening in the pre-annealing was out of the definition of the present invention, and in Comparative Examples 10 and 11, the degree of work in the second rolling was out of the definition of the present invention. Beyond the provisions of the invention, the bending workability was poor. In Comparative Example 12, the Ni and Si concentrations were lower than those of the present invention, and the bending workability was good, but the 0.2% proof stress did not reach 500 MPa.
本発明合金は、本発明が規定する濃度のNi及びSiを含有し、本発明が規定する条件で製造したものであり、結晶方位及びn値が本発明の規定を満たし、MBR/tが0.5以下と良好な曲げ加工性が得られた。
一方、比較例6は、第三圧延の歪速度が本発明の規定から外れたため、n値が0.2を超え、その曲げ加工性は悪かった。比較例7、8及び9は、予備焼鈍での軟化度が本発明の規定から外れたため、比較例10及び11は第二圧延の加工度が本発明の規定から外れたため、その結晶方位が本発明の規定から外れ、曲げ加工性は悪かった。比較例12は、Ni及びSi濃度が本発明の規定を下回ったものであり、その曲げ加工性は良好であったが、0.2%耐力が500MPaにも達しなかった。 Evaluation similar to Example 1 was performed about the sample after pre-annealing, and a product sample. Tables 2 and 3 show test conditions and evaluation results, respectively. When the strain relief annealing is not performed, “none” is written in the temperature column.
The alloy of the present invention contains Ni and Si at the concentrations specified by the present invention, and is manufactured under the conditions specified by the present invention. The crystal orientation and the n value satisfy the specifications of the present invention, and MBR / t is 0. Bending workability as good as .5 or less was obtained.
On the other hand, in Comparative Example 6, since the strain rate of the third rolling deviated from the definition of the present invention, the n value exceeded 0.2 and the bending workability was poor. In Comparative Examples 7, 8 and 9, the degree of softening in the pre-annealing was out of the definition of the present invention, and in Comparative Examples 10 and 11, the degree of work in the second rolling was out of the definition of the present invention. Beyond the provisions of the invention, the bending workability was poor. In Comparative Example 12, the Ni and Si concentrations were lower than those of the present invention, and the bending workability was good, but the 0.2% proof stress did not reach 500 MPa.
Claims (6)
- 1.0~4.5質量%のNi及び0.2~1.0質量%のSiを含有し、残部が銅及び不可避的不純物からなり、EBSD(Electron Back-Scatter Diffraction:電子後方散乱回折)測定を行い、結晶方位を解析したときに、Cube方位{0 0 1}<1 0 0>の面積率が5%以上、Brass方位{1 1 0}<1 1 2>の面積率が20%以下、Copper方位{1 1 2}<1 1 1>の面積率が20%以下であり、加工硬化指数が0.2以下であるCu-Ni-Si系合金。 It contains 1.0 to 4.5 mass% Ni and 0.2 to 1.0 mass% Si, and the balance consists of copper and unavoidable impurities, EBSD (Electron Back-Scatter Diffraction). When measuring and analyzing the crystal orientation, the area ratio of Cube orientation {0 0 1} <1 0 0> is 5% or more, and the area ratio of Brass orientation {1 1 0} <1 1 2> is 20%. Hereinafter, a Cu—Ni—Si alloy having an area ratio of Copper orientation {1 1 2} <1 1 1> of 20% or less and a work hardening index of 0.2 or less.
- Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgのうち1種以上を総量で0.005~2.5質量%含有する請求項1に記載のCu-Ni-Si系合金。 The content of one or more of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr, and Ag is 0.005 to 2.5 mass% in total. Cu-Ni-Si alloy.
