WO2008038593A1 - Alliage de cu-ni-si - Google Patents

Alliage de cu-ni-si Download PDF

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Publication number
WO2008038593A1
WO2008038593A1 PCT/JP2007/068420 JP2007068420W WO2008038593A1 WO 2008038593 A1 WO2008038593 A1 WO 2008038593A1 JP 2007068420 W JP2007068420 W JP 2007068420W WO 2008038593 A1 WO2008038593 A1 WO 2008038593A1
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Prior art keywords
mass
less
alloy
rolling
stress relaxation
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PCT/JP2007/068420
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English (en)
Japanese (ja)
Inventor
Takaaki Hatano
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Nippon Mining & Metals Co., Ltd.
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Application filed by Nippon Mining & Metals Co., Ltd. filed Critical Nippon Mining & Metals Co., Ltd.
Priority to CN2007800326042A priority Critical patent/CN101512026B/zh
Priority to US12/311,401 priority patent/US20100000637A1/en
Priority to KR1020087031101A priority patent/KR101056973B1/ko
Publication of WO2008038593A1 publication Critical patent/WO2008038593A1/fr

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    • 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
    • C22C9/06—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
    • 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
    • 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 a Cu—Ni—Si based alloy suitable for use in various electronic components such as lead frames, connectors, pins, terminals, relays, and switches.
  • the present invention also relates to a method for producing the alloy. Furthermore, this invention relates to the electronic component using this alloy.
  • Copper alloys for electronic materials used in electronic parts and the like are required to have both high strength and high conductivity (or thermal conductivity) as basic characteristics.
  • bending workability, stress relaxation characteristics, heat resistance, adhesive properties such as heat release, solder wettability, etching workability, press punching properties, and corrosion resistance are also required.
  • Cu-Ni-Si alloys are copper alloys with relatively high electrical conductivity and strength, and are one of the alloys that are currently being actively developed in the industry. It is. In this copper alloy, strength and electrical conductivity are increased by the precipitation of fine Ni-Si intermetallic particles in the copper matrix.
  • Patent Document 1 discloses a Cu—Ni—Si alloy that achieves both high strength and bending workability.
  • the sum of the cold rolling processing ratios before and after the aging treatment should be 40% or less, and in the solution treatment, the recrystallized grains have a particle size of 5 to 15 m and heated to 15 m. It is disclosed that the conditions should be selected and that the aging treatment should be 30 to 300 minutes at 440 to 500 ° C.
  • the copper alloy specifically disclosed in this document does not generate cracks due to W-bending, and the conductivity is low. At the highest 53% IACS, the tensile strength is 520 MPa, and when the tensile strength is the highest, 710 MPa, the conductivity is 46% IACS (see Table 2 in the Examples).
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2001-207229
  • Fe, and / or Zr, Cr, Ti, and Mo are added to the Cu-Ni-Si alloy to adjust the components, and Mg, Zn, Sn, Al, P, It is described that inclusion of Mn, Ag, or Be can provide a material suitable as a copper alloy for electronic materials.
  • the copper alloy specifically disclosed in this document does not generate cracks when bent at 90 ° (not 180 °), and has a tensile strength of 640 MPa at 56% IACS, which has the highest conductivity.
  • the electrical conductivity is 44% IACS at the highest tensile strength of 698 MPa (see Table 1 in the Examples).
  • the working degree of cold rolling performed before and after aging treatment is set to 60% and 35.5% (97.5% in total), respectively.
  • Patent Document 3 describes a Cu having a conductivity of 60% IACS or higher, high strength, excellent stiffness strength, repeated bendability, and high heat resistance.
  • Ni—Si alloys are disclosed.
  • This document contains Mn: 0.02-1.0 wt%, Zn: 0.1—5.0 wt%, Mg: 0.001—0.01 wt% as additive elements, and Cr, Ti, Zr. It is stated that one or two or more selected from among them should be contained in an amount of 0.0001-0.01 wt% .
  • the tensile strength is 51.0 kgf / mm 2 (500 MPa), the electrical conductivity. 67. 0% IACS data and tensile strength 62.0 kgf / mm 2 (593 MPa), conductivity 60.0% IACS data and data are disclosed! /, (See Table 2).
  • the Cu-Ni-Si alloy is cold-rolled from 10 mm after hot rolling to 0.25 mm without recrystallization annealing.
