US20060204396A1 - Titanium copper alloy having excellent punchability - Google Patents

Titanium copper alloy having excellent punchability Download PDF

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Publication number
US20060204396A1
US20060204396A1 US11/371,469 US37146906A US2006204396A1 US 20060204396 A1 US20060204396 A1 US 20060204396A1 US 37146906 A US37146906 A US 37146906A US 2006204396 A1 US2006204396 A1 US 2006204396A1
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United States
Prior art keywords
copper alloy
titanium copper
mass
phase particles
excellent punchability
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Abandoned
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US11/371,469
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English (en)
Inventor
Yasutaka Sugawara
Kazuhiko Fukamachi
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JX Nippon Mining and Metals Corp
Nippon Mining Holdings Inc
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NIPPON MINING and METALS CO Ltd HITACHI (JP)
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Assigned to NIPPON MINING & METALS CO., LTD. reassignment NIPPON MINING & METALS CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FUKAMACHI, KAZUHIKO, SUGAWARA, YASUTAKA
Publication of US20060204396A1 publication Critical patent/US20060204396A1/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

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45B—WALKING STICKS; UMBRELLAS; LADIES' OR LIKE FANS
    • A45B9/00—Details
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/06—Making non-ferrous alloys with the use of special agents for refining or deoxidising
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45B—WALKING STICKS; UMBRELLAS; LADIES' OR LIKE FANS
    • A45B9/00—Details
    • A45B2009/005—Shafts
    • A45B2009/007—Shafts of adjustable length, e.g. telescopic shafts
    • A—HUMAN NECESSITIES
    • A45—HAND OR TRAVELLING ARTICLES
    • A45B—WALKING STICKS; UMBRELLAS; LADIES' OR LIKE FANS
    • A45B2200/00—Details not otherwise provided for in A45B
    • A45B2200/05—Walking sticks