- 1.0~4.5質量%のNi及び0.2~1.0質量%のSiを含有し、残部が銅及び不可避的不純物からなるインゴットを作製し、前記インゴットを熱間圧延した後、冷間圧延を行い、軟化度0.25~0.75の熱処理を行った後、加工度7~50%の冷間圧延を行い、次いで、溶体化処理を行った後、時効処理及び歪速度1×10-4(1/秒)以下の冷間圧延を任意の順で行う請求項1又は2に記載のCu-Ni-Si系合金の製造方法。 An ingot containing 1.0 to 4.5% by mass of Ni and 0.2 to 1.0% by mass of Si, the balance being made of copper and unavoidable impurities, and hot rolling the ingot, After cold rolling, heat treatment with a softening degree of 0.25 to 0.75, followed by cold rolling with a working degree of 7 to 50%, followed by solution treatment, aging treatment and strain rate The method for producing a Cu-Ni-Si based alloy according to claim 1 or 2, wherein cold rolling of 1 x 10 -4 (1 / second) or less is performed in an arbitrary order.
- 前記インゴットが、Sn、Zn、Mg、Fe、Ti、Zr、Cr、Al、P、Mn、Co、Cr及びAgのうち1種以上を総量で0.005~2.5質量%含有する請求項3に記載のCu-Ni-Si系合金の製造方法。 The ingot contains 0.005 to 2.5 mass% in total of at least one of Sn, Zn, Mg, Fe, Ti, Zr, Cr, Al, P, Mn, Co, Cr and Ag. 4. A method for producing a Cu—Ni—Si alloy according to 3.
- 請求項1又は2に記載の銅合金を備えた伸銅品。 A copper product comprising the copper alloy according to claim 1 or 2.
- 請求項1又は2に記載の銅合金を備えた電子機器部品。 An electronic device part comprising the copper alloy according to claim 1.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020147007915A KR101628583B1 (en) | 2011-08-29 | 2012-04-04 | Cu-ni-si alloy and method for manufacturing same |
CN201280042580.XA CN103781925A (en) | 2011-08-29 | 2012-04-04 | Cu-Ni-Si alloy and method for manufacturing same |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011185962A JP5117604B1 (en) | 2011-08-29 | 2011-08-29 | Cu-Ni-Si alloy and method for producing the same |
JP2011-185962 | 2011-08-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013031279A1 true WO2013031279A1 (en) | 2013-03-07 |
Family
ID=47692792
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/059207 WO2013031279A1 (en) | 2011-08-29 | 2012-04-04 | Cu-ni-si alloy and method for manufacturing same |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP5117604B1 (en) |
KR (1) | KR101628583B1 (en) |
CN (2) | CN107354342A (en) |
TW (1) | TWI465591B (en) |
WO (1) | WO2013031279A1 (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103509970A (en) * | 2013-08-16 | 2014-01-15 | 中国船舶重工集团公司第七二五研究所 | Copper, nickel, aluminum and silicon elastic alloy and preparation method thereof |
JP6310538B1 (en) * | 2016-12-14 | 2018-04-11 | 古河電気工業株式会社 | Copper alloy wire rod and method for producing the same |
Families Citing this family (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6246454B2 (en) * | 2011-11-02 | 2017-12-13 | Jx金属株式会社 | Cu-Ni-Si alloy and method for producing the same |
JP6113061B2 (en) * | 2013-11-25 | 2017-04-12 | Jx金属株式会社 | Copper alloy sheet with excellent electrical conductivity, stress relaxation resistance and formability |
CN106460099B (en) * | 2014-05-30 | 2020-03-17 | 古河电气工业株式会社 | Copper alloy sheet material, connector made of copper alloy sheet material, and method for manufacturing copper alloy sheet material |
CN106661673A (en) * | 2014-07-09 | 2017-05-10 | 古河电气工业株式会社 | Copper alloy sheet material, connector, and method for producing copper alloy sheet material |
KR20170132146A (en) | 2015-04-01 | 2017-12-01 | 후루카와 덴끼고교 가부시키가이샤 | Manufacturing method of flat rolled copper foil, flexible flat cable, rotary connector and flat rolled copper foil |