  • the rolling degree is remarkably high at 97.5%, and it is assumed that the bending workability is extremely deteriorated.
  • annealing is performed at 450 ° C during and after cold rolling. In the case of Cu-Ni-Si alloys, this temperature is used. Although the precipitation reaction proceeds, recrystallization does not proceed! /.
  • Patent Document 4 a specific amount of Sn, Mg, or further Zn is added, the S and O contents are limited, and the crystal grain size exceeds 1 ⁇ m.
  • a Cu—Ni—Si alloy having excellent mechanical properties, conductivity, stress relaxation properties and bending workability is disclosed.
  • the document also states that recrystallization should be performed at 700 to 920 ° C after cold working in order to adjust the crystal grain size to the above range.
  • a Cu—Ni—Si-based alloy capable of 180 ° tight bending with a tensile strength of 610 to 710 MPa is disclosed.
  • the conductivity of this alloy is 31-42% IACS, and the stress relaxation rate when heated at 150 ° C for 1000 hours is 14-22%.
  • Patent Document 5 Japanese Patent No. 3520034 (Patent Document 5) includes a specific amount of Mg, Sn, Zn, S, a crystal grain size of more than 0.001 mm and less than 0.025 mm, and final plastic working.
  • the ratio (a / b) of the major axis a of the crystal grain in the cross section parallel to the direction to the major axis b of the crystal grain in the cross section perpendicular to the final plastic working direction is 0.8 or more and 1.5 or less.
  • a Cu-Ni-Si alloy characterized by excellent stress relaxation properties is disclosed.
  • non-patent documents 1 and 2 etc. have reported a technique for improving strength and bendability by focusing on the precipitation-free zone (PFZ). ing.
  • the non-precipitation zone is a band-like region that is formed in the vicinity of a grain boundary by grain boundary reaction type precipitation (discontinuous precipitation) during aging and does not have fine precipitates. Since there are no fine precipitates that contribute to strength, when no external force is applied, the precipitate-free zone preferentially undergoes plastic deformation, leading to a decrease in tensile strength and bending workability.
  • Non-Patent Document 1 the addition of P and Sn and two-stage aging are effective in suppressing the precipitation-free zone. Regarding the latter, it is described that the strength was greatly increased without impairing the elongation by adding the pre-aging of 250 ° CX 48h before the normal aging of 450 ° CX 16h. Specifically, an 11 ⁇ 31 series alloy having a tensile strength of 770 to 900 MPa and an electrical conductivity of 34 to 36% 1 to 3 is disclosed.
  • Non-Patent Document 2 describes that the width of PFZ increases as the aging time increases.
  • Patent Document 1 Japanese Patent Laid-Open No. 2002-260442
  • Patent Document 2 Japanese Patent Laid-Open No. 2001-207229
  • Patent Document 3 Japanese Patent Laid-Open No. 61-194158
  • Patent Document 4 JP-A-11 222641
  • Patent Document 5 Japanese Patent No. 3520034
  • Non-Patent Document 1 Chihiro Watanabe, Masaru Miyakoshi, Fumiya Nishijima, Ryoichi Monzen: "Cu 4. Omass% Ni-0. 95mass% Si-0. 02mass% P alloy improved mechanical properties", copper and copper alloy, Japan Copper and Brass Association, 2006, Vol. 45, No. 1, p. 16-22
  • Non-Patent Document 2 Goro Ito, Toshiaki Suzuki, A To T Keihei, Yamamoto Yoshinori, Ito Nobuhide, "Effects of Ni, Si content and aging conditions on the bending workability of Cu-Ni Si alloy sheet", copper Copper Alloy, Japan Copper and Brass Association, 2006, Vol. 45, No. 1, p. 71-75
  • ⁇ is the temperature rise
  • J is the current
  • E is the conductivity
  • H is the thermal conductivity
  • L and S are the length and cross-sectional area of the current-carrying part, respectively. Since H is proportional to E, the temperature rise is inversely proportional to the square of conductivity.
  • an object of the present invention is to provide a Cu—Ni—Si based alloy for electronic materials that does not contain other alloy elements as much as possible and has improved conductivity, strength, bendability and stress relaxation characteristics. Is to provide.
  • Another object of the present invention is to provide a method for producing the Cu—Ni—Si based alloy. Still another object of the present invention is to provide an elongation using the Cu—Ni—Si based alloy. To provide copper products and electronic components.
