EP3511432B1 - Erweichungsbeständige kupferlegierung, herstellungsverfahren und anwendung davon - Google Patents

Erweichungsbeständige kupferlegierung, herstellungsverfahren und anwendung davon Download PDF

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Publication number
EP3511432B1
EP3511432B1 EP17847871.5A EP17847871A EP3511432B1 EP 3511432 B1 EP3511432 B1 EP 3511432B1 EP 17847871 A EP17847871 A EP 17847871A EP 3511432 B1 EP3511432 B1 EP 3511432B1
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Prior art keywords
phase
copper alloy
temperature
softening
copper
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English (en)
French (fr)
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EP3511432A1 (de
EP3511432A4 (de
Inventor
Yongjun PEI
Jijun Wang
Er ZHANG
Yubo SONG
Renchang Hu
Juan Li
Weiwei Li
Mengtao TIAN
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Ningbo Powerway Alloy Plate & Strip Co Ltd
Ningbo Powerway Alloy Material Co Ltd
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Ningbo Powerway Alloy Plate & Strip Co Ltd
Ningbo Powerway Alloy Material Co Ltd
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Publication of EP3511432A1 publication Critical patent/EP3511432A1/de
Publication of EP3511432A4 publication Critical patent/EP3511432A4/de
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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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C2202/00—Physical properties