KR101627696B1 (en) * | 2015-12-28 | 2016-06-07 | 주식회사 풍산 | Copper alloy material for car and electrical and electronic components and process for producing same |
WO2017168803A1 (en) * | 2016-03-31 | 2017-10-05 | Dowaメタルテック株式会社 | Cu-ni-si copper alloy sheet and manufacturing method |
CN106591623B (en) * | 2016-12-05 | 2018-04-17 | 宁波博威合金板带有限公司 | A kind of high temperature resistant iron bronze and its preparation method and application |
JP6609590B2 (en) * | 2017-03-30 | 2019-11-20 | Jx金属株式会社 | High-strength titanium copper strip and foil having a layered structure |
JP6609589B2 (en) * | 2017-03-30 | 2019-11-20 | Jx金属株式会社 | High-strength titanium copper strip and foil having a layered structure |
JP6378819B1 (en) * | 2017-04-04 | 2018-08-22 | Dowaメタルテック株式会社 | Cu-Co-Si-based copper alloy sheet, manufacturing method, and parts using the sheet |
CN107326215A (en) * | 2017-08-15 | 2017-11-07 | 徐高杰 | A kind of processing method of slot wedge copper alloy |
JP6670277B2 (en) * | 2017-09-14 | 2020-03-18 | Jx金属株式会社 | Cu-Ni-Si based copper alloy with excellent mold wear |
CN111485132B (en) * | 2020-04-10 | 2021-09-10 | 宁波博威合金板带有限公司 | Copper alloy strip with excellent comprehensive performance and preparation method thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002266042A (en) * | 2001-03-09 | 2002-09-18 | Kobe Steel Ltd | Copper alloy sheet having excellent bending workability |
JP2011017072A (en) * | 2009-07-10 | 2011-01-27 | Furukawa Electric Co Ltd:The | Copper alloy material |
WO2011068135A1 (en) * | 2009-12-02 | 2011-06-09 | 古河電気工業株式会社 | Copper alloy sheet and process for producing same |
JP2011117034A (en) * | 2009-12-02 | 2011-06-16 | Furukawa Electric Co Ltd:The | Copper-alloy material |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP4584692B2 (en) | 2004-11-30 | 2010-11-24 | 株式会社神戸製鋼所 | High-strength copper alloy sheet excellent in bending workability and manufacturing method thereof |
JP4566048B2 (en) | 2005-03-31 | 2010-10-20 | 株式会社神戸製鋼所 | High-strength copper alloy sheet excellent in bending workability and manufacturing method thereof |
JP4006460B1 (en) * | 2006-05-26 | 2007-11-14 | 株式会社神戸製鋼所 | Copper alloy excellent in high strength, high conductivity and bending workability, and method for producing the same |
EP2184371B1 (en) * | 2007-08-07 | 2016-11-30 | Kabushiki Kaisha Kobe Seiko Sho | Copper alloy sheet |
WO2009154239A1 (en) * | 2008-06-17 | 2009-12-23 | 古河電気工業株式会社 | Electric wire conductor for wiring, electric wire for wiring, and method for manufacturing electric wire conductor for wiring |
-
2011
- 2011-08-29 JP JP2011185962A patent/JP5117604B1/en active Active
-
2012
- 2012-04-04 CN CN201710574487.8A patent/CN107354342A/en active Pending
- 2012-04-04 WO PCT/JP2012/059207 patent/WO2013031279A1/en active Application Filing
- 2012-04-04 CN CN201280042580.XA patent/CN103781925A/en active Pending
- 2012-04-04 KR KR1020147007915A patent/KR101628583B1/en active IP Right Grant
- 2012-04-23 TW TW101114306A patent/TWI465591B/en active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002266042A (en) * | 2001-03-09 | 2002-09-18 | Kobe Steel Ltd | Copper alloy sheet having excellent bending workability |
JP2011017072A (en) * | 2009-07-10 | 2011-01-27 | Furukawa Electric Co Ltd:The | Copper alloy material |
WO2011068135A1 (en) * | 2009-12-02 | 2011-06-09 | 古河電気工業株式会社 | Copper alloy sheet and process for producing same |
