WO2006009538A1 - Bande d’alliage de beryllium et de cuivre - Google Patents

Bande d’alliage de beryllium et de cuivre Download PDF

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Publication number
WO2006009538A1
WO2006009538A1 PCT/US2004/019647 US2004019647W WO2006009538A1 WO 2006009538 A1 WO2006009538 A1 WO 2006009538A1 US 2004019647 W US2004019647 W US 2004019647W WO 2006009538 A1 WO2006009538 A1 WO 2006009538A1
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WO
WIPO (PCT)
Prior art keywords
alloy
age hardening
strip
heat treatment
ksi
Prior art date
Application number
PCT/US2004/019647
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English (en)
Inventor
John C. Harkness
Original Assignee
Brush Wellman Inc.
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 Brush Wellman Inc. filed Critical Brush Wellman Inc.
Priority to PCT/US2004/019647 priority Critical patent/WO2006009538A1/fr
Publication of WO2006009538A1 publication Critical patent/WO2006009538A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C9/00—Alloys based on copper
    • 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

Definitions

  • Chip sockets for personal computers are composed of numerous tiny preformed current-carrying springs mounted in close proximity to one another. These sockets are typically made by forming the individual springs from metal strip, then assembling the springs into a large grid array in a non-conducting base plate.
  • Such springs should be made from a metal which exhibits a particular combination of properties, specifically (1) high yield strength, (2) an electrical conductivity of at least 45 %IACS and (3) bend formability of no more than about 2 R/t to about 3 R/t in the transverse and longitudinal directions. Bend formability is the ability of a metal sample to bend without cracking and is normally described in terms of the minimum radius R to which a metal sample of thickness t can bent 90 degrees without cracking.
  • a transverse bend (traditionally termed a "Bad Way" bend in the connector industry) has its bend axis parallel to the rolling direction of the strip.
  • a longitudinal bend (traditionally termed a "Good Way” bend) has its bend axis perpendicular to the rolling direction of the strip. Bend formability is another measure of alloy ductility.
  • the maximum 0.2% yield strength that can be obtained in the "high conductivity" copper- beryllium alloys used today, when manufactured to exhibit the desired electrical conductivity of at least 45 %IACS and bend formability of 1.5 to 5 R/t, is 125 ksi.
  • IDC's insulation displacement connectors
  • Evolving designs of IDC's have also created a need for higher strength materials with conductivity in excess of the existing commercial "high strength" copper-beryllium alloys such as C 17200.
  • Desirable properties for such new IDC applications include 0.2% yield strength of at least about 130 ksi to about 140 ksi, with electrical conductivity of at least about 45 %IACS. Because these IDC's are essentially flat, excellent bendability is not a significant performance requirement. Hence, "Good Way" bendability of no more than about 5 R/t and “Bad Way” bend formability of no more than about 9 R/t are adequate for the task.
  • alloys UNS C 17410 and C 17460 can be made to exhibit these improved yield strengths, without sacrificing electrical conductivity or bendability, by age hardening the alloys with two separate heat treatment steps, with cold working being carried out between these heat treatments rather than before heat treatment begins as in current technology.
  • the present invention provides a new copper-beryllium alloy comprising about 0.15 to 0.5 wt.% Be, about 0.35 to 1.40 wt.% Ni and/or Co, up to about 0.5 wt.% Zr, with the balance being copper and incidental impurities, wherein the alloy exhibits an electrical conductivity of at least about 45 %IACS, a bend formability of less than about 3 R/t in the "Good Way” or longitudinal direction and less than about 9 R/t in the "Bad Way” or transverse direction, and a 0.2% yield strength of at least about 130 ksi.
  • the present invention provides a new process for manufacturing a copper- beryllium alloy having an improved combination of electrical conductivity, bend formability and yield strength, the alloy mass containing 0.15 to 0.5 wt.% Be, about 0.35 to 1.40 wt.% Ni and/or Co and up to about 0.5 wt.% Zr, with the balance being copper and incidental impurities, the process comprising age hardening the alloy by heat treating the alloy in a first age hardening heat treatment step carried out directly after final solution annealing, cold rolling the mass before age hardening is completed, and finalizing age hardening by subjecting the mass to at least a second age hardening heat treatment.
