US20100000637A1 - Cu-ni-si system alloy - Google Patents

Cu-ni-si system alloy Download PDF

Info

Publication number
US20100000637A1
US20100000637A1 US12/311,401 US31140107A US2010000637A1 US 20100000637 A1 US20100000637 A1 US 20100000637A1 US 31140107 A US31140107 A US 31140107A US 2010000637 A1 US2010000637 A1 US 2010000637A1
Authority
US
United States
Prior art keywords
mass
less
concentration
rolling
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US12/311,401
Other languages
English (en)
Inventor
Takaaki Hatano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JX Nippon Mining and Metals Corp
Nippon Mining Holdings Inc
Original Assignee
Nippon Mining and Metals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nippon Mining and Metals Co Ltd filed Critical Nippon Mining and Metals Co Ltd
Assigned to NIPPON MINING & METALS CO., LTD. reassignment NIPPON MINING & METALS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HATANO, TAKAAKI
Publication of US20100000637A1 publication Critical patent/US20100000637A1/en
Assigned to NIPPON MINING HOLDINGS, INC. reassignment NIPPON MINING HOLDINGS, INC. MERGER (SEE DOCUMENT FOR DETAILS). Assignors: NIPPON MINING & METALS CO., LTD.
Assigned to JX NIPPON MINING & METALS CORPORATION reassignment JX NIPPON MINING & METALS CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: NIPPON MINING HOLDINGS, INC.
Abandoned legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/04—Alloys based on copper with zinc as the next major constituent
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18—Hardening; Quenching with or without subsequent tempering
    • C21D1/25—Hardening, combined with annealing between 300 degrees Celsius and 600 degrees Celsius, i.e. heat refining ("Vergüten")
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/0002—Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00