  • the present inventor has intensively studied to solve the above-mentioned problems.
  • the rate of temperature increase in aging treatment the maximum temperature reached by the material, and the aging It has excellent electrical conductivity, tensile strength, stress relaxation resistance and bendability by giving special conditions to the time and further optimizing the solution treatment conditions and the rolling degree before and after the aging treatment.
  • Cu-Ni-Si alloys can be obtained.
  • the present invention completed on the basis of the above knowledge is: 1. 2 to 3.5 mass% Ni, Ni concentration (mass%) 1/6 to; 1/4 concentration (mass%)
  • Ni concentration (mass%) 1/6 to; 1/4 concentration (mass%)
  • This is a Cu-Ni-Si alloy characterized in that it contains Si and the balance is composed of Cu and impurities of 0.05 mass% or less in total, and has the following characteristics.
  • Zn when Zn is added to the above alloy, the electrical conductivity is slightly reduced, but since the effect of improving the heat-resistant peelability of Sn plating is great, the above alloy is particularly desirable when seeking good heat-resistant peelability of Sn plating.
  • Zn may be added up to an upper limit of 0.5 mass%! /.
  • 1.2 to 3.5 mass% Ni, Ni concentration (mass% ) With a concentration (mass%) of l / 6 to l / 4, Zn of 0.5 mass% or less, with the balance being Cu and a total amount of impurities of 0.05 mass% or less. It is a Cu-Ni-Si alloy characterized by having the above characteristics.
  • the copper alloy according to the present invention has a cross-sectional metallographic structure parallel to the rolling surface, the average grain size in the direction perpendicular to the rolling direction of the crystal grains is a, the direction parallel to the rolling direction When the average particle size of b is b,
  • the average width of the precipitation-free zone in the metal structure is 10 to 100 nm.
  • electronic components such as a lead frame, a connector, a pin, a terminal, a relay, a switch, and a foil material for a secondary battery using the copper alloy.
  • the method for producing a Cu-Ni-Si-based alloy including sequentially performing the steps of solution treatment, cold rolling, aging treatment, and cold rolling,
  • the above-mentioned Cu—Ni—Si alloy production method is characterized in that the process is performed under the following conditions. (Solution treatment)
  • the average crystal grain size is adjusted to a range of !! to 15 m.
  • the maximum temperature of the material during the heat treatment is 550 ° C or lower, and the material is kept in the temperature range of 450 to 550 ° C for 5 to 15 hours.
  • the average heating rate of the material in each temperature zone of 200 to 250 ° C, 250 to 300 ° C, and 300 to 350 ° C in the temperature rising process shall be 50 ° C / h or less.
  • Cold rolling The sum of the rolling work in cold rolling before aging and the rolling work in cold rolling after aging is 5-40%.
  • the Si concentration (mass%) is in the range of 1/6 to 1/4 of the Ni concentration (mass%). This is because good conductivity (for example, 55% IACS or more) cannot be obtained if Si is out of this range.
  • a preferred Si range is 1 / 5.5-1 / 4.2 of Ni, and a more preferred Si range is 1/5 ⁇ 2 ⁇ 1 / 4 ⁇ 5 of Ni.
  • Ni is 1.2 to 3.5 mass%. When Ni is less than 1.2% by mass, good tensile strength (eg, 550 MPa or more) cannot be obtained. If Ni exceeds 3.5 mass%, good bending workability cannot be obtained (for example, cracking occurs in 180-degree contact bending).
  • a preferable Ni concentration is 1.4 to 2.5% by mass, and a more preferable range of Ni is 1.5 to 2.0% by mass.
  • the total amount of impurities is controlled to 0.05% by mass or less, preferably 0.02% by mass or less, more preferably 0.01% by mass or less. Therefore, in a preferred embodiment of the present invention, alloy elements other than Ni and Si are not present in the Cu—Ni—Si alloy except for inevitable impurities.
  • Zn has a relatively small effect on electrical conductivity, it has a large effect on improving the heat-resistant peelability of Sn plating. May be.
  • the decrease in conductivity per 1% by mass of ZnO is about 0.5% IACS.
  • the Zn force SO. Exceeds 5% by mass, it becomes difficult to obtain a sufficient conductivity (for example, 55% IACS or more), and when the Zn content is less than 0.05% by mass, the heat resistance of the Sn plating is improved. There is almost no improvement effect. Therefore, the preferable Zn concentration is 0.05 to 0.5% by mass, A more preferable Zn concentration is 0.;! To 0.3% by mass.