Definitions

  • the present invention relates to the field of copper alloy manufacturing, and in particular to a softening-resistant copper alloy, a preparation method thereof and applications thereof, belonging to the technical field of novel alloy materials.
  • Welding is a manufacturing technology that joins metals or other materials by heating, at high-temperature or under high-pressure.
  • fusion welding there are mainly three methods for joining materials: fusion welding, pressure welding and braze welding.
  • a workpiece and the solder are molten to form a molten area, and the molten pool is cooled and solidified to form a connection between the materials.
  • sources of energy for welding including gas flame, electric arc, laser, electron beams, friction, ultrasonic waves and the like.
  • the only welding process was metal forging already used by the blacksmith for hundreds of years. The earliest modern welding techniques appeared at the end of the 19 th century, first arc welding and oxygen-fuel welding and then resistance welding.
  • the actually popularized products such as conductive nozzles for welding equipment, electrode caps and electrified railway contact lines, mostly use conventional copper chromium zirconium alloy (e.g., American Standard C18150) which has been widely applied in the above fields due to its excellent strength and electrical conductivity.
  • conventional copper chromium zirconium alloy e.g., American Standard C18150
  • This change will present new requirements on the raw material performances of parts, among which high-temperature softening resistance comes first. This is because the wear of the parts will be less if the high-temperature softening resistance is better. Accordingly, the service life of the parts is prolonged and the precision during the welding process is also improved.
  • the conventional copper chromium zirconium alloy e.g., American Standard C18150
  • the Chinese patent application CN102534291 A discloses a Cu alloy containing Cr and Zr that offers improved strength and electrical conductivity and is intended for use in applications such as resistance sleeves for welding electrodes, overhead poweline wires and electrical contact materials.
  • An objective of the present invention is to provide a copper alloy with better high-temperature softening resistance, in order to solve the problem that the high-temperature softening resistance of the existing copper chromium zirconium alloy is to be improved.
  • the softening-resistant copper alloy comprises: 0.1%-1.0 wt% Cr, 0.01% -0.2 wt% Zr, 0.01%-0.10 wt% Si, and ⁇ 0.10 wt% Fe, 0.0001-0.10 wt.% Mg, 0.01-2.5 wt.% of at least one of Co, Zn, Mn, Sn and Nb, with their total amount not exceeding 3.5 wt.% and with the remaining of copper and inevitable impurities, characterized in that, the microstructure of the copper alloy comprises: an elemental Cr phase, a Cu 5 Zr phase, and a Cr 3 Si phase and wherein the elemental Cr phase and the Cr 3 Si phase satisfy the following relationship; if the weight of the elemental Cr phase is X and the weight of the Cr 3 Si phase is Y, then the ratio X/Y is greater than zero and msaller than twenty (0 ⁇ X/Y ⁇ 20).
  • the high-temperature softening resistance effect of the material is improved by adding a proper amount of Si to form a compound Cr 3 Si, and the strength and the high-temperature softening resistance of the material are further improved by strengthening the copper alloy matrix by the elemental Cr phase and the Cu 5 Zr phase, using the synergistic effect of the Cr 3 Si phase and the elemental Cr phase and by controlling the content of the impurity Fe.
  • the solid solubility of chromium in copper at the normal temperature is very small (less than 0.5%), but the solid solubility of chromium in copper at a high temperature is relatively high (up to 0.65%). Therefore, chromium is able to realize precipitation strengthening and used as a main strengthening element in the copper alloy of the present invention.
  • dispersion strengthening phase particles of the elemental Cr can be obtained by heat treatment, so the copper matrix is strengthened. While strengthening the copper matrix, Cr will also form a compound Cr 3 Si with Si solid-dissolved in the copper matrix.
  • the compound Cr 3 Si is a compound phase that is stable at a high temperature and will not be dissolved even at a high temperature of 800 °C, so that the high-temperature softening resistance is very high.
  • the content of chromium in the copper alloy of the present invention is 0.1% to 1.0%. If the content of chromium is less than this range, Cr and Si are difficult to form Cr 3 Si or can form a small amount of Cr 3 Si so that the desired effect cannot be achieved; however, if the content of chromium is greater than this range, chromium will be largely precipitated to form a strengthening phase, so that the chromium will be largely accumulated at the crystal boundary and the plasticity of the material is damaged.
  • Zirconium has a certain solubility in the copper alloy. By adding zirconium, the recrystallization temperature of the copper matrix can be increased and the high-temperature softening resistance of the copper alloy can be thus improved. Moreover, zirconium and copper will form an intermediate compound Cu 5 Zr, strengthening the copper matrix and also improving the electrical performance of the copper alloy.
  • the content of zirconium in the copper alloy of the present invention is 0.01% to 0.2%. If the content of zirconium is less than this range, the desired effect cannot be achieved; however, if the content of zirconium is greater than this range, although the alloy can be strengthened, the electrical conductivity of the alloy will be greatly reduced and the overall performance of the alloy will be influenced.
  • Silicon has a certain solid solubility in copper. Silicon can strengthen the copper alloy matrix, but will greatly influence the electrical conductivity of copper and will greatly reduce the electrical conductivity of the copper alloy. However, when there is a proper amount of chromium in the copper alloy, silicon and chromium can form a Cr 3 Si phase compound. Since Cr 3 Si is a precipitated phase, the electrical conductivity of the material can be greatly improved after Cr 3 Si is precipitated, so that the overall performance of the copper alloy is positively influenced.