Definitions

  • the present invention relates to Cu—Ni—Si system alloys suitable for use in a variety of electronic components such as a lead frame, connector, pin, terminal, relay and switch. Further, the present invention relates to a method for manufacturing the alloys. Further, the present invention relates to electronic components made of the alloys.
  • a copper alloy for electronic materials used in electronic components and the like is required to satisfy both high strength and high electrical conductivity (or thermal conductivity) as a basic characteristic. Further, the copper alloy is also required to have bending workability, stress relaxation performance, thermal resistance, thermal peel resistance of plating, solderability, etching workability, press punching quality, corrosion resistance and the like.
  • a Cu—Ni—Si system alloy is a copper alloy having relatively high electrical conductivity and strength, and therefore it is one of the alloys that have been actively developed in the industry in these days.
  • fine particles of Ni—Si intermetallic compounds are precipitated in the copper matrix, thereby the strength and electrical conductivity increase.
  • Patent document 1 discloses Cu—Ni—Si system alloys aiming high strength and excellent bending workability. It also discloses that, in preparing the copper alloys, a summation of reduction ratios of cold rolling before and after conducting the age hardening should be 40% or less, heat conditions where a diameter of recrystallized grains is 5 to 15 ⁇ m should be selected in the solution treatment, and the age hardening should be conducted for 30 to 300 minutes at 440 to 500° C.
  • the copper alloys that are specifically described in Patent document 1 do not generate cracks by W-bending, the tensile strength is 520 MPa when the electrical conductivity is at its highest point of 53% IACS, and the electrical conductivity is 46% IACS when the tensile strength is at its highest point of 710 MPa (see Table 2 of working examples).
  • Patent document 2 discloses examples of development of Cu—Ni—Si system alloys having excellent bending workability in addition to high strength and electrical conductivity. It discloses that excellent bending workability is provided by bringing the mass ratio of Ni and Si in an alloy close to the concentration of the intermetallic compound, Ni 2 Si, namely, by adjusting the mass ratio of Ni and Si such that the ratio Ni/Si becomes 3 to 7.
  • suitable materials as a copper alloy for electronic materials are obtainable by adding Fe and/or one or more selected from Zr, Cr, Ti and Mo to a Cu—Ni—Si system alloy, conducting quality governing and then adding Mg, Zn, Sn, Al, P, Mn, Ag or Be as needed.
  • the copper alloys that are specifically described in Patent document 2 do not generate cracks by 90°-bending (not 180°-bending), the tensile strength is 640 MPa when the electrical conductivity is at its highest point of 56% IACS, and the electrical conductivity is 44% IACS when the tensile strength is at its highest point of 698 MPa (see Table 1 of working examples). Further, reduction ratios of cold rolling before and after conducting the ge hardening are 60% and 37.5% (a summation of those rates is 97.5%).
  • Patent document 3 discloses Cu—Ni—Si system alloys having excellent electrical conductivity of 60% IACS or more, high strength, excellent stiffness strength and repetitive bending workability, and high thermal resistance. It discloses that the alloys should contain 0.02 to 1.0 wt % Mn, 0.1 to 5.0 wt % Zn, 0.001 to 0.01 wt % Mg, and 0.001 to 0.01 wt % elements selected one or more from Cr, Ti and Zr.
  • Patent document 4 discloses Cu—Ni—Si system alloys having excellent mechanical characteristics, electrical conductivity, stress relaxation performance and bending workability by adding specified amount of Sn, Mg, or additionally Zn, limiting contained amount of 5 and 0, and adjusting crystal grain size to more than 1 ⁇ m and equal to or less than 25 ⁇ m. Further, it discloses that recrystallization after cold rolling should be conducted at 700 to 920° C. in order to adjust the crystal grain size within the above range.
  • Working examples of the document disclose Cu—Ni—Si system alloys that have 610 to 710 MPa tensile strength and could be conducted 180° bending test of 0 radius.
  • the electrical conductivity of the alloys is 31 to 42% IACS and a rate of the stress relaxation is 14 to 22% by heating at 150° C. for 1000 hours.
  • Patent document 5 discloses Cu—Ni—Si system alloys, wherein specified amount of Mg, Sn, Zn and S is contained, a crystal grain size is more than 0.001 mm and 0.025 mm or less, the ratio (a/b) which is a major axis (a) of the crystal grain in its cross-section parallel to a final work processing way to a major axis (b) of the crystal grain in its cross-section transverse to the final work processing way is 0.8 or more and 1.5 or less, and the bending workability and stress relaxation performance are excellent.
  • Working examples of the document disclose Cu—Ni—Si system alloys that have 685 to 710 MPa tensile strength, 32 to 40% IACS electrical conductivity and could be conducted 180° bending test of 0 radius.
  • the precipitate-free zone is a band-like zone that is formed near a crystal grain boundary by a grain boundary reactive deposition at age hardening (discontinuous precipitation) and does not have fine precipitates. If an external force is applied, a plastic deformation occurs in the precipitate-free zone by priority because fine precipitates contributing to strength are not in the zone, and as a result, the tensile strength and bending workability are deteriorates.
  • Non-patent document 1 discloses an addition of P and Sn and a double age hardening are effective for restraining an emergence of the precipitate-free zone. It discloses the strength increases considerably without diminishing elongation by adding preliminary age hardening at 250° C. for 48 hours prior to age hardening at 450° C. for 16 hours in the double age hardening. In particular, it discloses Cu—Ni—Si system alloys having 770 to 900 MPa tensile strength and 34 to 36% IACS electrical conductivity.
  • Non-patent document 2 discloses a range of PFZ increases in association with an increase of time of age hardening.
  • Patent document 1 Japanese patent laid-open publication No. 2002-266042
  • Patent document 2 Japanese patent laid-open publication No. 2001-207229
  • Patent document 3 Japanese patent laid-open publication No. 61-194158
  • Patent document 4 Japanese patent laid-open publication No. 11-222641
  • Patent document 5 Japanese patent No. 3520034
  • Non-patent document 1 Chizuru WATANABE, Masaru MIYAKOSHI, Fumiya NISHIJIMA, Ryoichi KADOMAE: “Improvement of mechanical characteristics of Cu-4.0 mass % Ni-0.95 mass % Si-0.02 mass % P alloys”, Cu and Cu alloys, Japan Copper and Brass Association, 2006, Vol. 45, Number 1, page 16 to 22.