  • b / a When b / a is less than 1.05, good tensile strength cannot be obtained (for example, less than 550 MPa). On the other hand, if b / a exceeds 1.67, good bendability cannot be obtained (for example, cracking occurs due to 180 degree contact bending).
  • the average width of the precipitation-free zone in the metal structure is 10 to! OOnm. If the width of the precipitation-free zone is increased, sufficient bendability, stress relaxation resistance and tensile strength cannot be obtained. When the width of the precipitation-free zone exceeds lOOnm, good bendability cannot be obtained (for example, cracking occurs by 180 ° contact bending), and good stress relaxation rate cannot be obtained (for example, more than 30%).
  • the width of the precipitation-free zone is preferably as narrow as possible.
  • a preferable average width of the precipitation-free zone for improving the conductivity, bending workability and stress relaxation resistance in a well-balanced manner is 20 to 90 nm, and a more preferable average width of the precipitation-free zone is 30 to 80 nm.
  • the copper alloy according to the present invention has the following characteristics.
  • the copper alloy according to the present invention has the following characteristics.
  • the copper alloy according to the present invention has the following characteristics:
  • the copper alloy according to the present invention to which Zn is added is another preferred! /, And in the embodiment, the following characteristics can be achieved at the same time.
  • the "Sn plating heat-resistant peeling test” refers to a method for evaluating the Sn plating peeling of a test piece in the following manner.
  • the copper alloy according to the present invention has the same composition and is comparable to the copper alloy according to the present invention, that is, conductivity, strength, bending workability and stress relaxation characteristics. No example has been achieved in a balanced manner up to the level of the present invention.
  • Ni and Si compounds dissolved in the solution treatment are precipitated as fine particles by heating at a temperature range of about 350 to about 550 ° C for lh or more.
  • This aging treatment increases strength and conductivity.
  • cold rolling may be performed before and / or after aging.
  • strain relief annealing low temperature annealing
  • overaging may be performed.
  • good conductivity eg, about 60% IACS
  • the compressive force, pliable force, and tensile strength decrease (for example, up to about 500 MPa), which causes deterioration of stress relaxation resistance and bendability rather than force and glue.
  • the tensile strength recovers to about 600 MPa, the bendability is significantly deteriorated due to processing strain, and the stress relaxation resistance cannot be improved.
  • Conventional high-conductivity Cu-Ni-Si alloys disclosed in Patent Document 3 etc. were basically technologies that applied this overaging.
  • the present inventor has made studies in order to improve the electrical conductivity, strength, bendability and stress relaxation resistance in a well-balanced manner. As a result, in the manufacturing process of a Cu-Ni-Si alloy with as few impurities as possible. Excellent electrical conductivity is achieved by applying special conditions to the rate of temperature rise in aging treatment, the highest temperature reached for the material, and the aging time, and further optimizing the solution treatment conditions and the degree of rolling before and after the aging treatment. The present inventors have found that a Cu-Ni-Si based alloy having tensile strength, stress relaxation resistance and bendability can be obtained.
  • the rate of temperature rise, the maximum material temperature, the time during which the material is maintained at a temperature of 450 to 550 ° C, and the rate of temperature rise of the material are specified.
  • the average heating rate of the material in each temperature range of C must be 50 ° C / h or less. From the viewpoint of production efficiency, the average rate of temperature rise is preferably 10 ° C / h or more. Typically, the average heating rate is 20-40. C / h.
  • the method of temperature increase rate control of the present invention is an industrially extremely effective method that hardly reduces the production efficiency.
  • the temperature is preferably 530 ° C or lower, more preferably 500 ° C or lower.
  • the maximum temperature is preferably 450 ° C or more, more preferably 480 ° C or more.
  • the width of the precipitate-free zone becomes narrow (for example, less than lOnm), but sufficient conductivity cannot be obtained even if the rate of temperature rise is suppressed. If it exceeds 15 hours, the width of the precipitation-free zone becomes wider (for example, more than 100 nm). A more preferable time considering production efficiency is 6 to 10 hours.
  • the heating temperature and heating conditions of the solution treatment for obtaining the above crystal grain size are well known, and can be appropriately set by those skilled in the art.
  • the material is heated to an appropriate temperature of 700 to 800 ° C.