  • Fig. 1 is a schematic representation illustrating the combination of properties exhibited by the alloys of the present invention in relation to the properties of prior art alloys;
  • Fig. 2 is a schematic representation illustrating the thermal and mechanical processing profile experienced by a BeCu alloy which is manufactured into strip by conventional technology, Fig. 2 also illustrating the effect on properties of the different processing steps in this manufacturing method;
  • Fig. 3 is a schematic representation similar to Fig. 2 illustrating the thermal and mechanical processing profile and effect on properties of the manufacturing method of the present invention.
  • Fig. 1 is a schematic representation of the alloys of the present invention in relation to alloys of the prior art in terms of electrical conductivity, bendability and yield strength.
  • prior art alloys having electrical conductivities of 45 %IACS or higher and good bend formability when made by conventional technology, exhibit 0.2% yield strengths less than 125 ksi.
  • Other prior art alloys, such as C 17200 can be made to exhibit good bend foraiability and 0.2% yield strengths greater than 125 ksi.
  • Such alloys however, exhibit poor electrical conductivities, i.e., values of 25 %1ACS or less.
  • inventive alloys because of the way they are made, exhibit all three excellent properties, i.e. electrical conductivities of at least 45 %IACS, bend formabilities of 1 to 8 R/t in both the longitudinal and transverse directions, and 0.2% yield strengths of at least about 130 ksi, preferably at least about 140 ksi.
  • the present invention is directed to making copper-beryllium alloy strip and wire.
  • strip and wire is meant metal products which are produced by subjecting an ingot to a series of hot and cold working steps, usually with one or more intermediate solution anneals, to reduce the thickness of the metal mass by a factor of at least about 200 between ingot and finished product.
  • Strip products are typically rectangular in configuration and are worked by hot and cold rolling steps.
  • Wire products are normally circular in cross-section and are worked, at least in later stages of reduction, by drawing through a die one or more times.
  • Wire products of the invention will normally have thicknesses (diameters) of no more than about 0.5 inch, more typically no more than about 0.38 inch, with thicknesses on the order of about 0.25 to 0.001 inch being more typical.
  • Strip products of the invention will normally have thicknesses of and no more than about 0.02 inch. Thickness of about 0.01 inch or less, and especially about 0.003 to about 0.008 inch, are more typical, with 0.002 inch or even less anticipated in future chip socket designs.
  • the present invention is applicable to BeCu alloys comprising
  • Preferred alloys are C17460, which contains about 0.15 to 0.5 wt.% Be, about 1.0 to 1.40 wt.% Ni, up to 0.5 wt.% Zr and the balance Cu plus incidental impurities, as well as C17410, which contains about 0.15 to 0.5 wt.% Be, about 0.35 to 0.60 wt.% Co and the balance Cu plus incidental impurities.
  • These alloys may contain additional ingredients, provided that the properties of the alloys are not adversely affected to any significant degree.
  • additional ingredients are Fe, Al, Si, Sn, Zn, Cr, V, Mo, Mn, W, Ag, Au, Ta, Nb, Ti, Hf, P, Mg, Ca, Se, Te, S and Pb.
  • the total amount of such additional ingredients should not exceed 0.5 wt.%.
  • Fig. 2 illustrates conventional technology for manufacturing strip products from C 17410, C 17460, C 17510 and other "high conductivity" copper-beryllium alloys such as C 17500, etc.
  • a melt of the alloy is cast into an ingot, allowed to cool to low temperature, typically room temperature, and then reheated to a temperature above its solvus temperature where it is hot rolled for thickness reduction. Cooling to a low temperature can be omitted if desired. After hot rolling, the ingot is cooled to a low temperature, then cold rolled to further reduce its thickness.
  • One or more optional intermediate anneals may be imparted to soften the cold worked alloy and enable greater total cold reduction.
  • Such cold reduction is carried out to reach a desired ready-to-fmish thickness at which the strip is given a final solution anneal at a temperature above its solvus temperature, followed by rapid quenching.
  • Pickling or other surface treating can be used to clean and smooth the strip surfaces.
  • the alloy is age hardened to increase its strength.