  • Non-patent document 2 Goro ITO, Shunsuke SUZUKI, Yoshihira TOU, Yoshinori YAMAMOTO, Nobuhide ITO, “Influence of the amount of Ni and Si and the condition of age hardening to bending workability of plate materials of Cu—Ni—Si system alloys”, Cu and Cu alloys, Japan Copper and Brass Association, 2006, Vol. 45, Number 1, page 71 to 75.
  • ⁇ T stands for the thermal elevation
  • J stands for the current of electricity
  • E stands for the electric conductivity
  • H stands for the heat thermal conductivity
  • L and “S” each stands for the length and the cross-section area of the current-carrying part.
  • the thermal elevation is inversely related to square of the electric conductivity because “H” is proportional to “E”. If the cross-section area of parts diminishes, the strength of a spring deteriorates in the use of connectors and the like. Accordingly, characteristics of the strength of a spring such as the tensile strength and stress relaxation performance are attached a high value. Therefore, it is unacceptable to deteriorate the tensile strength and stress relaxation performance in exchange for improving the electric conductivity. In a similar way, it is also unacceptable to deteriorate the bendability because a miniaturization of parts complicate processes of parts.
  • the inventor has diligently studied to cope with the requirements, and eventually have found out that Cu—Ni—Si system alloys having excellent electric conductivity, tensile strength, stress relaxation performance and bendability are provided by adding particular conditions to a rate of temperature increase of age hardening, maximum reaching temperature of materials and time of age hardening, and by correcting conditions of solution treatment and a reduction ratio of before and after conducting age hardening in a manufacturing process for Cu—Ni—Si system alloys that contain impurities as little as possible.
  • the present invention that has been made based on these findings is the Cu—Ni—Si system alloy comprising 1.2 to 3.5 mass % Ni, Si in a concentration (mass %) of 1 ⁇ 6 to 1 ⁇ 4 of Ni concentration (mass %) and the balance Cu and impurities whose total amount is 0.05 mass % or less, and having the following characteristics:
  • the present invention is the Cu—Ni—Si system alloy comprising 1.2 to 3.5 mass % Ni, Si in a concentration (mass %) of 1 ⁇ 6 to 1 ⁇ 4 of Ni concentration (mass %), 0.5 mass % or less of Zn and the balance Cu and impurities whose total amount is 0.05 mass % or less, and having the following characteristics:
  • an average grain size transverse to a rolling way is set to “a” and an average grain size parallel to the rolling way is set to “b” in a crystal structure whose cross-section is parallel to a rolling direction
  • an average range of precipitate-free zone in metal structure is 10 to 100 nm.
  • the present invention is wrought copper product made of the alloys.
  • the present invention is electronic components such as a lead frame, a connector, pin, a terminal, a relay, switch, foil materials for a secondary battery and the like made of the alloys.
  • the present invention is a method for manufacturing Cu—Ni—Si system alloys comprising steps of solution treatment, cold rolling, age hardening and cold rolling in this order, wherein the each step is conducted on the following condition:
  • the invention could provide Cu—Ni—Si system alloys for electronic materials that are not added alloy elements other than Ni and Si or alloy elements other than Ni, Si and Zn, and have improved excellent electric conductivity, strength, bending workability and stress relaxation performance.
  • FIG. 1 is a illustration to explain the method of the stress relaxation test.
  • FIG. 2 is a temperature chart in the age hardening.
  • (a) and (b) are the examples of the present invention.
  • (c) is the conventional example.)
  • Zn may be contained in the alloys because its effect on the electrical conductivity is relatively small and its effect on the improvement of thermal peel resistance of Sn plating is profound.
  • a decreasing rate of the electrical conductivity per 0.1 mass % of Zn is about 0.5% IACS.
  • Zn concentration is preferably 0.05 to 0.5 mass % and more preferably 0.1 to 0.3 mass %.
  • b/a is less than 1.05, excellent tensile strength could not be provided (for example, tensile strength is less than 550 MPa). Meanwhile, if “b/a” is more than 1.67, excellent bendability could not be provided (for example, cracks are generated by 180° bending test of 0 radius). “b/a” is preferably 1.10 to 1.40, and more preferably 1.20 to 1.30.
  • An average range of the precipitate-free zone of the crystal structure is set to 10 to 100 nm in the crystal structure whose cross-section is parallel to a rolling direction. If the range of the precipitate-free zone is large, sufficient bendability, stress relaxation performance and tensile strength could not be provided. If the range of precipitate-free zone is more than 100 nm, excellent bendability could not be provided (for example, cracks are generated by 180° bending test of 0 radius), and excellent stress relaxation performance could not either (for example, stress relaxation performance is more than 30%). It is preferable that the range of precipitate-free zone is small.
  • the average range of the precipitate-free zone to advance electrical conductivity, bending workability and stress relaxation performance in proper balance is preferably 20 to 90 nm, and more preferably 30 to 80 nm.
  • the copper alloy of the present invention has the following characteristics at the same time in one embodiment.
  • the copper alloy of the present invention has the following characteristics at the same time in a preferable embodiment.
  • the copper alloy of the present invention has the following characteristics at the same time in another preferable embodiment.
  • the copper alloy of the present invention containing Zn has the following characteristics at the same time in another embodiment.
  • the copper alloy of the present invention containing Zn has the following characteristics at the same time in a preferable embodiment.
  • the copper alloy of the present invention containing Zn has the following characteristics at the same time in another preferable embodiment.
  • thermo peel resistance test indicates a method for evaluation of the peeling of Sn plating of a test piece in the following way.
  • s adhesive tape a masking tape for plating, for example: #851A of SUMITOMO 3M
  • the surface of the bending inner periphery part is examined with a microscope (20 magnifications) and the presence or absence of peelings of the plating is measured.
  • the electrical conductivity monotonously increases with the time.
  • the tensile strength generally increases to relative maximum at a certain temperature, and after that, decreases with the time.
  • the electrical conductivity monotonously increases with the time, and the tensile strength increases to relative maximum and then decreases.