JP2011117034A (en) * | 2009-12-02 | 2011-06-16 | Furukawa Electric Co Ltd:The | Copper-alloy material |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103509970A (en) * | 2013-08-16 | 2014-01-15 | 中国船舶重工集团公司第七二五研究所 | Copper, nickel, aluminum and silicon elastic alloy and preparation method thereof |
CN103509970B (en) * | 2013-08-16 | 2017-03-01 | 中国船舶重工集团公司第七二五研究所 | A kind of cupro-nickel aluminum silicon elastic alloy and preparation method thereof |
JP6310538B1 (en) * | 2016-12-14 | 2018-04-11 | 古河電気工業株式会社 | Copper alloy wire rod and method for producing the same |
WO2018110037A1 (en) * | 2016-12-14 | 2018-06-21 | 古河電気工業株式会社 | Copper alloy wire rod material and production method therefor |
JP2018095928A (en) * | 2016-12-14 | 2018-06-21 | 古河電気工業株式会社 | Copper alloy wire rod material and method for producing the same |
Also Published As
Publication number | Publication date |
---|---|
JP5117604B1 (en) | 2013-01-16 |
CN103781925A (en) | 2014-05-07 |
TW201309817A (en) | 2013-03-01 |
CN107354342A (en) | 2017-11-17 |
JP2013047360A (en) | 2013-03-07 |
KR101628583B1 (en) | 2016-06-08 |
TWI465591B (en) | 2014-12-21 |
KR20140053376A (en) | 2014-05-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5117604B1 (en) | Cu-Ni-Si alloy and method for producing the same | |
JP4857395B1 (en) | Cu-Ni-Si alloy and method for producing the same | |
JP5417366B2 (en) | Cu-Ni-Si alloy with excellent bending workability | |
JP5619389B2 (en) | Copper alloy material | |
WO2016006053A1 (en) | Copper alloy sheet material, connector, and method for producing copper alloy sheet material | |
JP6196435B2 (en) | Titanium copper and method for producing the same | |
JP5039862B1 (en) | Corson alloy and manufacturing method thereof | |
KR101917416B1 (en) | Copper-cobalt-silicon alloy for electrode material | |
JP6228725B2 (en) | Cu-Co-Si alloy and method for producing the same | |
JP5539932B2 (en) | Cu-Co-Si alloy with excellent bending workability | |
JP6214126B2 (en) | Titanium copper and method for producing the same, as well as copper products and electronic device parts using titanium copper | |
JP2016199808A (en) | Cu-Co-Si-BASED ALLOY AND PRODUCTION METHOD THEREFOR | |
JP6111028B2 (en) | Corson alloy and manufacturing method thereof | |
JP2013104082A (en) | Cu-Co-Si-BASED ALLOY AND METHOD FOR PRODUCING THE SAME | |
WO2013069376A1 (en) | Cu-co-si-based alloy and method for producing same | |
WO2013058083A1 (en) | Corson alloy and method for producing same | |
JP4987155B1 (en) | Cu-Ni-Si alloy and method for producing the same | |
JP2013100586A (en) | Copper-titanium alloy and method of manufacturing the same | |
WO2013121620A1 (en) | Corson alloy and method for manufacturing same | |
JP6246454B2 (en) | Cu-Ni-Si alloy and method for producing the same | |
JP2016211078A (en) | Cu-Ni-Si-BASED ALLOY AND MANUFACTURING METHOD THEREFOR | |
KR102345805B1 (en) | Cu-Ni-Si-BASED ALLOY STRIP EXCELLENT IN STRENGTH AND BENDING WORKABILITY IN ROLLING PARALLEL DIRECTION AND ROLLING ORTHOGONAL DIRECTION | |
JP2013147687A (en) | Titanium copper excellent in bendability | |
JP2016084542A (en) | Corson alloy and manufacturing method therefor |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12827408 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20147007915 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12827408 Country of ref document: EP Kind code of ref document: A1 |