  • copper-beryllium alloys also exhibit enhanced response to age hardening if they are cold worked first. Therefore, as illustrated in Fig. 2, the alloy after the final solution anneal at the ready-to-finish thickness is conventionally subjected to a final cold rolling step, typically in the amount of about 10% to as much as about 90% in thickness reduction to achieve the final product thickness and to prepare the metal for the subsequent age hardening heat treatment step. Thereafter, the alloy is heated to an age hardening temperature below the solvus temperature where it is held long enough for the alloy to develop a significant increase in yield strength. See, U.S. Patent No. 6,387,195, the disclosure of which is incorporated herein by reference, for a further discussion of age hardening.
  • Fig. 2 also illustrates the effect of the various metallurgical treatments described above on the properties of the alloy.
  • this age hardening procedure including the final cold rolling step, increases the 0.2% yield strength of the alloy essentially to its maximum attainable value, which in the case of alloys C 17410, C 17460 and C17510 is about 120 to 125 ksi.
  • Fig. 2 also shows that, although age hardening reduces ductility (elongation), the final product is still quite ductile. This is particularly desirable in alloy strip to be used for forming chip socket springs, since bendability and ductility are closely related properties.
  • a modified procedure is used to age harden the alloy. This is illustrated in Fig. 3, which shows that after final solution anneal the alloy is directly subjected to age hardening heat treatment rather than being cold rolled first.
  • directly means that there is no intermediate cold rolling step.
  • the desired intermediate strength after the first age hardening treatment is preferably the "peak", or essentially maximum, strength attainable in the solution annealed and directly age hardened state; or may range into the slightly “overaged” heat treatment regime.
  • "Peak” aging attends thermal treatment in a narrow range of aging temperature and soak time at this temperature, resulting in highest achievable strength and a particular level of electrical conductivity.
  • Underaging refers to thermal treatment at temperatures less than and/or at times shorter than "peak” aging conditions for a given solution annealed alloy, and results in lower strength with lower conductivity.
  • “Overaging” refers to aging at higher temperatures and/or longer times than “peak” aging conditions and generates lower strength with higher conductivity.
  • age hardening of strip products can be carried out in batch operation, in which a coil or other bulk arrangement of the strip is heat heated in an age hardening furnace for a suitable period of time, typically about 3 to about 20 hours.
  • the strip can be age hardened continuously by passing a continuous length of the strip through an age hardening furnace, from a pay-off coil on the input side of the furnace to a take-up coil on the output side of the furnace, for a much shorter period of time, normally no more than 10 minutes, more typically no more than 5 minutes.
  • Age hardening in batch operation occurs as a practical matter in a fairly narrow temperature range roughly midway between the solvus temperature and room temperature. See, U.S. Patent No. 6,387,195, mentioned above.
  • this temperature range is generally about 500° F to 1000° F, more typically 500° F to 900° F.
  • Age hardening in continuous operation normally occurs at higher temperatures, which for the inventive alloys is generally at 750° F to 1200° F, more typically 750° F to 1000° F.
  • the first age hardening is preferably carried out to achieve the "peak" or a slightly “overaged” strength level of which the solution annealed and directly age hardened alloy is capable.
  • the thermal treatment conditions producing this first age hardened strength level in the inventive alloy are most conducive to bulk age hardening conditions. Strength superior to the maximum strength attainable from conventionally processed "high conductivity" copper-beryllium alloys is then achieved by cold working the material after the first age hardening, resulting is an increase in strength from work hardening, with attendant loss of ductility. This cold working is then followed by a second thermal treatment.
  • One aim of the second thermal treatment is to at least stress relieve the first age hardened and cold worked strip in order to restore ductility to provide satisfactory bendability, yet retain much or all of the first age hardened plus work hardened strength.
  • a continuous-type second thermal treatment step is particularly suited to this objective, although batch-type thermal cycles can also be selected to achieve a similar end.
  • the second thermal treatment step is carried out to superimpose a further aging response atop the first age hardened plus cold worked strength level, resulting in very high final strength, coupled with quite useful ductility and bendability.
  • Batch-type second thermal treatment conditions are well-suited to this task, but appropriate continuous-type thermal treatment cycles can also be selected for this purpose.
  • alloy strip having a 0.2% yield strength of at least about 140 ksi, an electrical conductivity of at least about 45% IACS and a bend formability of about 3 R/t or less, preferably about 2.5 R/t or less, in both longitudinal and transverse directions can be produced. This can be accomplished by carrying out
  • final solution anneal at about 25 to 50° F higher than the normal solution anneal temperatures, i.e., at temperatures of about 1700 to 1750 ° F, more preferably about 1725° F (with anneal times concomitantly shorter so as to achieve a small to moderate average grain size, e.g., on the order of 0.015 mm - 0.030 mm, preferably 0.015 mm - 0.025 mm),
  • the first age hardening heat treatment step at about 700 to 800 ° F, more preferably about 750° F, for at least about 3 and preferably at least about 5 hours, preferably to achieve approximate peak or slight overaging
  • the second age hardening step in bulk at about 450° F to 700° F, more typically about 500 to 600° F, for at least about 3 hours and-preferably at least about 5 hours.
  • alloy strip having a 0.2% yield strength of at least about 130 ksi, an electrical conductivity of at least about 45% IACS and a bend formability of 3 R/t or less, preferably about 2.5 R/t or less, in both longitudinal and transverse directions can be produced. This is accomplished by carrying out
  • final solution anneal at normal solution anneal temperatures i.e. about 1650 to 1725 ° F, more preferably about 1675 to 1700 ° F (with anneal times chosen to achieve a small to moderate average grain size, e.g., on the order of 0.015 mm — 0.030 mm, preferably 0.015 mm - 0.025 mm),
  • the first age hardening heat treatment step at about 850 to 950° F, more preferably about 900° F, for at least about 5 hours, preferably to achieve slight overaging
  • the second age hardening step in continuous fashion at about 725° F to 825° F, more typically about 750 to 800° F for no more than about 5 minutes, preferably no more than about 3 minutes.
  • alloy strip having a 0.2% yield strength of at least about 130 ksi, an electrical conductivity of at least about 45% IACS and a bend formability in the transverse direction of about 2 to 2.5 R/t and a bend formability in the longitudinal direction of about 5 to 8 R/t can be produced. This is accomplished by carrying out
  • final solution anneal at normal solution anneal temperatures i.e. about 1650 to 1725 ° F, more preferably about 1675 to 1700 ° F (with anneal times chosen to achieve a small to moderate average grain size, e.g., on the order of 0.015 mm - 0.030 mm, preferably 0.015 mm - 0.025 mm),
  • the first age hardening heat treatment step at about 725 to 825° F, more preferably about 750 to 800° F, preferably for at least about 3 hours and preferably at least about 5 hours, preferably to achieve approximate peak aging,
  • the second age hardening step o in bulk at about 550° F to 800° F for at least about 3 hours and preferably at least about 5 hours, or o in continuous fashion at about 750° F to 900° F, for no more than 5 minutes, preferably no more than 3 minutes.
  • Comparative Examples A and B represent an alloy outside the composition range of the alloys of the present invention, i.e., commercial C17510, subjected to processing consistent with Embodiment II of the present invention.
  • Comparative Examples C to F show manufacturers' published properties for commercial "high conductivity" copper-beryllium alloys of the prior art. See, “Guide to Copper Beryllium", Brush Wellman Inc., 2002. Comparative Example F also used an alloy conforming to C 17460.
  • Comparative Examples C and D employed alloys conforming to UNS C 17510.
  • Comparative Example E employed an alloy conforming to UNS C 17410.
  • Table 1 The compositions of each of these alloys is set forth in the following Table 1:
  • the finish thicknesses of alloy strip products produced in these examples was as follows o Example 1 0.004 inch o Examples 2-19 0.00787 inch o Examples 20-26 0.00394 inch o Comp. Ex A-B 0.00394 inch o Comp. Ex. C-F Thickness not specified (commercial strip) [0031]
  • the strip products made in accordance with the present invention were age hardened using a two-step heating process in which the first heating step began directly after final solution anneal, i.e., without cold rolling first. After the first heating step, these strip products were cold rolled by amounts ranging from 20 to 60% in thickness reduction and then subjected to a second age hardening heating step.
  • the second age hardening step was carried out in batch operation by placing the alloy in bulk in an aging furnace for 5 hours, hi Examples 12 to 19 the second stage age hardening step was carried out by a simulated continuous process in which the strip was placed in a molten salt bath for 2 minutes.
  • the foregoing data show that the present invention can reliably and consistently produce alloys exhibiting electrical conductivities of at least 45% IACS, bend formabilities of 1 to 2.5 R/t in the longitudinal direction and no more than about 8 R/t in the transverse direction, and a 0.2% yield strengths of about 130 ksi or more.
  • the foregoing data further show that preferred embodiments of the present invention can produce such alloys which exhibit bend formabilities of about 3 R/t or less in both the longitudinal and transverse directions as well as 0.2% yield strengths of as high as 140 ksi and even higher.
  • alloys outside the scope of the present invention whether because of being made by conventional technology (Comparative Examples C to E), or because of having a different chemical composition (Comparative Examples A and B), do not exhibit these properties.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Conductive Materials (AREA)

Abstract

La résistance à la déformation de l’alliage BeCu UNS C17460 peut être significativement améliorée sans compromettre la conductivité électrique ou l’aptitude au formage en coude en durcissant par précipitation l’alliage au cours de la fabrication en utilisant deux étapes de traitement thermique distinctes et en laminant à froid l’alliage pour améliorer la réponse au durcissement par précipitation entre ces deux étapes de traitement thermique plutôt qu’avant que le durcissement par précipitation ne débute comme dans la technologie actuelle.
PCT/US2004/019647 2004-06-16 2004-06-16 Bande d’alliage de beryllium et de cuivre WO2006009538A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102451893A (zh) * 2010-10-26 2012-05-16 苏州金江铜业有限公司 合金线材的制造方法
CN110699571A (zh) * 2019-11-23 2020-01-17 西安斯瑞先进铜合金科技有限公司 一种具有电磁屏蔽性能的铜铁合金材料的制备方法
CN114959352A (zh) * 2022-06-16 2022-08-30 宁波兴敖达金属新材料有限公司 航空航天电气用铍青铜合金及其绿色制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4565586A (en) * 1984-06-22 1986-01-21 Brush Wellman Inc. Processing of copper alloys
US4657601A (en) * 1983-11-10 1987-04-14 Brush Wellman Inc. Thermomechanical processing of beryllium-copper alloys
US4724013A (en) * 1984-06-08 1988-02-09 Brush Wellman, Inc. Processing of copper alloys and product
US4792365A (en) * 1986-11-13 1988-12-20 Ngk Insulators, Ltd. Production of beryllium-copper alloys and alloys produced thereby
US4935202A (en) * 1987-10-30 1990-06-19 Ngk Insulators, Ltd. Electrically conductive spring materials
US6095905A (en) * 1998-07-01 2000-08-01 Molecular Optoelectronics Corporation Polishing fixture and method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4657601A (en) * 1983-11-10 1987-04-14 Brush Wellman Inc. Thermomechanical processing of beryllium-copper alloys
US4724013A (en) * 1984-06-08 1988-02-09 Brush Wellman, Inc. Processing of copper alloys and product
US4565586A (en) * 1984-06-22 1986-01-21 Brush Wellman Inc. Processing of copper alloys
US4792365A (en) * 1986-11-13 1988-12-20 Ngk Insulators, Ltd. Production of beryllium-copper alloys and alloys produced thereby
US4935202A (en) * 1987-10-30 1990-06-19 Ngk Insulators, Ltd. Electrically conductive spring materials
US6095905A (en) * 1998-07-01 2000-08-01 Molecular Optoelectronics Corporation Polishing fixture and method

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102451893A (zh) * 2010-10-26 2012-05-16 苏州金江铜业有限公司 合金线材的制造方法
CN102451893B (zh) * 2010-10-26 2013-09-04 苏州金江铜业有限公司 合金线材的制造方法
CN110699571A (zh) * 2019-11-23 2020-01-17 西安斯瑞先进铜合金科技有限公司 一种具有电磁屏蔽性能的铜铁合金材料的制备方法
CN110699571B (zh) * 2019-11-23 2021-03-12 西安斯瑞先进铜合金科技有限公司 一种具有电磁屏蔽性能的铜铁合金材料的制备方法
CN114959352A (zh) * 2022-06-16 2022-08-30 宁波兴敖达金属新材料有限公司 航空航天电气用铍青铜合金及其绿色制备方法

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