  • the aging conducted on the condition that the tensile strength is at relative maximum is called a peak aging.
  • the aging conducted on the range that the tensile strength increases with the time or the temperature is called an overaging.
  • the overaging could be conducted in order to increase the electrical conductivity of Cu—Ni—Si system alloys. That is, the excellent electrical conductivity (for example, about 60% IACS) could be provided with relative ease if appropriate aging times and temperatures are selected. However, the tensile strength decreases (for example, to about 500 MPa), and in addition, the stress relaxation performance and the bendability deteriorate. If the cold rolling with high reduction ratio is conducted after that, the tensile strength makes a recovery to about 600 MPa. However, the bendability deteriorates significantly due to processing strains and the improvement of the stress relaxation performance could not be desired.
  • the existing highly conductive Cu—Ni—Si system alloys described in Patent document 3 and the like were techniques basically applying the excessive aging.
  • the inventor of the present invention has examined in order to advance the electrical conductivity, bendability and stress relaxation performance in proper balance, and found out that Cu—Ni—Si system alloys having excellent electric conductivity, tensile strength, stress relaxation performance and bending workability are provided by adding particular conditions to a rate of temperature increase of the age hardening, maximum reaching temperature of materials and times of the age hardening, and by correcting conditions of the solution treatment and a reduction ratio of the cold rolling before and after conducting the age hardening in a manufacturing process for Cu—Ni—Si system alloys that contain impurities as little as possible.
  • the rate of temperature increase, the maximum reaching temperature, the time of maintaining the temperature of materials at 450 to 550° C. and the rate of temperature increase of materials are regulated as conditions of the aging.
  • the precipitate-free zone grows and the excellent mechanical characteristics could not be provided if the aging time is prolonged in order to improve the electrical conductivity.
  • the present invention has high significance in that it has the above two conflicting characteristics in the same time. The above mechanism presumed in the present invention does not restrict the present invention.
  • the average rate of temperature increase of materials is 50° C./h or less in each temperature province of 200 to 250° C., 250 to 300° C. and 300 to 350° C.
  • the average rate of temperature increase is preferably 10° C./h or more in the light of the manufacturing efficiency.
  • the average rate of temperature increase is typically 20 to 40° C./h.
  • a certain degree of restrictive effect of the precipitate-free zone could be provided by adding preliminary heat treatment at 250° C. for 48 hr described in Non-patent document 1.
  • the manufacturing efficiency deteriorates significantly by the preliminary heat treatment.
  • the method of controlling the rate of temperature increase of the present invention hardly deteriorates the manufacturing efficiency. Therefore, it is an industrially extremely useful method.
  • the maximum reaching temperature of materials The temperature is set to 550° C. or less, because the range of the precipitate-free zone broadens (for example, over 100 nm) regardless of controlling the rate of temperature increase if the temperature is over 550° C.
  • the temperature is preferably 530° C. or less, and more preferably 500° C. or less. Meanwhile, if the maximum reaching temperature is less than 450° C., the excellent electrical conductivity could not be provided. Accordingly, the maximum reaching temperature is preferably 450° C. or more, and more preferably 480° C. or more.
  • the time of maintaining the temperature at 450 to 550° C. The time is set to 5 to 15 hours. If the heat time is less than 5 hours, the range of the precipitate-free zone narrows (for example, less than 10 nm). However, sufficient electrical conductivity could not be provided even if the rate of temperature increase is controlled. If the time is over 15 hours, the range of the precipitate-free zone broadens (for example, over 100 nm). The preferable time is 6 to 10 hours in consideration of the manufacturing efficiency additionally.
  • the average grain size is regulated to 1 to 15 ⁇ m.
  • the average grain size after the solution treatment is substantively same as “a” regulated above in the stage of products. Accordingly, “a” derived from a crystal structure is less than 1 ⁇ m if the average grain size is less than 1 ⁇ m, and “a” will be more than 15 ⁇ m if the average grain size is more than 15 ⁇ m.
  • the average grain size is preferably 2 to 10 ⁇ m, and in this case, “a” of 2 to 10 ⁇ m can be obtained.
  • the heat temperature and the heat conditions of the solution treatment for providing the above grain size are the public knowledge themselves. A person skilled in the art could set them appropriately. For example, the temperature of materials is maintained in an appropriate temperature of 700 to 800° C. for appropriate times of 5 to 600 seconds, air cooling or water cooling is conducted shortly thereafter, and the above grain size could be provided.
  • the summation of reduction ratios of the intermediate rolling and the last rolling is set to 5 to 40%. “b/a” derived from a metal structure of products is less than 1.05 if the summation of reduction ratios will be less than 5%, and “b/a” will be more than 1.67 if the summation of reduction ratios is more than 40%.
  • the summation of reduction ratios is more preferably 10 to 25%, and in this case, “b/a” of 1.10 to 1.40 can be obtained.
  • the reduction ratio “R” is defined by the following formula.
  • the annealing to remove strains may be conducted after the last cold rolling in order to improve a spring limit value.
  • the annealing to remove strains may be conducted at low temperature for long time (for example, 300° C. ⁇ 30 minutes), and may be conducted at high temperature for short time (for example, 500° C. ⁇ 30 seconds). If the temperature is too high or the time is too long, the tensile strength extremely decreases. It is preferable to set the decreasing amount of the tensile strength to 10 to 50 MPa and set the conditions.
  • the effect of the present invention is also maintained if Cu—Ni—Si system alloys of the present invention are conducted the surface treatment with Sn plating or gold plating.
  • a method for manufacturing copper alloys of the present invention comprises the following steps in this order in a preferable embodiment:
  • the step of melt cast to make ingots comprising 1.2 to 3.5 mass % Ni, Si in a concentration (mass %) of 1 ⁇ 6 to 1 ⁇ 4 of Ni concentration (mass %), 0.5 mass % or less Zn as an optional ingredient, the balance Cu and impurities whose total amount is 0.05 mass % or less,
  • the step of age hardening wherein the maximum temperature of materials during heat treating is 550° C. or less, the temperature of materials is maintained within 450 to 550° C. for 5 to 15 hours, and an average rate of temperature increase of materials is 50° C./h or less in each temperature province of 200 to 250° C., 250 to 300° C. and 300 to 350° C. during a temperature increase process,
  • a reduction ratio is 0 to 40% (a sum of said rate and the reduction ratio at the cold rolling before age hardening is 5 to 40%), and
  • the step of annealing to remove strains optionally, the step of annealing to remove strains.
  • Cu—Ni—Si system alloys of the present invention could be processed to various sorts of wrought copper product such as plates, stripes, tubes, bar and wires. Further, Cu—Ni—Si system alloys of the present invention could be preferably used as, in particular, conductive spring components such as connector, pin, relay, switch, and lead frame components of semiconductor devices such as transistors and integrated circuits.
  • the ingot was heated at 950° C. for 3 hours, hot-rolled to 8 mm thickness, and oxidized scales on the surface were removed by grinding with a grinder. Then the cold rolling, the solution treatment, the cold rolling (intermediate rolling), the age hardening, the cold rolling (last rolling), and the annealing to remove strains as processes and the heat treatments were conducted in this order. The degree of processing and the board thickness at the heat treatments in each rolling were adjusted in order that the board thickness may be 0.25 mm after the last rolling.
  • a pickling with 10 mass % sulfuric acid and 1 mass % hydrogen peroxide solution and a machine polish with #1200 emery papers were conducted in sequence in order to remove surface oxide films produced by the heat treatment after the solution treatment, after the age hardening and after the annealing to remove strains.
  • the sample was set in an electric furnace adjusted to a predetermined temperature for a predetermined time, then was instantly ejected from the electric furnace and air-cooled.
  • the sample was heated on the conditions of different temperatures with the electric furnace. During the age hardening, the sample was contacted with a thermocouple and changes of the temperature of the sample were examined.
  • the sample was set in the electric furnace adjusted to 300° C. for 30 minutes, then was ejected from the electric furnace and air-cooled. The annealing to remove strains was not conducted in the case where the last rolling was not conducted.
  • a crystal structure whose cross-section is parallel to a rolling direction was examined for the sample after the solution treatment and the sample after the annealing to remove strains or the sample after the last rolling if the annealing to remove strains was not conducted (hereinafter called “products”).
  • the rolling direction was conducted mirror finishing with a mechanical polish and an electrolytic polish, a crystal grain boundary was produced by an etching, and then a picture of the crystal structure was taken.
  • a solution mixed with ammonia water and hydrogen peroxide solution was used as the etching liquid.
  • a light microscope and an electron scanning microscope were accordingly used for taking pictures of the crystal structure.
  • the vicinity of the crystal grain boundary of the products in the cross-section parallel to a rolling direction was examined by the transmission electron microscope of about one hundred thousand magnifications, and the average width of the precipitate-free zone (the average width about random 30 points) was calculated.
  • the electric conductivity of the products was examined by the four terminal method with reference to JIS-H0505.
  • the test piece of JIS13B was produced by press that a tensile direction may be parallel to a rolling direction.
  • the tension test of the test piece was conducted with reference to JIS-Z2241 and the tensile strength was examined.
  • a test piece with 10 mm width was obtained from the products, and a 180° bending test of 0 radius test was conducted to Good Way (GW: a direction where the bending axis is transverse to the rolling direction) and Bad Way (BW: a direction where the bending axis is parallel to the rolling direction) with reference to JIS-Z2248.
  • the presence or absence of cracks was examined from the surface and cross-section of the bending part of the sample after bending. The case where the cracks were not seen was set to ⁇ and the case where the cracks were seen was set to X. In this case, cracks with over 10 ⁇ m depth were qualified as the cracks.
  • a test piece with 10 mm width and 100 mm length was obtained from the products in order that a longer direction of the test piece may be parallel to the rolling direction.
  • the y 0 was calculated by the following formula:
  • E Young's modulus
  • t is a thickness of the test piece.
  • the stress was unloaded after heating at 150° C. for 1000 hours, the amount of permanent set (height “y”) was measured as shown in FIG. 1-B , and y/y 0 ⁇ 100 was calculated as a stress relaxation performance (%).
  • test piece was degreased by alkali and pickled by 10% sulfuric acid, under-plated with Cu 0.3 ⁇ m thick, upper-plated with Sn 1 ⁇ m thick, and then heated at 300° C. for 20 seconds as a reflow process.
  • the condition of the plating is as follows:
  • Plating bath composition 200 g/L copper sulfate and 60 g/L sulfuric acid
  • Plating bath composition 41 g/L stannous oxide, 268 g/L phenolsulfonic acid and 5 g/L surface active agent
  • a test piece with 10 mm width was obtained from the sample after the reflow process and heated at 150° C. for 1000 hours in the atmosphere. Then 90-bending of 0.5 mm in radius to Good Way (GW: a direction where the bending axis is transverse to the rolling direction) and returning of the bend (a both-way 90-bending) were conducted, and the adhesive tape (#851A of SUMITOMO 3M) was attached to a surface of a bending inner periphery part and peeled from the surface. Then the surface of the bending inner periphery part was examined with a light microscope (20 magnifications) and the presence or absence of peelings of the plating was measured.
  • GW radius to Good Way
  • the adhesive tape #851A of SUMITOMO 3M
  • the case where the peelings of the plating were not seen at all was set to ⁇ .
  • the case where the plating was detached in sheet shapes was set to X.
  • the case where the plating was locally detached in point shapes was set to ⁇ . From a practical standpoint for applications of a connector and the like, the level of ⁇ has no problem.
  • Sample compounds are set to Cu-1.60 mass % Ni-0.35 mass % Si alloy, the products are produced by changing conditions of the solution treatment, the age hardening and the rolling.