  • the crystal grain size is obtained by holding for an appropriate time of 5 to 600 seconds and then quickly cooling with air or water.
  • the total workability of intermediate rolling and final rolling is 5-40%.
  • the total workability is less than 5%, the b / a required from the metal structure of the product is less than 1.05, and when the total workability exceeds 40%, the b / a exceeds 1.67.
  • strain relief annealing may be performed for the purpose of improving the spring limit value and the like.
  • the strain relief annealing may be performed at a low temperature for a long time (for example, 300 ° C x 30 minutes) !, or at a high temperature for a short time (for example, 500 ° C for 30 seconds). If the temperature is too high or the time is too long, the decrease in tensile strength will increase. It is preferable to select the conditions with a decrease in tensile strength of 10 to 50 MPa.
  • the maximum temperature of the material during heat treatment is 550 ° C or less, and the material is kept in the temperature range of 450-550 ° C for 5 to 15 days. C, 250-300.
  • steps such as grinding, polishing, and shot blast pickling for removing oxide scale on the surface can be appropriately performed between the above steps.
  • the Cu-Ni-Si alloy of the present invention is applied to various copper products such as plates, strips, tubes, rods and wires. Furthermore, the Cu Ni Si-based copper alloy according to the present invention is particularly suitable as a lead frame material for semiconductor devices such as conductive spring materials such as connectors, terminals, relays and switches, transistors and integrated circuits. Can be used.
  • the concentration in the ingot was determined by the semi-quantitative analysis of all elements by glow discharge mass spectrometry, and the total amount was about 0.01% by mass.
  • Fe (0.005 mass%), S (0.001 mass%), and C (0.001 mass%) were elements with relatively high concentrations.
  • the ingot was heated at 950 ° C for 3 hours and then hot-rolled to a thickness of 8 mm, and the oxidized scale on the surface was removed with a grinder. Thereafter, cold rolling, solution treatment, cold rolling (intermediate rolling), aging treatment, cold rolling (final rolling), and strain relief annealing were performed in this order. The degree of processing in each rolling and the thickness during heat treatment were adjusted so that the final rolled thickness would be 0.25 mm. After solution treatment, aging treatment and strain relief annealing, pickling with 10% sulfuric acid 1% hydrogen peroxide solution and mechanical polishing with # 1200 emery paper to remove surface oxide film generated by heat treatment Were sequentially performed.
  • the sample was inserted into an electric furnace adjusted to a predetermined temperature for a predetermined time, then immediately removed from the electric furnace and air-cooled.
  • the sample was heated under various temperature conditions using an electric furnace.
  • the sample temperature was measured by bringing the sample into contact with a thermocouple.
  • strain relief annealing the sample was placed in a 300 ° C electric furnace for 30 minutes, then removed from the electric furnace and air-cooled. If final rolling is not performed, this strain relief annealing was not performed.
  • an EBSP Electro Backscattering Pattern
  • the vicinity of the grain boundary of the product was observed with a transmission electron microscope at a magnification of about 100,000 times, and the average width of the precipitation-free zone (average value at any 30 power points) was obtained.
  • the electrical conductivity of the product was measured by the 4-terminal method in accordance with JIS H 0505.
  • the JIS 13 B test piece was produced using the press so that the tensile direction might be parallel to the rolling direction.
  • a tensile test was performed on the specimen in accordance with JIS-Z2241 to determine the tensile strength.
  • a strip-shaped test piece having a width of 10 mm and a length of 100 mm was taken from the product so that the longitudinal direction of the test piece was parallel to the rolling direction.
  • the specimen is given yo deflection and is 0.2% resistant (measured in accordance with JIS Z2241). Stress corresponding to% ( ⁇ ⁇ ) was applied.
  • yo was obtained from the following equation.
  • E Young's modulus
  • t the thickness of the sample.
  • Plating bath composition copper sulfate 200g / L, sulfuric acid 60g / L
  • 'Plating bath composition stannous oxide 41g / L, phenolsulfonic acid 268g / L, surfactant 5g / L
  • the composition of the sample was Cu-1.60 mass% Ni—0.35 mass% 31 alloy, and it was processed into a product by changing solution treatment conditions, aging treatment conditions, and rolling conditions.
  • Figure 2 is a typical aging treatment temperature chart. The broken line indicates the temperature of the atmosphere in contact with the sample, and the solid line indicates the sample temperature.