Definitions

  • the present invention relates to copper alloys used for connector materials and the like.
  • the present invention provides a producing method of titanium copper alloy having excellent punchability compatible with bendability retaining high strength.
  • Titanium copper alloy forms supersaturated solid solution by means of solution treatment. Aging at low temperature of the supersaturated solid solution develops a modulated structure which is metastable phase, resulting in remarkable hardening at a point in the course of the developing process (age-hardening).
  • the foregoing modulated structure of titanium copper alloy is caused by the fluctuation of the concentration of solid solution titanium in a matrix formed by spinodal decomposition.
  • the titanium copper alloy having a developed modulated structure has the second strength next to beryllium copper, and excellent stress relaxation properties superior to beryllium copper. Thus they are used for connector materials and the like.
  • the market demand for titanium copper alloy tends to increase, along with the demand for further high strengthening retaining excellent bendability. In order to respond to the above demands, various researches and developments have been worked on further high strengthening of titanium copper alloy.
  • JP6-248375A disclosed is the method in which at least one selected from Cr, Zr, Ni and Fe is added to titanium copper alloy.
  • JP 2002-356726A disclosed is that a method in which at least one selected from Zn, Cr, Zr, Fe, Ni, Sn, In, P and Si is added to titanium copper alloy. All of the foregoing publications are herein fully incorporated by reference.
  • the press die When titanium copper alloy is punched, the press die more easily wears away than when the other copper alloy is punched. Therefore, since the third element group(s) (Fe, Co, Ni, Si, Cr, V, Nb, Zr, B or P) is added to titanium copper alloy in the conventional method in order to achieve high strength by means of the precipitation of the second phase comprising the third element moiety, punch press work of the strengthened materials causes a more problem of a press mold wear because the precipitates themselves harden the alloy.
  • the third element group(s) Fe, Co, Ni, Si, Cr, V, Nb, Zr, B or P
  • the press working of the titanium copper alloy highly strengthened by the above means makes a die easily worn away resulting in the decrease of the dimensional accuracy.
  • minute parts such as narrow pitch connectors and the like
  • the object of the present invention is to improve punchability of high strengthened titanium copper alloy by adding the third element, and to provide a titanium copper alloy having excellent punchability by achieving excellent bendability.
  • the inventors has discovered when the composition of titanium copper alloy is a Cu—Ti—X system containing a third elements (X is the third element), the development of the second phase particles at grain boundaries is inhibited resulting in tendency of fine distribution.
  • the present invention provides (1) to (7) as follows.
  • a titanium copper alloy consisting of 2.0 to 4.0 mass % of Ti, 0.05 to 0.50 mass % of Fe and the balance of Cu and impurities characterized in that;
  • a titanium copper alloy consisting of 2.0 to 4.0 mass % of Ti, 0.05 to 0.50 mass % in total of Fe and at least one selected from a group consisting of Co, Ni, Si, Cr, V, Nb, Zr, B and P, and the balance of Cu characterized in that;
  • a titanium copper alloy consisting of 2.0 to 4.0 mass % of Ti, 0.05 to 0.50 mass % in total of at least one selected from a group consisting of Co, Ni, Si, Cr, V, Nb, Zr, B and P, and the balance of Cu characterized in that;
  • the number of Cu—Ti—Fe type composition particles in the second phase particles having an area of 0.01 ⁇ m 2 or more measured by a cross sectional observation is 50% or more.
  • the number of Cu—Ti—X type composition particles (wherein X is an element selected from Fe, Co, Ni, Si, Cr, V, Nb, Zr, B and P) in the second phase particles having an area of 0.01 ⁇ m 2 or more measured by a cross sectional observation is 50% or more.
  • the average particle size of the second phase having an area of 0.01 ⁇ m 2 or more measured by a cross sectional observation is 2.0 ⁇ m or less.
  • the coefficient of variation Cv standard deviation/mean value of the density of the second phase particles having an area of 0.01 ⁇ m 2 or more, observed in each crystal grains by means of a cross sectional observation, is 0.3 or less.
  • the present invention achieves a titanium copper alloy having excellent punchability while retaining high strength by adjusting the content of the third element group and the crystal orientation and excellent bendability by controlling the distribution of the second phase particles. Therefore, the titanium copper alloy of the present invention is a copper alloy having excellent bendability compatible with excellent punchability while retaining high strength able to be used for connector materials and the like.
  • FIG. 1 is a diagram showing the generation of cracks during punch press work.
  • FIG. 2 is a diagram showing a burr generated after press punching.
  • FIG. 3 is a diagram showing a die set used in evaluation.
  • FIG. 4 ( a ) is a diagram showing a generation process of the second sheared surface
  • Figure ( b ) is a diagram showing the generated second sheared surfaces.
  • the present invention defines the amount of Ti as 2 to 4 mass % since sufficient strength is not obtained by Ti of less than 2 mass %, on the contrary Ti of more than 4 mass % easily causes coarse precipitations resulting in deteriorated bendability.
  • the more preferred range of the Ti amount is 2.5 to 3.5 mass %.
  • One embodiment of the present invention specifies an alloy composition with addition of the third element group.
  • the effect of the elements is that the addition in even a small amount enables to obtain fine crystal structure by solid solution treatment at high temperature at which Ti is satisfactorily solved into matrix without easy generation of coarse crystal grain.