  • FIG. 2 is a typical temperature chart of the age hardening.
  • the broken line shows atmospheric temperature of electric furnace which heats the test piece and the continuous line shows temperatures of the test piece.
  • materials are set in the electric furnace adjusted to 200° C., and the temperature is maintained for 1 hour. Then the temperature of the electric furnace is increased from 200° C. to 350° C. in 5 hours. Next, the temperature of the electric furnace is increased to 500° C. in 1 hour and maintained for 8 hours, and then ejected from the electric furnace and air-cooled.
  • materials are set in the electric furnace adjusted to 200° C., and the temperature is maintained for 1 hour. Then the temperature of the electric furnace is increased from 200° C. to 250° C. in 3 hours, increased to 300° C. in 2 hours and then increased to 350° C. in 1 hour. Next, the temperature of the electric furnace is increased to 490° C. and maintained for 10 hours, and then ejected from the electric furnace and air-cooled. In (c), materials are set in the electric furnace adjusted to 500° C., and ejected from the electric furnace after 9 hours and air-cooled. These correspond to steps of a conventional heating procedure.
  • No. 1 and 2 produced on the conditions of the present invention fill the requirements of the crystal structures and the characteristics regulated in the present invention.
  • the rate of temperature increase of No. 3 that is the conventional example is larger than that of the present invention, and the conditions except that are same as those of No. 1.
  • the precipitate-free zone was significantly over 100 nm. Accordingly, the tensile strength was below 550 MPa, cracks were generated by the 180° bending test of 0 radius and the stress relaxation performance was over 30%.
  • No. 4 is also the conventional example and conducted the high degree reduction ratio of cold rolling, to increase the tensile strength of No. 3 up to 550 MPa.
  • the reduction ratio was high, and in addition, the precipitate-free zone was over 100 nm. Accordingly, the heavy shaking at the level where the test piece was broken by the 180° bending test of 0 radius was generated, and the stress relaxation performance was over 30%.
  • Table 2 shows the data in the case where the rate of temperature increase in aging in No. 1 is changed. It shows that the width of the precipitate-free zone is narrowed by reducing the rate of temperature increase. The tensile strength, bendability and stress relaxation performance improve because of the narrowed width of the precipitate-free zone.
  • the rate of temperature increase was over 50° C./h in some temperature provinces in the comparative examples No. 9 and 10. Accordingly, the precipitate-free zone was over 100 nm, the tensile strength was below 550 MPa, cracks were generated by the 180° bending test of 0 radius and the stress relaxation performance was over 30%.
  • Table 3 shows the data in the case where the maximum reaching temperature and the time of maintaining 450 to 550° C. in aging in No. 2 is changed.
  • the electrical conductivity improves.
  • the precipitate-free zone broadens.
  • the width of the precipitate-free zone is less than 10 nm and the electrical conductivity is less than 55% IACS.
  • the width of the precipitate-free zone is more than 100 nm
  • the tensile strength is less than 550 MPa
  • cracks are generated by the 180° bending test of 0 radius and the stress relaxation performance is more than 30%.
  • the width of the precipitate-free zone broadens.
  • the width of the precipitate-free zone is more than 100 nm
  • the tensile strength is less than 550 MPa
  • cracks are generated by the 180° bending test of 0 radius and the stress relaxation performance is more than 30%.
  • Table 4 shows the data in the case where the rolling reduction ratio in No. 1 is changed. It shows that “b/a” which is calculated from the metal structure of the products and the tensile strength increase as the reduction ratio increases.
  • Table 5 shows the data in the case where the grain size after the solution treatment in No. 2 is changed. It shows that “a” which is calculated from the crystal structure of the products increases and the stress relaxation performance decreases as the grain size after the solution treatment increases.
  • Table 6 shows the data in the case where Ni concentration is fixed to 1.60 mass % and Si concentration is changed.
  • the test pieces of No. 1 and 5 are same as that of Table 1.
  • the test piece of No. 5 is the conventional alloy whose electrical conductivity is less than 55% IACS and its manufacturing condition is different from those of other test pieces.
  • the result of the evaluation for the thermal peel resistance of Sn plating of the alloys in the present invention is ⁇ (detached in point shapes).
  • the results of the evaluation for No. 5 and 34 are X. This is because the solid solution of Si deteriorates the thermal peel resistance. That is, the solid solution of Si increased because the amount of precipitation of Ni 2 Si in No. 5 was small and Si was added excessively compared to Ni in No. 34.
  • Table 7 shows the data in the case where Ni concentration/Si concentration is maintained within the range of that in the present invention and Ni concentration is changed.
  • the tensile strength in No. 35, where Ni concentration is less than 1.2 mass %, is less than 550 MPa.
  • the tensile strength in No. 41, where Ni concentration is more than 3.5 mass %, is more than 700 MPa and cracks are generated by the 180° bending test of 0 radius.
  • Table 8 shows the data in the case where Zn of different concentrations is added in No. 1.
  • the result of the evaluation for the thermal peel resistance of Sn plating of the alloys in the present invention became ⁇ (no peeling) by adding more than 0.05 mass % Zn.
  • the electrical conductivity decreased as the amount of Zn increased.
  • the electrical conductivity was more than 55% IACS in the range of less than 0.5 mass % Zn.
  • Table 9 shows the data in the case where the impurities in No. 43 increased.
  • the total amount of the impurities is changed by adding Sn for supposed interfusion of Sn plated Cu materials and adding Mg for supposed residual deoxidation elements at melting.
  • the electrical conductivity is less than 55% IACS in the case where the impurities is more than 0.05 mass %.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Thermal Sciences (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Conductive Materials (AREA)
  • Lead Frames For Integrated Circuits (AREA)
US12/311,401 2006-09-25 2007-09-21 Cu-ni-si system alloy Abandoned US20100000637A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2006259294A JP4143662B2 (ja) 2006-09-25 2006-09-25 Ｃｕ−Ｎｉ−Ｓｉ系合金
JP2006-259294 2006-09-25
PCT/JP2007/068420 WO2008038593A1 (fr) 2006-09-25 2007-09-21 Alliage de cu-ni-si