  • the material was placed in an electric furnace adjusted to 200 ° C and held for 1 hour, and then the furnace temperature was increased from 200 ° C to 350 ° C over 5 hours. Next, the furnace temperature is raised to 500 ° C over 1 hour and held for 8 hours, then taken out of the electric furnace and air cooled.
  • the material was placed in an electric furnace adjusted to 200 ° C and held for 1 hour, then the furnace temperature was increased from 200 ° C to 250 ° C over 3 hours, and over 2 hours. The temperature was raised to 300 ° C and raised to 350 ° C over 1 hour. Next, the furnace temperature was raised to 490 ° C over 1 hour and held for 10 hours, after which it was removed from the electric furnace and air-cooled.
  • (c) shows the case where the material was put into an electric furnace adjusted to 500 ° C, taken out of the electric furnace after 9 hours and air-cooled. This corresponds to a conventional heat treatment procedure.
  • Fig. 2 Nichiera effect turn ⁇ , 200 ⁇ 250 ° C, 250 ⁇ 300 ° C and 300 ⁇ 350 ° C (average heating rate, maximum material temperature, 450-550 ° The retention time was determined in the temperature range of C.
  • the product was processed under the solution treatment conditions and rolling conditions of the present invention, and the structure and properties were investigated.
  • (A) (b) (c) in Fig. 2 These correspond to No. 1, 2, and 3 in Table 1, respectively.
  • Nos. 1 and 2 produced under the conditions of the present invention satisfy the metal structure and properties of the product defined by the present invention.
  • the temperature increase rate of No. 3 which is a conventional example is larger than the range of the present invention, and other conditions are the same as No. 1. Since the precipitation-free zone greatly exceeded lOOnm, the tensile strength was less than 550 MPa, cracking occurred at 180 ° contact bending, and the stress relaxation rate exceeded 30%.
  • No. 4 is also a conventional example.
  • the rolling degree is increased.
  • the precipitation-free zone exceeded lOOnm, so the 180 degree contact bending resulted in severe cracking at the level at which the specimen broke, and the stress relaxation exceeded 30%.
  • No. 5 is a conventional general Cu-Ni-Si alloy. Peak aging is performed and properties are created with priority given to tensile strength. The bendability and stress relaxation resistance are good. The power conductivity is less than 50% IACS.
  • Table 2 shows the data when No. 1 is heated at different aging rates. It can be seen that the width of the precipitation-free zone becomes smaller by slowing the heating rate. As the width of the precipitation-free zone becomes smaller, the tensile strength, bendability, and stress relaxation resistance are improved. In Comparative Example No. 9.10, the rate of temperature rise exceeded 50 ° C / h in any temperature zone, so the width of the precipitation-free zone exceeded 10 Onm, the tensile strength was less than 550 MPa, 180 degrees Cracks occurred due to close contact bending, and the stress relaxation rate exceeded 30%.
  • Table 3 shows the data for No. 2 when the maximum temperature at aging and the holding time at 450 to 550 ° C were changed.
  • Table 4 shows the data when the degree of rolling is changed for No.1.
  • the b / a obtained from the metal structure of the product increases and the tensile strength increases.
  • No. 17 b / a is less than 1.05 and the total strength of intermediate rolling and final rolling is less than 5%, and the tensile strength is less than 550 MPa.
  • the b / a of No. 23 the sum of the intermediate rolling and final rolling degrees exceeding 40%, was greater than 1.67, the tensile strength exceeded 700 MPa, and cracking occurred in 180 degree contact bending.
  • Table 5 shows the data for No. 2 when the crystal grain size after solution treatment was changed. As the crystal grain size after solution treatment increases, a obtained from the metal structure of the product increases and the stress relaxation rate decreases. The crystal grain size after solution treatment was less than 1 ⁇ m. No. 24's a was less than 1 Hm, the stress relaxation rate exceeded 30%, and the tensile strength was less than 3 ⁇ 450 MPa due to insufficient solutionization. In the case of No. 29 where the crystal grain size after solution treatment exceeded 15 m, No. a exceeded 15 m, and cracking occurred at 180 ° contact bending.
  • Table 6 shows the data when Ni is fixed at 1.60 mass% and the Si concentration is changed.
  • No. 1 and No. 5 are the same as the samples in Table 1.
  • No. 5 is a conventional alloy whose conductivity is less than 55% IACS, and its manufacturing conditions are different from those of other alloys.
  • the conductivity will be less than 55% IACS. ing. Also, the force that increases the tensile strength as the Ni concentration / Si concentration ratio decreases. This is because the amount of Ni Si deposited increases as the Si concentration increases.
  • the Sn plating heat release resistance evaluation result of the alloy of the present invention was ⁇ (dot-like peeling).
  • the evaluation results of No. 5 and 34 are X. This is because solute Si reduces the heat-resistant peelability. In other words, in No. 5, the amount of Ni Si deposited was small, and in No. 34, Si was excessively added to Ni, so the amount of dissolved Si increased.
  • Table 7 shows the data obtained by changing the Ni concentration while maintaining the Ni concentration / Si concentration ratio within the range of the present invention.
  • the tensile strength was less than 3 ⁇ 450 MPa.
  • the tensile strength exceeded 700 MPa, and cracking occurred at 180 ° close contact bending.
  • Table 8 shows the data when various concentrations of Zn were added to No. 1 as the effect of Zn addition. Addition of 0.05 mass% or more of Zn resulted in a Sn plating heat release resistance evaluation result of ⁇ (no peeling). On the other hand, the conductivity decreased as the Zn content increased. Zn force SO. Conductivity of 55% IACS or higher was obtained in the range of 5 mass% or less.
  • Table 9 shows data obtained by increasing the No. 43 impurity as impurities.
  • the total amount of impurities is changed by adding Sn, assuming the inclusion of Sn-plated copper material, and adding Mg, assuming the presence of deoxidizing elements during dissolution.
  • Conductivity is less than 55% IACS when impurities exceed 0.05% by mass.
  • FIG. 2 is a diagram showing a temperature chart of aging treatment ((a) and (b) are invention examples, and (c) is a conventional example).

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Abstract

L'invention concerne un alliage de Cu-Ni-Si pour un matériau électronique qui, avec l'addition d'autres éléments d'alliage minimisés, présente simultanément une meilleure conductivité électrique, une meilleure résistance, une meilleure flexibilité et une meilleure performance de relaxation en contrainte. L'alliage de Cu-Ni-Si comprend 1,2 à 3,5 % en masse de Ni, Si dans une concentration (% en masse) de 1/6 à 1/4 de la concentration de Ni (% en masse) et le reste de Cu, les impuretés n'excédant pas 0,05 % en masse. L'alliage de Cu-Ni-Si a une configuration de grains de cristaux et une largeur de zone de non précipitation organisées de manière à rester dans les limites appropriées par une gestion des conditions de traitement de la solution, des conditions de vieillissement et du degré de laminage. Il est ainsi possible d'obtenir une bande d'alliage de cuivre d'électroconductivité IACS allant de 55 à 62 % et une résistance à la traction allant de 550 à 700 MPa, cette bande étant exempte de fissures au fléchissement par contact de 180° et présentant un rapport de relaxation en contrainte ne dépassant pas 30 % après chauffage à 150 C° pendant 1000 heures.
PCT/JP2007/068420 2006-09-25 2007-09-21 Alliage de cu-ni-si WO2008038593A1 (fr)

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CN2007800326042A CN101512026B (zh) 2006-09-25 2007-09-21 Cu-Ni-Si系合金
US12/311,401 US20100000637A1 (en) 2006-09-25 2007-09-21 Cu-ni-si system alloy
KR1020087031101A KR101056973B1 (ko) 2006-09-25 2007-09-21 Ｃｕ-Ｎｉ-Ｓｉ 계 합금

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JP2006259294A JP4143662B2 (ja) 2006-09-25 2006-09-25 Ｃｕ−Ｎｉ−Ｓｉ系合金
JP2006-259294 2006-09-25

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JP (1) JP4143662B2 (fr)
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CN (1) CN101512026B (fr)
TW (1) TW200823302A (fr)
WO (1) WO2008038593A1 (fr)

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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
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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
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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
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
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

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JP2008075172A (ja) 2008-04-03
TWI355426B (fr) 2012-01-01
CN101512026A (zh) 2009-08-19
KR101056973B1 (ko) 2011-08-16
US20100000637A1 (en) 2010-01-07
JP4143662B2 (ja) 2008-09-03
TW200823302A (en) 2008-06-01
CN101512026B (zh) 2011-03-09
KR20090016485A (ko) 2009-02-13

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