  • the content of silicon in the copper alloy of the present invention is 0.01% to 0.1%.
  • the content of silicon is less than this range, the Cr 3 Si phase formed in the copper alloy is not enough to achieve the desired effect; however, if the content of silicon is greater than this range, although sufficient Cr 3 Si phase can be formed, the precipitation of Cr will be greatly reduced and the overall performance of the alloy will thus be influenced.
  • Fe is controlled as an impurity element.
  • a small amount of Fe facilitates the improvement of strength, but a too high content of Fe will affect the electrical conductivity. Therefore, in the present invention, the content of Fe is controlled below 0.1 wt.%.
  • the elemental Cr phase, the Cu 5 Zr phase and the Cr 3 Si phase in the microstructure of the copper alloy of the present invention have the following effects.
  • the Cr 3 Si phase is generated during the liquid state and crystallization process of the alloy, is stable in both structure and performance at a high temperature, and will not be dissolved at 800 °C while still maintaining its original structure. Accordingly, the high-temperature softening resistance of the alloy can be greatly improved.
  • the Cu 5 Zr phase is completely dissolved in the copper matrix to form a supersaturated solid solution after solid solution treatment on the alloy, then precipitated out of the copper matrix during the subsequent aging process and dispersedly distributed in the alloy. After the Cu 5 Zr phase is precipitated, a pinning effect on the dislocation is achieved, so that the strength and hardness of the copper matrix are improved.
  • Another strengthening phase in the copper alloy of the present invention is the elemental Cr phase.
  • the elemental Cr phase is also generated during the heat treatment of the alloy.
  • the elemental Cr phase is completely dissolved in the copper matrix to form a supersaturated solid solution after the solid solution treatment, then precipitated out of the copper matrix during the subsequent aging process and dispersedly distributed in the alloy.
  • the elemental Cr phase plays a crucial role in the improvement of the strength of the alloy.
  • the three main strengthening phases in the alloy of the present invention exist independently and have a certain dependence.
  • the addition of a suitable proportion of alloy elements to form a rational proportion of phases is very important for the performance of the alloy.
  • the elemental Cr phase as the main strengthening phase in the alloy, plays a leading role in the strengthening of the alloy
  • the Cr 3 Si phase as a high-temperature phase, plays a leading role in the high-temperature softening resistance of the alloy
  • the Cu 5 Zr phase as another moderate strengthening phase, can strengthen the alloy and can also increase nucleating particles, refine the elemental Cr phase and the Cr 3 Si phase and allow the elemental Cr phase and the Cr 3 Si phase to be dispersedly distributed, so that both the strength and the high-temperature softening resistance are further improved.
  • the elemental Cr phase and the Cr 3 Si phase satisfy the following relationship: if the weight of the elemental Cr phase is X and the weight of the Cr 3 Si phase is Y, then 0 ⁇ X/Y ⁇ 20.
  • both the high-temperature softening resistance and the strength of the copper alloy will be greatly improved.
  • the ratio of the strengthening phases is greater than 20, the amount of the Cr 3 Si phase in the alloy is very small. As a result, the high-temperature softening resistance of the alloy cannot satisfy the requirements.
  • the copper alloy further comprises: 0.0001 % - 0.10 wt% Mg.
  • the copper alloy further comprises: 0.01% to 2.5 wt% of any one or more of Co, Zn, Mn, Sn and Nb, and their total amount does not exceed 3.5 wt% of the copper alloy.
  • the softening temperature of the copper alloy is greater than or equal to 580°C.
  • the softening temperature of the copper alloy is greater than or equal to 580°C, the demands for various welding processes by the material can be greatly increased, and the service life of the welding material is prolonged.
  • the softening temperature of the copper alloy is determined by tests. Generally, when the material is kept at a certain temperature for 2 hours and then cooled in water, the hardness of the treated material is tested. If the hardness loss of the treated material is within 15%, it is considered that the material is not softened at this temperature; or otherwise, it is considered that the material is softened.
  • the softening temperature of the conventional copper chromium zirconium alloy is about 550°C.
  • the hardness loss of the treated material is about 13% to 15%; and, if the conventional copper chromium zirconium alloy is kept at 580°C, the hardness loss is far greater than 15%.
  • the softening temperature of the conventional copper chromium zirconium alloy is 550 °C .
  • the hardness loss of the material at 550°C is 4% to 8%, and the hardness loss of the material at 550°C does not exceed 10%. Therefore, the softening temperature of the copper alloy of the present invention is greater than or equal to 580°C.
  • the present invention further discloses a method for preparing copper alloy, the method comprising: alloying and refining-casting into an ingot-ingot sawing, heating and extruding-solid solution heat treatment-stretching and drawing-aging heat treatment-straightening and finalizing;
  • the casting temperature for the alloying treatment and the covered refining is 1150°C to 1350°C; the temperature for the hot extrusion is 850°C to 950°C; the temperature for the solid solution treatment is 850°C to 1000°C; the cooling medium is water, and the cooling rate is 10°C/min to 150°C/s; the machining rate of the cold stretching and drawing is 20% to 60%; the temperature for the aging heat treatment is 420 °C to 520 °C; and the copper alloy is insulated for 2h to 4h.
  • the elemental Cr phase, the Cu 5 Zr phase and the Cr 3 Si phase are rational in size and more dispersive in distribution, so that various performances of the copper alloy of the present invention are improved.
  • the present invention discloses a method of using the copper alloy, the method comprising using the softening-resistant copper alloy in contact lines and welding materials..
  • the present invention has the following advantages:
  • the high-temperature softening resistance effect of the material is improved by adding a proper amount of Si to form a compound Cr 3 Si, and the strength and the high-temperature softening resistance of the material are further improved by strengthening the copper alloy matrix by the elemental Cr phase and the Cu 5 Zr phase, using the synergistic effect of the Cr 3 Si phase and the elemental Cr phase and by controlling the content of the impurity Fe.
  • the softening temperature of the copper alloy of the present invention is greater than or equal to 580°C, the requirements on various performances of the copper alloy in the fields of welding and contact lines are better satisfied.
  • %IACS used for representing the electrical conductivity of a metal or alloy (reference to the standard annealed pure copper).
  • the electrical conductivity of the standard annealed pure copper is generally defined as 100%IACS, i.e., 5.80F+7(1/ ⁇ m ) or 58(m/ ⁇ mm 2 ).
  • the value is the ratio of the resistivity (in volume or mass) specified by the International Annealed Copper Standard to the resistivity of the sample in the same unit multiplied by 100.
  • Embodiments 1-20 (embodiments 1-17 and all further embodiments produced using these compositions are not part of the invention)
  • the finished softening-resistant copper alloy products in Embodiments 21-40 of the present invention were obtained by preparing materials according to the components and their mass percentages of the softening-resistant copper alloy in Embodiments 1-20 in Table 1, then smelting, casting into an ingot, processing and molding, heating to 450°C to 520°C at an average heating rate of 1 °C/min to 30°C/min and holding this temperature for 2h to 4h (Embodiments 21-40 where the finished products were obtained, corresponding to the components and their mass percentages of the softening-resistant copper alloy in Embodiments 1-20, respectively).
  • the materials were prepared according to the components and their mass percentages of the softening-resistant copper alloy in Embodiments 1-20 in Table 1, and then treated under the following conditions: the casting temperature for the alloying treatment and the covered refining was 1150°C to 1350°C, the temperature for hot extrusion was 850°C to 950°C, the temperature for solid solution treatment was 850°C to 1000°C, the cooling medium was water, the cooling rate was 10°C/min to 150°C/s, the machining rate of cold drawing was 20% to 60%, the temperature for aging heat treatment was 420°C to 520°C, and the temperature holding time was 2 h to 4 h. Finally, the finished softening-resistant copper alloy bar products in ⁇ 8 in Embodiments 41-60, corresponding to the components and their mass percentages of the softening-resistant copper alloy in Embodiments 1-20, were obtained by finishing.
  • the tensile strength, hardness, electrical conductivity and softening temperature of the softening-resistant copper alloy bars in Embodiments 58-60 of the present invention were tested by methods specified by the related national and industrial Embodiments 41-57 fall outside the scope of the invention.
  • the test results are shown in Table 3.
  • the room-temperature tensile tests were carried out by an electronic universal mechanical property testing machine according to GB/T228.1-2010 Metal Material Tensile Test Section 1: Test at Room Temperature.
  • the samples were circular cross-section proportional samples having a proportional coefficient of 5.65.
  • the electrical conductivity tests were carried out according to GB/T228.1-2010 Test Methods for Electrical Performance of Electric Wires and Cables Section 2: Metal Material Resistivity Test.
  • test instrument a ZFD microcomputer bridge DC resistance tester was used, and the samples were 1000 mm in length.
  • the electrical conductivity was represented by %IACS.
  • the hardness tests were carried out by a hardometer according to GB/T 230.1-2009 Metal Material: Rockwell Hardness Test.
  • the tensile strength is higher than or equal to 470MPa, the Rockwell hardness is above 75, and the electrical conductivity is above 75%IACS.
  • Embodiments 61-80 The components and their mass percentages of the softening-resistant copper alloys in Embodiments 61-80 are the same as those in Embodiments 41-60. That is, the materials were prepared according to the components and their mass percentages of the softening-resistant copper alloy in Embodiments 1-20 in Table 1, and then treated under the following conditions: the casting temperature for the alloying treatment and the covered refining was 1150°C to 1350°C, the temperature for hot extrusion was 850°C to 950°C, the temperature for solid solution treatment was 850°C to 1000°C, the cooling medium was water, the cooling rate was 10°C/min to 150°C/s, the machining rate of cold drawing was 20% to 60%, the temperature for aging heat treatment was 420 °C to 520 °C, and the temperature holding time was 2h to 4h. Finally, the finished softening-resistant copper alloy bar products in ⁇ 8 were obtained by finishing.
  • the softening temperature tests were carried out by methods specified by HB5420-89 Copper and Copper Alloys for Resistance Welding Electrodes and Auxiliary Devices.
  • the test temperature was 580°C.
  • the test results are shown in Table 4. Embodiments 61-77 fall outside of the scope of the invention.
  • the hardness loss of the copper alloy of the present invention at 580°C is below 8%, while the hardness loss of the conventional copper chromium zirconium alloy in the comparison embodiment is greater than 18%. It is indicated that the high-temperature softening resistance of the copper alloy of the present invention is greatly improved.
  • the softening-resistant copper alloy bars in anyone of Embodiments 41-60 are machined into appliances for welding.
  • the softening-resistant copper alloy bars in anyone of Embodiments 41-60 are machined into contact lines for electrified railways.
  • the softening-resistant copper alloy of the present invention has high strength, good electrical performance and excellent high-temperature softening resistance, and is particularly applied in industrial fields such as welding appliances and contact lines for electrified railways.

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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)

Claims (3)

  1. Eine erweichungsbeständige Kupferlegierung, umfassend:
    0,1 - 1,0 Gew.-% Cr,
    0,01 - 0,2 Gew.-% Zr,
    0,01 - 0,10 Gew.-% Si,
    ≤ 0,10 Gew.-% Fe,
    0,0001 - 0,10 Gew.-% Mg, und
    0,01 - 2,5 Gew.-% mindestens eines der folgenden Elemente Co, Zn, Mn, Sn und Nb, wobei deren Gesamtmenge 3,5 Gew.-% der Kupferlegierung nicht übersteigt,
    wobei der Rest aus Kupfer und unvermeidlichen Verunreinigungen besteht,
    wobei das Mikrogefüge der Kupferlegierung umfasst:
    eine elementare Cr-Phase,
    eine Cu5Zr-Phase, und
    eine Cr3Si-Phase, und
    wobei die elementare Cr-Phase und die Cr3Si -Phase die folgende Beziehung erfüllen:
    wenn das Gewicht der elementaren Cr-Phase X und das Gewicht der Cr3Si -Phase Y ist, dann ist das Verhältnis X/Y größer als null und kleiner als zwanzig (0< X/Y <20).
  2. Verfahren zur Herstellung der Kupferlegierung nach Anspruch 1, wobei das Verfahren die folgenden Schritte umfasst: Legieren und Raffinieren -- Gießen zu einem Barren -- Sägen des Barrens, Erhitzen und Strangpressen -- Wärmebehandlung in fester Lösung - Strecken und Ziehen -- Wärmebehandlung durch Alterung -- Richten und Endbearbeitung;
    dadurch gekennzeichnet, dass die Gießtemperatur für die Legierungsbehandlung und das verdeckte Raffinieren 1150 °C bis 1350 °C beträgt; die Temperatur für das Warmstrangpressen 850 °C bis 950 °C beträgt; die Temperatur für die Wärmebehandlung in fester Lösung 850 °C bis 1000 °C beträgt; das Kühlmedium Wasser ist und die Kühlrate 10 °C/min bis 150 °C/s beträgt; die Dehnungsrate bei Kaltstrecken und Ziehen 20 % bis 60 % beträgt; die Temperatur bei der Alterungswärmebehandlung 420 °C bis 520 °C beträgt; und die Kupferlegierung für 2 h bis 4 h isoliert wird.
  3. Verwendung der erweichungsbeständigen Kupferlegierung nach Anspruch 1 in Oberleitungen und Schweißmaterialien.
EP17847871.5A 2016-09-09 2017-08-18 Erweichungsbeständige kupferlegierung, herstellungsverfahren und anwendung davon Active EP3511432B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610813189.5A CN106350698B (zh) 2016-09-09 2016-09-09 抗软化铜合金、制备方法及其应用
PCT/CN2017/000536 WO2018045695A1 (zh) 2016-09-09 2017-08-18 抗软化铜合金、制备方法及其应用