Publications (1)

Publication Number Publication Date
US20100000637A1 true US20100000637A1 (en) 2010-01-07

Family

ID=39230028

Family Applications (1)

Application Number Title Priority Date Filing Date
US12/311,401 Abandoned US20100000637A1 (en) 2006-09-25 2007-09-21 Cu-ni-si system alloy

Country Status (6)

Country Link
US (1) US20100000637A1 (ko)
JP (1) JP4143662B2 (ko)
KR (1) KR101056973B1 (ko)
CN (1) CN101512026B (ko)
TW (1) TW200823302A (ko)
WO (1) WO2008038593A1 (ko)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120299690A1 (en) * 2011-05-27 2012-11-29 Yoshihiro Nakanishi Circuit breaker and battery pack including the same
US20150354048A1 (en) * 2013-01-22 2015-12-10 Korea Institute Of Machinery & Materials Metal composite comprising aligned precipitate and preparation method therefor
US20160071632A1 (en) * 2013-06-07 2016-03-10 VDM Metals GmbH Method for producing a metal film
US9514856B2 (en) 2011-08-04 2016-12-06 Kobe Steel, Ltd. Copper alloy

Families Citing this family (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101946014A (zh) * 2008-02-18 2011-01-12 古河电气工业株式会社 铜合金材料
JP5468798B2 (ja) * 2009-03-17 2014-04-09 古河電気工業株式会社 銅合金板材
JP2010255042A (ja) * 2009-04-24 2010-11-11 Hitachi Cable Ltd 銅合金及び銅合金の製造方法
EP2508631A1 (en) * 2009-12-02 2012-10-10 Furukawa Electric Co., Ltd. Copper alloy sheet material, connector using same, and copper alloy sheet material production method for producing same
KR101419147B1 (ko) 2009-12-02 2014-07-11 후루카와 덴키 고교 가부시키가이샤 구리합금 판재 및 그 제조방법
JP5476149B2 (ja) * 2010-02-10 2014-04-23 株式会社神戸製鋼所 強度異方性が小さく曲げ加工性に優れた銅合金
JP5319578B2 (ja) * 2010-03-01 2013-10-16 Ｊｘ日鉱日石金属株式会社 電子部品用チタン銅の製造方法
WO2011125153A1 (ja) * 2010-04-02 2011-10-13 Jx日鉱日石金属株式会社 電子材料用Ｃｕ－Ｎｉ－Ｓｉ系合金
JP4630387B1 (ja) * 2010-04-07 2011-02-09 古河電気工業株式会社 銅合金展伸材、銅合金部品および銅合金展伸材の製造方法
EP2557187A1 (en) 2010-04-07 2013-02-13 Furukawa Electric Co., Ltd. Wrought copper alloy, copper alloy part, and process for producing wrought copper alloy
KR101703679B1 (ko) * 2010-07-07 2017-02-07 미츠비시 신도 가부시키가이샤 딥 드로잉 가공성이 우수한 Ｃｕ―Ｎｉ―Ｓｉ계 동합금판 및 그 제조 방법
KR101811080B1 (ko) * 2010-08-27 2017-12-20 후루카와 덴키 고교 가부시키가이샤 구리합금판재 및 그의 제조방법
JP4824124B1 (ja) * 2010-09-17 2011-11-30 古河電気工業株式会社 銅合金展伸材、銅合金部品および銅合金展伸材の製造方法
CN102021359B (zh) * 2010-11-03 2013-01-02 西安理工大学 高Ni、Si含量的Cu-Ni-Si合金的制备方法
JP5192536B2 (ja) * 2010-12-10 2013-05-08 三菱伸銅株式会社 深絞り加工性及び耐疲労特性に優れたＣｕ−Ｎｉ−Ｓｉ系銅合金板及びその製造方法
JP5180283B2 (ja) * 2010-12-24 2013-04-10 三菱伸銅株式会社 曲げ加工後の耐疲労特性及びばね特性に優れたＣｕ−Ｎｉ−Ｓｉ系銅合金板及びその製造方法
TWI461549B (zh) * 2012-02-14 2014-11-21 Jx Nippon Mining & Metals Corp Carbene alloy and its manufacturing method
WO2014016934A1 (ja) * 2012-07-26 2014-01-30 三菱電機株式会社 銅合金及びその製造方法
JP6301618B2 (ja) * 2013-09-17 2018-03-28 古河電気工業株式会社 銅合金材およびその製造方法
CN107119247B (zh) * 2017-06-08 2018-10-30 西安交通大学 一种可改善中高吨位熔炼CuNiSiCr合金性能稳定性的热处理方法
CN112813368B (zh) * 2020-12-25 2022-05-13 大连交通大学 一种高性能Cu-Ni-Si合金板带材及其生产工艺
CN113249666A (zh) * 2021-05-14 2021-08-13 太原晋西春雷铜业有限公司 一种降低Cu-Ni-Si合金热收缩率的制备方法
CN115029581B (zh) * 2022-06-10 2022-12-09 中铁建电气化局集团轨道交通器材有限公司 硅青铜锻件及其无内应力一体式锻压及热处理方法
CN115613043A (zh) * 2022-11-11 2023-01-17 安徽鑫科铜业有限公司 一种铜镍硅合金带材表面处理溶液及铜镍硅合金带材表面处理方法
CN115627380B (zh) * 2022-11-11 2023-07-25 安徽鑫科铜业有限公司 一种低浓度铜镍硅合金材料及其制备方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020155021A1 (en) * 2001-01-30 2002-10-24 Hifumi Nagai Copper-alloy foil to be used for laminate sheet