  • Fe achieves the highest effect as the third element group. Any one of Co, Ni, Si, Cr, V, Nb, Zr, B and P shows the better effect next to Fe, thus a partial amount of added Fe can be replaced with any one of Co, Ni, Si, Cr, V, Nb, Zr, B and P. Further, these elements can be added alone or in the form of mixture of two or more elements achieving the same effect. Fe and these elements show their effects when they are contained in an amount of 0.01 mass % or more in total. On the contrary, when the amount exceeds 0.5 mass %, the range of solid solution of Ti becomes narrow, the second phase coarse particles tend to precipitate, thus bendability is deteriorated while strength is improved.
  • the term “the second phase particle” refers to a region having a discrete boundary distinct from matrix in the composition, and it includes Cu—Ti—X type particle and Cu—Ti type particle in the titanium copper alloy of the present invention.
  • the preferred content range of the third elements is 0.17 to 0.23 mass % of Fe, 0.15 to 0.25 mass % of Co, Ni, Cr, Si, V or Nb, 0.05 to 0.10 mass % of Zr, B or P.
  • the present invention regards the relationship between I(311) and I(111) and found the following. No prior arts refer to the relationship between I(311) and I(111).
  • the edge of the punch digs into the plate on the shearing cut-away surface of the plate, and the side of the edge scrapes the cut-away surface forming a sheared surface shown in FIG. 2 .
  • the materials adjacent to the edges of punch and die are hardened locally, cracks are generated by tensile stress (at break) on the both edges and the cracks are transmitted to associate with each other so that the plate is fractured.
  • the surface generated by the transmission of the cracks is the fractured surface shown in FIG. 2 .
  • the second sheared surface refers to the surface generated by crossing of a crack derived from a punch and a crack derived from a die without meeting shown in FIG. 4 ( a ) so as to form a fractured surface and further shearing of the fractured surface (see FIG. 4 ( b )).
  • the alloy system of the present invention satisfies I(311)/I(111) ⁇ 0.5, preferably I(311)/I(111) ⁇ 1.0, more preferably I(311)/I(111) ⁇ 1.5.
  • the specific embodiment of the present invention defines the composition, average particle size, and dispersion of the density of the second phase.
  • the second phase particles include extrinsic inclusions derived from furnace materials and the like, reaction products generated during melting, precipitations generated during solidification, and precipitations formed during heat treatment.
  • the alloy system relating to the present invention most of the second phase particles are precipitations formed during heat treatment.
  • the second phase particles finely and homogeneously dispersed in crystal grains contribute to the improvement of strength as well as bendability. Coarse particles or a locally segregated distribution deteriorate bendability. Concretely, when the average grain particle of the second phase exceeds 2.0 ⁇ m, or when the coefficient of variation Cv (standard deviation/average of density of the second phase particles exceeds 0.3, bendability remarkably deteriorates.
  • the term “a particle size” refers to a diameter of the corresponding circle and “a diameter of the corresponding circle” refers to a diameter of a perfect circle having the same area.
  • the fine second phase particles homogeneously dispersed in crystal grains, it is effective that heating is carried out under the condition such that solute atoms are completely dissolved in the form of solid solution and the final solution treatment is conducted at a temperature range slightly above the solid solution curve.
  • the “temperature range” refers to a temperature preferably 20° C., more preferably 10° C. more than the temperature on the solid solution curve.
  • the Cu—Ti—X type second phase particles themselves are not easily coarsened in relation to the Cu—Ti type second phase particles, when the number of the Cu—Ti—X type second phase particles is 50% or more of the total number of the second phase particles, the above desirable size and distribution of the second phase particles are achieved and fine recrystallization grains are obtained.
  • the property such that the Cu—Ti—X type second phase particles are not easily coarsened in relation to the Cu—Ti type second phase particles is derived from the matter that the second phase particles of the latter develops only by diffusion of Ti while the second phase particles of the former essentially develops by diffusions of both Ti and X. This property is shown at a low temperature, the Cu—Ti—X type second phase particles are not easily coarsened even during aging treatment of final step. From the above, it is preferred that the second phase particles composition is maintained as Cu—Ti—X system during final solution treatment as much as possible.
  • the first solution treatment refers to a solution treatment before intermediate rolling before final rolling. After melting the raw materials adjusted to the specified composition, casting, and hot rolling, a set of cold rolling and annealing is repeated appropriately until the desired thickness, then the first solution treatment is conducted, alternatively the first solution treatment can be carried out immediately after hot rolling.
  • the second solution treatment refers to a solution treatment before final rolling, corresponding to the above final solution treatment, hereinbelow referred as “the final solution treatment”.
  • homogeneous annealing is preferably carried out at 900° C. or more for 3 hours or more. At this point, when segregation and crystallized particles generated during casting disappear completely, precipitations of the second phase particles can be dispersed finely and homogeneously at intragranular regions and formation of duplex grain structure is prevented.
  • the second phase particles are formed, thus these steps are conducted at a temperature such that the second phase particles are completely solved into matrix.
  • a temperature of 800° C. is acceptable for usual titanium copper alloy to which the third element group is not added.
  • the temperature is preferably 900° C. or more. The rising rate and cooling rate of the temperature should be as high as possible such that the second phase particles are not precipitated.
  • the second phase particles generated at grain boundaries at this point develop in final aging, it is preferred that the second phase particles at this point is as small and few as possible.
  • cold rolling and aging treatment are carried out.
  • a reduction ratio of 25% or less is preferable since the higher a reduction ratio, the more precipitation at grain boundaries occurs in the next aging treatment.
  • aging treatment the lower the temperature is, the less precipitation at grain boundaries occurs. Even in the condition that the same strength is obtained, a combination of low temperature and long period more inhibits precipitation at grain boundaries than a combination of high temperature and short period. In the range of 420 to 450 ° C. which is considered as an appropriate range in prior art, the strength is improved according to the aging process, however precipitation at grain boundaries tends to occur and slight over-aging deteriorates bendability.
  • An appropriate aging condition which varies depending on the added elements, is 380° C. ⁇ 3 hs at the highest temperature, or 360° C. ⁇ 24 hs at the low temperature while a long period of heating is accepted.
  • examples 1 to 7 and comparative examples 8 to 12 in order to obtain the composition shown in Table 1, main raw materials Cu, Ti and additional elements (Fe, Co, Ni, Cr, Si, V, Nb, Zr, B or P) are compounded and melted. The molten metal is maintained sufficiently such that the solution residue is solved so that the third element groups act effectively, then Ti is added. The above prepared molten metal is poured into a mold under the atmosphere of Ar to produce approximately 2 kg of ingot.
  • additional elements Fe, Co, Ni, Cr, Si, V, Nb, Zr, B or P
  • the above ingot is coated with an antioxidant. After 24 hours of drying at a room temperature and heating at 950° C. for 12 hours, hot rolling was conducted to obtain a plate having a thickness of 10 mm. Subsequently in order to inhibit segregation, further antioxidant is coated on the plate and the plate was heated at 950° C. for 2 hours and cooled with water. The above water-cooling is employed for completion of solid solution as far as possible, and the coating with an antioxidant is employed for protecting grain boundary oxidation and internal oxidation causing generation of inclusions as much as possible, which internal oxidation is caused by the reaction of oxygen entered from the surface with additional elements.
  • Each hot rolled plate was ground mechanically and descaled by pickling, then processed by cold rolling to the thickness of 0.2 mm.
  • the plate was inserted into an annealing furnace to conduct rapid heating at rising rate of 50° C./second to the temperature slightly above the solid solution curve (for example, 800° C. for the alloy having 3 mass % of added Ti and 0.2 mass % of added Fe), then maintained for 2 minutes and water-cooled.
  • the water-cooled plate was pickled for descaling and cold rolled to the plate thickness of 0.15 mm, then aged under the atmosphere of inert gas to obtain a sample piece for an example.
  • Diffraction intensity values of (111) and (311) planes of each sample pieces were measured by X-ray diffractometer (XRD) and I(311)/I(111) was calculated.
  • the distribution of the second phase particles was evaluated by use of Field Emission Auger Electron Spectroscopy analyzing apparatus (FE-AES) and Image Analysis device connected therewith.
  • the second phase particles having an area of 0.01 ⁇ m 2 existing in a scanning visual field unit was evaluated.
  • value “A” ((Sx/S) ⁇ 100) was obtained.
  • areas of 5000 optional second phase particles were averaged and a diameter of a corresponding circle thereof is defined as an average particle size “D” of the second phase particles.
  • Wear of a press die was evaluated by actual punching using a press for certain times and measuring the ratio of a burr height of the material and the ratio of an area of the fractured surface which varies depending on the wear of a mold. During the mold wear test, the mold was sharpened after an evaluation thus the pressing was conducted in the same condition.
  • the burr height means a height of convex part shown in FIG. 2 , wherein the burr rises along with the wear of die.
  • the wear of a press mold is accompanied by the increase of the ratio of the sheared surface and decrease of the ratio of fractured surface h 2 /(h 1 +h 2 ) shown in FIG. 2 .
  • FIG. 3 A set of press tools used in the evaluation is shown in FIG. 3 .
  • the tool has a square shape having 4 sides of approximately 5 mm and 4 angles of various curvatures whose curvature radius are 0.05 mm, 0.1 mm, 0.2 mm and 0.3mm respectively.
  • the observation of the edge of the punched out piece is easier than the edge of a hole. According to the above, the evaluation in the invention is conducted by the observation of the edge of the punched out piece at the angle having a curvature radius of 0.1 mm.
  • each example has a 0.2% offset yield strength of 850 MPa or more, a MBR/t value of 2.0 or less, and a fractured surface ratio of 0.10 or more and a burr height of 40 ⁇ m or less after 100,000 times punching without a lubricant. These examples achieve high punchability in addition to high strength and excellent bendability compatibly. In examples 3 to 7, since the amount of added Ti is in the especially preferred range (2.5 to 3.5 mass %), 0.2% offset yield strength is significantly improved to more than 900 MPa.
  • the amount of the added third elements is small, thus the ratio of Cu—Ti—X type particle existence is less than 50%, resulting in inferior bendability to other examples.
  • a heating temperature is low in comparative example 12, a rising rate is low in comparative example 13, and a cooling rate is low in comparative example 14.
  • the heating temperature is 800° C. in comparative example 12, the rising rate is 5° C./sec in comparative example 13, and the cooling rate is 30° C./sec in comparative example 14.
  • intermediate cold rolling was conducted while Cu—Ti—X type precipitations were remaining, finally I(311)/I(111) values regarding the above comparative examples were less than 0.5, resulting in poor punchability.

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US11/371,469 2005-03-14 2006-03-09 Titanium copper alloy having excellent punchability Abandoned US20060204396A1 (en)

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JP2005072006A JP4191159B2 (ja) 2005-03-14 2005-03-14 プレス加工性に優れたチタン銅

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100132851A1 (en) * 2008-11-28 2010-06-03 Dowa Metaltech Co., Ltd. Copper alloy plate and method for producing same
CN113802026A (zh) * 2021-09-18 2021-12-17 宁波博威合金板带有限公司 钛青铜带材及其制备方法

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JP2008081767A (ja) * 2006-09-26 2008-04-10 Nikko Kinzoku Kk 電子部品用チタン銅
JP2008248355A (ja) * 2007-03-30 2008-10-16 Nikko Kinzoku Kk 電子部品用チタン銅及びこれを用いた電子部品
EP2196548B1 (en) 2008-12-02 2012-05-16 Dowa Metaltech Co., Ltd. Cu-Ti based copper alloy sheet material and method of manufacturing same
US8097102B2 (en) 2008-12-08 2012-01-17 Dowa Metaltech Co., Ltd. Cu-Ti-based copper alloy sheet material and method of manufacturing same
EP2612934A1 (en) 2010-08-31 2013-07-10 Furukawa Electric Co., Ltd. Copper alloy sheet material and process for producing same
JP5393629B2 (ja) * 2010-09-30 2014-01-22 Ｊｘ日鉱日石金属株式会社 チタン銅及びこれを用いた伸銅品、電子部品及びコネクタ
JP5611773B2 (ja) 2010-10-29 2014-10-22 Jx日鉱日石金属株式会社 銅合金及びこれを用いた伸銅品、電子部品及びコネクタ及び銅合金の製造方法
JP5226057B2 (ja) * 2010-10-29 2013-07-03 Ｊｘ日鉱日石金属株式会社 銅合金、伸銅品、電子部品及びコネクタ
JP6214126B2 (ja) * 2011-10-07 2017-10-18 Ｊｘ金属株式会社 チタン銅及びその製造方法、並びにチタン銅を用いた伸銅品及び電子機器部品
JP6247812B2 (ja) * 2012-03-30 2017-12-13 Ｊｘ金属株式会社 チタン銅及びその製造方法
JP5470483B1 (ja) * 2012-10-22 2014-04-16 Ｊｘ日鉱日石金属株式会社 導電性及び応力緩和特性に優れる銅合金板
JP6368518B2 (ja) * 2014-03-28 2018-08-01 Ｄｏｗａメタルテック株式会社 Ｃｕ−Ｔｉ系銅合金板材およびその製造方法並びに通電部品
JP2016188435A (ja) * 2016-06-22 2016-11-04 Ｊｘ金属株式会社 チタン銅及びその製造方法、並びにチタン銅を用いた伸銅品及び電子機器部品
JP2017014625A (ja) * 2016-09-06 2017-01-19 Ｊｘ金属株式会社 チタン銅及びその製造方法

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JPH06248375A (ja) * 1992-10-26 1994-09-06 Nikko Kinzoku Kk 高強度高導電銅合金
KR100513947B1 (ko) * 2002-03-29 2005-09-09 닛코 킨조쿠 가부시키가이샤 프레스성이 양호한 구리 합금 소재 및 그 제조방법

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US20040136861A1 (en) * 2002-11-29 2004-07-15 Nikko Metal Manufacturing Co., Ltd. Copper alloy and producing method therefor

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100132851A1 (en) * 2008-11-28 2010-06-03 Dowa Metaltech Co., Ltd. Copper alloy plate and method for producing same
EP2194149A1 (en) * 2008-11-28 2010-06-09 Dowa Metaltech Co., Ltd. Copper alloy plate and method for producing the same
US8871041B2 (en) 2008-11-28 2014-10-28 Dowa Metaltech Co., Ltd. Copper alloy plate and method for producing same
US10174406B2 (en) 2008-11-28 2019-01-08 Dowa Metaltech Co., Ltd. Copper alloy plate and method for producing same
CN113802026A (zh) * 2021-09-18 2021-12-17 宁波博威合金板带有限公司 钛青铜带材及其制备方法

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TW200632114A (en) 2006-09-16
JP4191159B2 (ja) 2008-12-03
JP2006249565A (ja) 2006-09-21
KR20070106944A (ko) 2007-11-06
CN1834273A (zh) 2006-09-20
TWI317762B (ko) 2009-12-01
CN100406597C (zh) 2008-07-30
KR20060100947A (ko) 2006-09-21

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