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EP3511432A1 EP3511432A1 (de) 2019-07-17
EP3511432A4 EP3511432A4 (de) 2019-07-17
EP3511432B1 true EP3511432B1 (de) 2021-07-21

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US (1) US20190161831A1 (de)
EP (1) EP3511432B1 (de)
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WO (1) WO2018045695A1 (de)

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CN106350698B (zh) * 2016-09-09 2018-03-27 宁波博威合金板带有限公司 抗软化铜合金、制备方法及其应用
JP6822889B2 (ja) * 2017-04-13 2021-01-27 株式会社Ｓｈカッパープロダクツ 銅合金材、銅合金材の製造方法およびかご型回転子
KR101810925B1 (ko) 2017-10-18 2017-12-20 주식회사 풍산 내열성 및 방열성이 우수한 구리 합금 판재
CN110512112B (zh) * 2018-05-21 2021-09-28 昆山微电子技术研究院 一种铜合金及其制备方法和天线材料
CN109913691A (zh) * 2019-04-22 2019-06-21 南通科誉德摩尔新材料有限公司 一种高强复合铬锆铜材料的制作工艺
CN110042273B (zh) * 2019-05-29 2020-11-06 南京达迈科技实业有限公司 一种高强高导铜合金管及其制备方法
CN111996411B (zh) * 2020-07-15 2021-11-30 宁波博威合金板带有限公司 一种高强高导铜合金材料及其制备方法和应用
CN113913642B (zh) * 2021-09-26 2022-07-05 宁波博威合金板带有限公司 一种铜合金带材及其制备方法
CN114807672B (zh) * 2022-03-23 2023-09-08 中南大学 Cu-Zn-Cr-Zr-Fe-Si系合金及其制备方法
CN114959350A (zh) * 2022-05-31 2022-08-30 西安理工大学 一种高性能Cu-Hf-RE合金及其制备方法
CN115418521B (zh) * 2022-07-11 2023-04-28 大连理工大学 一种耐高温铜合金及其制备方法
CN116005038B (zh) * 2022-12-08 2024-08-02 北京首钢吉泰安新材料有限公司 一种镍铬铁合金及其制备方法
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CN106350698A (zh) 2017-01-25
CN106350698B (zh) 2018-03-27
WO2018045695A1 (zh) 2018-03-15
US20190161831A1 (en) 2019-05-30
EP3511432A1 (de) 2019-07-17
EP3511432A4 (de) 2019-07-17

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