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03162553A (ja) * 1989-11-22 1991-07-12 Nippon Mining Co Ltd 曲げ加工性の良好な高強度高導電銅合金の製造方法
JP3334157B2 (ja) * 1992-03-30 2002-10-15 三菱伸銅株式会社 スタンピング金型を摩耗させることの少ない銅合金条材
JP2001207229A (ja) 2000-01-27 2001-07-31 Nippon Mining & Metals Co Ltd 電子材料用銅合金
JP2004315940A (ja) * 2003-04-18 2004-11-11 Nikko Metal Manufacturing Co Ltd Ｃｕ−Ｎｉ−Ｓｉ合金およびその製造方法
JP4255330B2 (ja) * 2003-07-31 2009-04-15 日鉱金属株式会社 疲労特性に優れたＣｕ−Ｎｉ−Ｓｉ系合金部材
JP4100629B2 (ja) * 2004-04-16 2008-06-11 日鉱金属株式会社 高強度高導電性銅合金
JP2006176886A (ja) * 2006-03-10 2006-07-06 Furukawa Electric Co Ltd:The 端子ないしはコネクタ用銅合金材

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020155021A1 (en) * 2001-01-30 2002-10-24 Hifumi Nagai Copper-alloy foil to be used for laminate sheet

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120299690A1 (en) * 2011-05-27 2012-11-29 Yoshihiro Nakanishi Circuit breaker and battery pack including the same
US9159985B2 (en) * 2011-05-27 2015-10-13 Ostuka Techno Corporation Circuit breaker and battery pack including the same
US9514856B2 (en) 2011-08-04 2016-12-06 Kobe Steel, Ltd. Copper alloy
US20150354048A1 (en) * 2013-01-22 2015-12-10 Korea Institute Of Machinery & Materials Metal composite comprising aligned precipitate and preparation method therefor
US20160071632A1 (en) * 2013-06-07 2016-03-10 VDM Metals GmbH Method for producing a metal film
US10923248B2 (en) * 2013-06-07 2021-02-16 Vdm Metals International Gmbh Method for producing a metal film

Also Published As

Publication number Publication date
TW200823302A (en) 2008-06-01
JP2008075172A (ja) 2008-04-03
WO2008038593A1 (fr) 2008-04-03
KR20090016485A (ko) 2009-02-13
JP4143662B2 (ja) 2008-09-03
KR101056973B1 (ko) 2011-08-16
CN101512026A (zh) 2009-08-19
TWI355426B (ko) 2012-01-01
CN101512026B (zh) 2011-03-09

Similar Documents

Publication Publication Date Title
US20100000637A1 (en) Cu-ni-si system alloy
JP5312920B2 (ja) 電子材料用銅合金板又は条
KR100515804B1 (ko) 고강도 티탄 구리 합금 및 그 제조법 및 그것을 사용한단자ㆍ커넥터
JP4494258B2 (ja) 銅合金およびその製造方法
JP5225787B2 (ja) 電子材料用Ｃｕ−Ｎｉ−Ｓｉ系合金板又は条
JP5506806B2 (ja) 電子材料用Ｃｕ−Ｎｉ−Ｓｉ−Ｃｏ系銅合金及びその製造方法
WO2009122869A1 (ja) 電子材料用Ｃｕ－Ｎｉ－Ｓｉ－Ｃｏ系銅合金及びその製造方法
JP4830035B2 (ja) 電子材料用Ｃｕ−Ｓｉ−Ｃｏ系合金及びその製造方法
KR101114116B1 (ko) 전기전자기기용 동합금 재료 및 전기전자부품
JP4787986B2 (ja) 銅合金およびその製造方法
JP2006152392A (ja) 曲げ加工性に優れた高強度銅合金板およびその製造方法
JP5619389B2 (ja) 銅合金材料
JP2008248333A (ja) 電子材料用Ｃｕ−Ｎｉ−Ｓｉ−Ｃｏ系銅合金及びその製造方法
KR101338710B1 (ko) Ｎｉ－Ｓｉ－Ｃｏ 계 구리 합금 및 그 제조 방법
JP5135914B2 (ja) 電気・電子部品用高強度銅合金の製造方法
JP2006291356A (ja) Ｎｉ−Ｓｎ−Ｐ系銅合金
WO2011152104A1 (ja) Ｃｕ－Ｃｏ－Ｓｉ系合金板及びその製造方法
JP2011219860A (ja) 電子材料用Ｃｕ−Ｓｉ−Ｃｏ系合金及びその製造方法
JP2010285671A (ja) 高強度高導電性銅合金とその製造方法
JP3049137B2 (ja) 曲げ加工性が優れた高力銅合金及びその製造方法
JP4225733B2 (ja) 端子、コネクター、リードフレーム用素材板
JP4664584B2 (ja) 高強度銅合金板および高強度銅合金板の製造方法
JP7227245B2 (ja) 強度及び導電率に優れた銅合金板材の製造方法及びこれから製造された銅合金板材
JPH0718355A (ja) 電子機器用銅合金およびその製造方法
JP2010236029A (ja) 電子材料用Ｃｕ−Ｓｉ−Ｃｏ系合金及びその製造方法

Legal Events

Date Code Title Description
AS Assignment

Owner name: NIPPON MINING & METALS CO., LTD., JAPAN

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:HATANO, TAKAAKI;REEL/FRAME:022524/0390

Effective date: 20090313

AS Assignment

Owner name: JX NIPPON MINING & METALS CORPORATION, JAPAN

Free format text: CHANGE OF NAME;ASSIGNOR:NIPPON MINING HOLDINGS, INC.;REEL/FRAME:024996/0272

Effective date: 20100701

Owner name: NIPPON MINING HOLDINGS, INC., JAPAN

Free format text: MERGER;ASSIGNOR:NIPPON MINING & METALS CO., LTD.;REEL/FRAME:024996/0137

Effective date: 20100701

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION