WO2018045695A1 - 抗软化铜合金、制备方法及其应用 - Google Patents

抗软化铜合金、制备方法及其应用 Download PDF

Info

Publication number
WO2018045695A1
WO2018045695A1 PCT/CN2017/000536 CN2017000536W WO2018045695A1 WO 2018045695 A1 WO2018045695 A1 WO 2018045695A1 CN 2017000536 W CN2017000536 W CN 2017000536W WO 2018045695 A1 WO2018045695 A1 WO 2018045695A1
Authority
WO
WIPO (PCT)
Prior art keywords
copper alloy
phase
softening
copper
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2017/000536
Other languages
English (en)
French (fr)
Inventor
裴勇军
王继军
张儿
宋玉波
胡仁昌
李娟�
李威威
田梦涛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Ningbo Powerway Alloy Plate & Strip Co Ltd
Ningbo Powerway Alloy Material Co Ltd
Original Assignee
Ningbo Powerway Alloy Plate & Strip Co Ltd
Ningbo Powerway Alloy Material Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ningbo Powerway Alloy Plate & Strip Co Ltd, Ningbo Powerway Alloy Material Co Ltd filed Critical Ningbo Powerway Alloy Plate & Strip Co Ltd
Priority to US16/321,756 priority Critical patent/US20190161831A1/en
Priority to EP17847871.5A priority patent/EP3511432B1/en
Publication of WO2018045695A1 publication Critical patent/WO2018045695A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

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
    • 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 invention relates to the field of copper alloy manufacturing, in particular to an anti-softening copper alloy, a preparation method and an application thereof, and belongs to the technical field of alloy new materials.
  • Welding is a manufacturing process that joins metals or other materials in a heated, high temperature or high pressure manner.
  • the traditional copper-chromium-zirconium alloy (such as American Standard C18150) has high temperature softening resistance at 580 °C, and its hardness loss value is above 15%, which can not meet the development requirements of related industries, therefore, improve the material's high temperature resistance. Softening performance has become an urgent need.
  • the object of the present invention is to provide a copper alloy which is more excellent in high temperature softening resistance, and solves the problem that the high temperature softening resistance of the current chromium zirconium copper alloy is to be improved.
  • an anti-softening copper alloy the composition of the alloy is: Cr: 0.1-1.0 wt%, Zr: 0.01-0.2 wt%, Si: 0.01-0.10 wt% Fe: ⁇ 0.10 wt%, the balance being copper and unavoidable impurities, and the microstructure of the copper alloy contains an elemental Cr phase, a Cu 5 Zr phase, and a Cr 3 Si phase.
  • the copper alloy of the invention adopts the addition of an appropriate amount of silicon element to form a Cr 3 Si compound to enhance the high temperature softening resistance of the material, and at the same time strengthens the copper alloy matrix with the elemental Cr phase and the Cu 5 Zr phase, and utilizes the synergistic action of the Cr 3 Si phase and the elemental Cr phase. And by controlling the content of Fe impurities, the strength and high temperature softening resistance of the material are further improved.
  • the solid solubility of chromium in copper at room temperature is very small, less than 0.5%, but the solid solubility is relatively large at high temperature, up to 0.65%, so precipitation strengthening can be achieved, which is the main strengthening in the copper alloy of the present invention. element.
  • the dispersion-strengthened phase particles of elemental Cr can be obtained by heat treatment to form a strengthening effect on the copper matrix.
  • Cr While strengthening the copper matrix, Cr also forms a Cr 3 Si compound with the solid solution of Si in the copper matrix. It has been found that the Cr 3 Si compound is a high-temperature stable compound phase, and does not dissolve even at a high temperature of 800 ° C. Its resistance to high temperature softening is extremely strong.
  • the chromium content of the bronze alloy of the invention is 0.1-1.0%. If the chromium content is less than this range, Cr and Si are difficult to form Cr 3 Si, and even if formed, the amount is not large and cannot function as intended, and if the chromium content is greater than In this range, chromium will precipitate in a large amount to form a strengthening phase, resulting in a large accumulation of chromium at the grain boundary, which destroys the plasticity of the material.
  • Zirconium has a certain solubility in copper alloys.
  • the addition of zirconium can increase the recrystallization temperature of the copper matrix and improve the high temperature softening resistance of the copper alloy.
  • zirconium forms a Cu 5 Zr intermediate compound with copper, which strengthens the copper matrix and enhances the electrical properties of the copper alloy.
  • the copper alloy of the invention has a zirconium content of 0.01-0.2%. If it is lower than the range, it does not function. Above this range, although the alloy can strengthen the effect, the conductivity of the alloy is greatly reduced, and the alloy is affected. Comprehensive performance.
  • Silicon has a certain solid solubility in copper, which can strengthen the copper alloy matrix, but has a great influence on the conductivity of copper, which can greatly reduce the electrical conductivity of the copper alloy.
  • chromium when there is an appropriate amount of chromium in the copper alloy, it can form a Cr 3 Si phase compound, and Cr 3 Si is a precipitated phase, which can greatly improve the conductivity of the material after precipitation, and thus has a good influence on the overall performance of the copper alloy.
  • the content of silicon in the copper alloy of the present invention is 0.01-0.1%. If the content is lower than this range, the Cr 3 Si phase formed in the copper alloy is insufficient, and if it is higher than this range, sufficient Cr 3 Si can be formed. Phase, but will greatly reduce the precipitation of Cr, affecting the overall performance of the alloy.
  • Fe is controlled as an impurity element, and a small amount of Fe contributes to an improvement in strength, but an excessively high Fe affects electrical conductivity. Therefore, in the present invention, the Fe content is controlled to 0.10% by weight or less.
  • the Cr 3 Si phase is the primary phase of the alloy, which is produced during the liquid phase and crystallization of the alloy. It has a stable structure and properties at high temperatures. It can still maintain the original structure at 800 ° C without dissolving, thus greatly improving the alloy. High temperature softening resistance.
  • the Cu 5 Zr phase is one of the main precipitation strengthening phases in the copper alloy of the present invention. After the alloy solution treatment, the copper matrix is completely dissolved into the copper matrix to form a supersaturated solid solution, which is precipitated from the copper matrix in the subsequent aging process and dispersed in the alloy. in.
  • Another strengthening phase in the copper alloy of the present invention is an elemental Cr phase, which is formed in a similar manner to Cu 5 Zr, and is produced in the heat treatment of the alloy. After solution treatment, all of the copper matrix is dissolved into a supersaturated solid solution, followed by During the aging process, it precipitates from the copper matrix and is dispersed in the alloy.
  • the elemental Cr phase is the most important strengthening phase in the alloy of the present invention and plays a vital role in the strength improvement of the alloy.
  • the three main strengthening phases of the alloy of the invention exist independently and have a certain dependence relationship. By adding a suitable ratio of alloying elements to form a reasonable proportion of phases, the performance of the alloy plays an important role.
  • the elemental Cr phase is the main strengthening phase in the alloy, which plays a major role in alloy strengthening.
  • the Cr 3 Si phase is a high temperature phase, which plays a major role in the high temperature softening of the alloy, while the Cu 5 Zr phase is another strengthening phase, which can not only strengthen
  • the alloy can simultaneously increase the nucleation point, refine the elemental Cr phase and the Cr 3 Si phase, and make it diffusely distributed, thereby enhancing the strength and resistance to high temperature softening.
  • the elemental Cr phase and the Cr 3 Si phase satisfy the following relationship:
  • the strengthening phase reaches the ratio, the high temperature softening resistance and strength of the copper alloy will be greatly improved.
  • the strengthening ratio is greater than 20, the amount of Cr 3 Si phase in the alloy is extremely small, and the high temperature softening resistance of the alloy is not satisfactory.
  • the copper alloy contains, Mg: 0.0001-0.10 wt%.
  • the magnesium in the ratio can be dissolved in the copper matrix to strengthen the copper alloy and have less influence on the electrical conductivity of the copper alloy.
  • the oxygen in the copper alloy can be effectively removed, and the oxygen of the copper alloy can be reduced. Content, improve material quality.
  • the copper alloy further comprises 0.01% to 2.5% by weight of any one or more of Co, Zn, Mn, Sn, and Nb elements, and the sum thereof does not exceed 3.5% by weight.
  • the above alloying elements are added to the copper alloy, the solid solution strengthening, the recrystallization temperature of the material, and the softening temperature of the material can be enhanced.
  • the above alloying elements should not be added too much, otherwise the electrical conductivity of the material will be greatly reduced.
  • the copper alloy has a softening temperature of ⁇ 580 °C.
  • the softening temperature of the copper alloy is ⁇ 580 °C, the demand for various welding processes can be greatly improved, and the service life of the welding material can be improved.
  • the softening temperature of the copper alloy was determined experimentally. Under normal circumstances, when the material is kept at a certain temperature for 2 hours, and then cooled in water, the hardness of the material after the test, such as the hardness loss of the treated material is less than 15%, it is considered that the material is not softened at this temperature, and vice versa The material softens.
  • the traditional copper-chromium-zirconium alloy has a softening temperature of about 550 ° C. It is kept at 550 ° C for 2 hours, and then cooled by water. The hardness loss of the treated material is about 13-15%. If it is 580 ° C, the hardness is The amount of loss is much greater than 15%.
  • the conventional copper-chromium-zirconium alloy has a softening temperature of 550 °C.
  • the copper alloy of the present invention has a material hardness loss of 8% at 550 ° C and a material hardness loss of not more than 10% at 580 ° C. Therefore, the softening temperature of the copper alloy of the present invention is ⁇ 580 ° C.
  • the invention also discloses a preparation method of an anti-softening copper alloy, comprising the following steps: alloying refining - casting ingot - sawing ingot extrusion - solution heat treatment - stretching and drawing - Aging heat treatment - straightening and finishing;
  • the casting temperature of the alloying treatment and the cover protection refining is 1150 ° C - 1350 ° C; the hot extrusion temperature is 850 ° C - 950 ° C; the solution treatment temperature is 850 ° C - 1000 ° C, the cooling medium is water
  • the cooling rate is 10 ° C / min - 150 ° C / s; the cold drawing processing rate is 20% - 60%; the aging heat treatment temperature is 450 ° C - 520 ° C, and the holding time is 2 h - 4 h.
  • the production process can make the material of the material, the elemental Cr phase, the Cu 5 Zr phase and the Cr 3 Si phase have a reasonable size and a more dispersed distribution, thereby improving the performance of the inventive copper alloy.
  • the invention discloses the application of an anti-softening copper alloy on a contact line and a solder material.
  • the copper alloy of the invention adopts adding appropriate amount of silicon element to form Cr 3 Si compound to enhance the high temperature softening resistance of the material, and strengthens the copper alloy matrix with the elemental Cr phase and the Cu 5 Zr phase, and utilizes the synergy of the Cr 3 Si phase and the elemental Cr phase. Function and further improve the strength and high temperature softening resistance of the material by controlling the content of Fe impurities;
  • the softening temperature of the copper alloy of the invention is ⁇ 580 ° C, which better meets the requirements of various properties of the copper alloy in the field of welding and contact wires.
  • %IACS Used to characterize the conductivity of a metal or alloy (reference to standard annealed pure copper).
  • the conductivity of standard annealed pure copper is generally defined as 100% IACS, which is 5.80E+7 (1/ ⁇ m) or 58 (m/ ⁇ mm 2 ). It is the ratio of the resistivity (whether volume and mass) specified by the International Annealed Copper Standard to the resistivity of the same unit of sample multiplied by 100.
  • Table 1 Examples of the composition of the anti-softening copper alloy of the present invention (% by weight):
  • the anti-softening copper alloy described in Table 1-20 and its mass percentage are obtained (the finished products of Examples 21-40, which respectively correspond to the anti-softening described in Examples 1-20)
  • the composition of the copper alloy and its mass percentage ingredients are obtained (the finished products of Examples 21-40, which respectively correspond to the anti-softening described in Examples 1-20)
  • the anti-softening copper alloys in the embodiments 21-40 of the present invention mainly form microscopic mesophases and simple substances of different properties by various alloying elements added and specific aging treatment, and these microscopic phases are dispersedly distributed in the copper matrix, so that copper The various properties of the alloy are effectively improved.
  • the relevant phases and their contents of the anti-softening copper alloy of Examples 21-40 of the present invention are shown in Table 2.
  • the casting temperature of the alloying treatment and the cover protection refining is 1150 ° C - 1350 ° C;
  • the hot extrusion temperature is 850 ° C -950 ° C;
  • the solution treatment temperature is 850 ° C -1000 ° C,
  • the cooling medium is water, the cooling rate is 10 ° C / min -150 ° C / s; cold drawing processing rate is 20% -60%;
  • the aging heat treatment temperature is 450 ° C - 520 ° C, the holding time is 2 h - 4 h, and the final composition is ⁇ 8 corresponding to the composition of the anti-softening copper alloy described in Examples 1-20 and the mass percentage thereof. 41-60 anti-softening copper alloy bar finished product.
  • the tensile strength, hardness, electrical conductivity and softening temperature of the 41-60 anti-softening copper alloy bar of the present invention were tested according to the relevant national and industry standards. The test results are shown in Table 3. Among them, the room temperature tensile test is carried out according to "GB/T228.1-2010 tensile test of metal materials Part 1: room temperature test method" on the electronic universal performance test machine, the sample adopts a circular cross-section ratio with a proportional coefficient of 5.65. Sample.
  • Conductivity test according to "GB/T3048-2007 wire and cable electrical performance test method Part 2: metal material resistivity test” the test instrument is ZFD microcomputer bridge DC resistance tester, sample length is 1000mm, expressed by %IACS.
  • the hardness test was carried out on a hardness tester in accordance with the GB/T 230.1-2009 Metallic Rockwell Hardness Test method.
  • the tensile strength of the invention is ⁇ 470 MPa, the Rockwell hardness is above 75, and the electrical conductivity is above 75% IACS.
  • compositions of the anti-softening copper alloys in Examples 61-80 and their mass percentages were the same as those in Examples 41-60, i.e., the components of the anti-softening copper alloy and the mass percentage thereof as described in Examples 1-20 of Table 1 respectively.
  • the casting temperature of the alloying treatment and the cover protection refining is 1150 ° C - 1350 ° C; the hot extrusion temperature is 850 ° C - 950 ° C; the solution treatment temperature is 850 ° C - 1000 ° C, the cooling medium is water
  • the cooling rate is 10 ° C / min - 150 ° C / s; the cold drawing processing rate is 20% - 60%; the aging heat treatment temperature is 450 ° C - 520 ° C, the holding time is 2 h - 4 h, and finally finished into ⁇ 8 anti-softening copper alloy bar finished product.
  • the softening temperature test was carried out in accordance with the requirements of "HB5420-89 Resistance Welding Electrodes and Copper and Copper Alloys for Auxiliary Devices".
  • the test temperature was chosen to be 580 ° C and the results are shown in Table 4.
  • the copper alloy of the present invention has a hardness loss value of less than 8% at 580 ° C according to a standard experimental method, while the conventional copper of the comparative example The hardness loss value is more than 10%, which proves that the high temperature softening resistance of the copper alloy of the present invention is greatly improved.
  • the anti-softening copper alloy bars of the optional embodiments 41-60 were made into welding equipment.
  • the anti-softening copper alloy bars of the optional embodiments 41-60 were made into contact wires for electrified railways.
  • the anti-softening copper alloy of the invention not only has high strength, good electrical properties, but also has excellent high temperature softening resistance, and is particularly suitable for use in industrial fields such as welding equipment and contact lines for electrified railways.

Landscapes

  • 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

一种抗软化铜合金、制备方法及其应用，其中抗软化铜合金的组成为：Cr：0.1-1.0wt%，Zr：0.01-0.2wt%，Si：0.01-0.10wt%，Fe：≤0.10wt%，其余为铜和不可避免的杂质，该铜合金微观结构含有单质Cr相，Cu 3Zr相和Cr 3Si。铜合金采用添加适量硅元素形成Cr 3Si化合物提升材料抗高温软化效果，同时以单质Cr相和Cu 5Zr相强化铜合金基体，利用Cr 3Si相和单质Cr相的协同作用，并通过控制Fe杂质的含量，进一步提升材料的强度和抗高温软化性能。该铜合金可在接触线与焊接材料上应用，提升材料的使用寿命。

Description

抗软化铜合金、制备方法及其应用 技术领域
本发明涉及铜合金制造领域，尤其涉及一种抗软化铜合金、制备方法及其应用，属于合金新材料技术领域。
背景技术
焊接是一种以加热、高温或高压的方式接合金属或其他材料的制造工艺技术。
目前主要有三种方式完成接合材料的目的；熔焊、压焊和钎焊。焊接过程中，工件和焊料熔化形成熔融区域，熔池冷却凝固后便形成材料之间的连接。这一过程中，通常还需要施加压力。焊接的能量来源有很多种，包括气体焰、电弧、激光、电子束、摩擦和超声波等。19世纪末之前，唯一的焊接工艺是铁匠沿用了数百年的金属锻焊。最早的现代焊接技术出现在19世纪末，先是弧焊和氧燃气焊，稍后出现了电阻焊。20世纪早期，随着第一次和第二次世界大战开战，对军用器材廉价可靠的连接方法需求极大，故促进了焊接技术的发展。随着焊接机器人在工业应用中的广泛应用，研究人员仍在深入研究焊接的本质，继续开发新的焊接方法，以进一步提高焊接质量。
纵观现代焊接技术装备的发展，焊接设备自动化及提升生产效率是焊接技术发展的主要驱动力。因铜合金具有良好的强度及电性能，故而在焊接设备中有许多耗材使用铜及其合金，如电阻焊中的电极帽、钎焊中的导电嘴等。随着现代自动化装备尤其是焊接机器人的使用，对导电嘴、电极帽等铜合金的要求日益提高，尤其是其抗高温软化的能力。焊接过程中，由于需加热、高温或高压，因此实际铜合金耗材的使用环境经常是在很高的温度下，所以对铜合金的要求也越来越高。在其他领域内，也存在材料在高温环境下使用的例子，比如电气化铁路接触线，其也需在比较高的温度下长时间使用。因此，开发一款抗高温软化性能更加优良的铜合金便成了迫切的要求。
目前，实际推广的焊接装备导电嘴、电极帽以及电气化铁路接触线等产品多采用传统的铜铬锆合金(如美标C18150)，因其具有优良的强度与导电性能，在上述领域内被广泛应用。但随着机械自动化水平的逐步提高，焊接等行业基本开始采用机器代人策略，以提升生产效率。这种改变就将对其零部件的原材料性能提出新的要求，首当其冲的就是抗高温软化性能，因为抗高温软化性能好，零部件的耗损就小，导致零部件的使用寿命提高，并且焊接过程中的精度也会随之提高。目前传统的铜铬锆合金(如美标C18150)其抗高温软化性能为在580℃下，其硬度损失值在15％以上，这已不能满足相关行业的发展要求，因此，提高材料的抗高温软化性能成了目前迫切的需求。
发明内容
本发明的目的是提供一种抗高温软化性能更加优异的铜合金，解决了目前铬锆铜合金的抗高温软化性能待提升的问题。
为解决上述问题，通过下面所述技术方案实现：一种抗软化铜合金，所述合金的组成为：Cr：0.1-1.0wt％，Zr：0.01-0.2wt％，Si：0.01-0.10wt％，Fe：≤0.10wt％，其余为铜和不可避免的杂质，该铜合金微观结构含有单质Cr相、Cu5Zr相和Cr3Si相。本发明铜合金采用添加适量硅元素形成Cr3Si化合物提升材料抗高温软化效果，同时以单质Cr相和Cu5Zr相强化铜合金基体，并利用Cr3Si相和单质Cr相的协同作用，并通过控制Fe杂质的含量，进一步提升材料的强度和抗高温软化性能。
各合金元素及相关析出相在铜中的作用如下：
铬常温下在铜中的固溶度很小，只有不到0.5％，但在高温时固溶度相对较大，可达0.65％，因此可实现析出强化，是本发明铜合金中的主要强化元素。在铜合金中，利用热处理可得到单质Cr的弥散强化相粒子，对铜基体形成强化效果。在强化铜基体的同时，Cr还会与铜基体中固溶的Si形成Cr3Si化合物，经研究发现Cr3Si化合物为高温稳定化合物相，即使在800℃高温下也不会发生溶解，因此其抗高温软化能力极强。本发明青铜合金铬含量为0.1-1.0％，若铬含量小于此范围，Cr与Si很难形成Cr3Si，即使形成，数量也不多，不能起到应有的作用，而若铬含量大于此范围，铬将大量析出形成强化相，导致铬在晶界处大量积聚，破坏材料的塑性。
锆在铜合金中有一定的溶解度。锆加入可提高铜基体的再结晶温度，提升铜合金的耐高温软化能力。而且锆会与铜形成Cu5Zr中间化合物，对铜基体起到强化作用，同时提升铜合金的电性能。本发明铜合金锆含量在0.01-0.2％，若低于此范围，则起不到作用，而高于此范围，虽对合金能够起到强化作用，但会大大降低合金的导电性，影响合金的综合性能。
硅在铜中有一定的固溶度，可强化铜合金基体，但对铜的导电性影响较大，可大幅降低铜合金的导电率。但当铜合金中有适量的铬时，其可形成Cr3Si相化合物，Cr3Si为析出相，析出后可大幅提升材料的导电性，因此对铜合金综合性能有好的影响。本发明铜合金硅含量在0.01-0.1％，若低于此范围，则铜合金中形成的Cr3Si相不足，无法起到作用，而若高于此范围，虽可形成足够的Cr3Si相，但会大大降低Cr的析出量，影响合金的综合性能。
在本发明中，Fe作为杂质元素而控制，少量的Fe有利于强度的提高，但过高的Fe会影响导电率，因此，在本发明中将Fe含量控制在0.10wt％以下。
本发明铜合金的微观结构中的单质Cr相、Cu5Zr相和Cr3Si相的作用分别如下：
Cr3Si相为合金初生相，在合金液态及结晶过程中产生，其在高温下其有稳定的结构和性能，在800℃下依旧可保持原始结构而不溶解，因此可大幅度提升合金的抗高温 软化能力。Cu5Zr相为本发明铜合金中主要析出强化相之一，其在合金固溶处理后全部溶入铜基体形成过饱和固溶体，在随后的时效过程中从铜基体中析出，弥散分布于合金中。Cu5Zr相析出后，对位错起到钉扎作用，从而提升铜基体的强度和硬度，同时由于其析出，使得铜基体变得纯净，对电子的阻碍作用减小，电阻率减小而导电率得以大幅度提升。本发明铜合金中的另外一种强化相是单质Cr相，其生成原理与Cu5Zr相类似，部产生于合金的热处理中，固溶处理后全部溶入铜基体形成过饱和固溶体，在随后的时效过程中从铜基体中析出，弥散分布于合金中。单质Cr相是本发明合金中最重要的强化相，对合金的强度提升起到至关重要的作用。
本发明合金的3个主要强化相既独立存在，又有一定的依存关系，通过添加合适的合金元素比列，形成合理比例的相，对合金的性能有重要作用。单质Cr相是合金中的主要强化相，对合金强化起主要作用，Cr3Si相为高温相，对合金抗高温软化起主要作用，而Cu5Zr相是另一中强化相，不仅可以强化合金，同时可以增加形核质点，细化单质Cr相和Cr3Si相，并使其弥散分布，进而提升强度和抗高温软化效果。
可选的，单质Cr相、Cr3Si相，满足如下关系：
设单质Cr相重量为X，Cr3Si相重量为Y，则：0＜X/Y＜20。
当强化相达到该比例要求时，该铜合金的抗高温软化性能及强度将得到大幅度的提升。当强化相比例大于20时，合金中的Cr3Si相数量极少，则合金的抗高温软化性能达不到要求。
可选的，该铜合金含有，Mg：0.0001-0.10wt％。设置该比例的镁，可固溶于铜基体中，对铜合金起到强化的效果，并对铜合金的导电性能影响较小；同时可以有效的清除铜合金中的氧，降低铜合金的氧含量，提升材料品质。
可选的，该铜合金还包括0.01％-2.5wt％的Co，Zn，Mn，Sn，Nb元素的任意一种或两种以上，其总和不超过3.5wt％。上述合金元素加入铜合金中，都可以起到固溶强化、提高材料再结晶温度，进而提升材料软化温度的作用。但上述合金元素加入量不宜太大，否则会大大降低材料的导电性能。
可选的，该铜合金的软化温度≥580℃。当铜合金的软化温度≥580℃时，可大幅提升材料对各类焊接工艺的需求，提升焊接材料的使用寿命。
铜合金的软化温度通过实验测定。一般情况下，当材料在某一温度下保温2小时，然后入水冷却，测试处理后的材料硬度，如处理后的材料硬度损失量在15％以内，则认为此温度下材料未软化，反之认为材料软化。传统铜铬锆合金其软化温度在550℃左右，其在550℃下保温2小时，然后入水冷却，其处理后的材料硬度损失量约为13-15％左右，如果是580℃，则其硬度损失量远大于15％。因此传统的铜铬锆合金其软化温度为550℃。而本发明铜合金在上述实验条件下，550℃时材料硬度损失量在4-8％，580℃时材料硬度损失量也不超过10％，因此本发明铜合金的软化温度≥580℃。
本发明还公开了一种抗软化铜合金的制备方法，包括下述步骤：合金化处理精炼——浇注铸锭——锯锭加热挤压——固溶热处理——拉伸及拉拔——时效热处理——矫直精整；
其中所述合金化处理和覆盖保护精炼的熔铸温度为1150℃-1350℃；所述热挤压温度为850℃-950℃；所述固溶处理温度为850℃-1000℃，冷却介质为水，冷却速度为10℃/min-150℃/s；冷拉拔加工率为20％-60％；所述的时效热处理温度为450℃-520℃，保温时间为2h-4h。利用该生产工艺可使生产出来的材料，其单质Cr相、Cu5Zr相、Cr3Si相尺寸合理，分布更弥散，提高了发明铜合金的各项性能。
本发明公开抗软化铜合金在接触线与焊接材料上的应用。
与现有技术相比，本技术方案具有以下优点；
1、本发明铜合金采用添加适量硅元素形成Cr3Si化合物提升材料抗高温软化效果，同时以单质Cr相和Cu5Zr相强化铜合金基体，并利用Cr3Si相和单质Cr相的协同作用，并通过控制Fe杂质的含量，进一步提升材料的强度和抗高温软化性能；
2、本发明铜合金的软化温度≥580℃，更好地满足焊接和接触线领域对铜合金各项性能的要求。
具体实施方式
下面通过具体实施例，对本发明的技术方案进行清楚、完整的描述。
为避免重复，现将本具体实施方式所涉及的技术参数统一描述如下，实施例中不再赘述：
wt％：重量百分比。
％IACS：用来表征金属或合金的导电率(参比于标准退火纯铜)。一般定义标准退火纯铜的导电率为100％IACS，即是5.80E+7(1/Ω·m)或58(m/Ω·mm2)。其值为国际退火铜标准规定的电阻率(不管是体积和质量的)对相同单位试样电阻率之比乘以100。
HR：洛氏硬度。
Rem.：余量。
实施例1-20
表1：本发明抗软化铜合金的成份组成实例(重量％)：
Figure PCTCN2017000536-appb-000001
Figure PCTCN2017000536-appb-000002
分别按表1实施例1-20中所述的抗软化铜合金的成份及其质量百分比配料，然后经熔炼、铸锭、加工成型，最后以1-30℃/min的平均升温速度升温至450℃-520℃，保温时间为2h-4h，得本发明实施例21-40的抗软化铜合金成品(得到成品的实施例21-40，其分别对应实施例1-20中所述的抗软化铜合金的成份及其质量百分比配料)。
对实施例21-40中抗软化铜合金成品的微观组织结构进行分析，结果如表2所示。
本发明实施例21-40中抗软化铜合金主要通过所添加的各种合金元素以及特定的时效处理，形成不同性质的微观中间相及单质，这些微观相弥散的分布于铜基体中，使得铜合金的各种性能得到有效改善，本发明实施例21-40抗软化铜合金的相关相及其含量见表2。
表2 本发明实施例21-40中抗软化铜合金的中间相及其含量
Figure PCTCN2017000536-appb-000003
分别按表1实施例1-20中所述抗软化铜合金的成份及其质量百分比配料，然后采用合金化处理和覆盖保护精炼的熔铸温度为1150℃-1350℃；所述热挤压温度为850℃-950℃；所述固溶处理温度为850℃-1000℃，冷却介质为水，冷却速度为10℃/min-150℃/s；冷拉拔加工率为20％-60％；所述的时效热处理温度为450℃-520℃，保温时间为2h-4h，最后精整成Φ8的与实施例1-20中所述抗软化铜合金的成份及其质量百分比配料相对应的实施例41-60的抗软化铜合金棒材成品。
按相关国家及行业标准规定方法检测本发明实施例41-60抗软化铜合金棒材时抗拉强度、硬度、导电率、软化温度，试验结果见表3。其中，室温拉伸试验按照《GB/T228.1-2010金属材料拉伸试验第1部分：室温试验方法》在电子万能力学性能试验机上进行，试样采用比例系数为5.65的圆形横截面比例试样。导电率测试按照《GB/T3048-2007电线电缆电性能试验方法第2部分：金属材料电阻率试验》，本试验仪器为ZFD微电脑电桥直流电阻测试仪，样品长度为1000mm，用％IACS表示。硬度测试按照《GB/T230.1-2009金属材料 洛氏硬度试验》方法在硬度计上进行测试。
表3：本发明实施例41-60中抗软化铜合金棒材的性能试验结果
Figure PCTCN2017000536-appb-000004
Figure PCTCN2017000536-appb-000005
本发明的抗拉强度≥470MPa，洛氏硬度在75以上，导电率在75％IACS以上。
实施例61-80
实施例61-80中抗软化铜合金的成份及其质量百分比与实施例41-60中的相同，即分别按表1实施例1-20中所述抗软化铜合金的成份及其质量百分比配料，然后采用合金化处理和覆盖保护精炼的熔铸温度为1150℃-1350℃；所述热挤压温度为850℃-950℃；所述固溶处理温度为850℃-1000℃，冷却介质为水，冷却速度为10℃/min-150℃/s；冷拉拔加工率为20％-60％；所述的时效热处理温度为450℃-520℃，保温时间为2h-4h，最后精整成Φ8的抗软化铜合金棒材成品。
按照《HB5420-89电阻焊电极及辅助装置用铜及铜合金》要求方法进行软化温度测试。测试温度选择为580℃，结果列于表4。
表4：本发明实施例61-80中抗软化铜合金棒材的软化温度试验结果
Figure PCTCN2017000536-appb-000006
Figure PCTCN2017000536-appb-000007
通过上述实施例，可以看出，本发明铜合金按标准实验方法，在580℃下，硬度损失值都在8％以下，而对比例的传统铜
Figure PCTCN2017000536-appb-000008
，其硬度损失值大于10％，证明本发明 铜合金的抗高温软化性能有较大提升。
应用实施例
任选实施例41-60中的抗软化铜合金棒材制成焊接用器材。
任选实施例41-60中的抗软化铜合金棒材制成电气化铁路用接触线。
综上所述，本发明抗软化铜合金不仅具有高强度、良好的电性能，还具有优异的抗高温软化性能，特别适合用于焊接器械、电气化铁路用接触线等工业领域。
本文中所描述的具体实施例仅仅是对本发明精神作举例说明。本发明所属技术领域的技术人员可以对所描述的具体实施例做各种修改或补充或采用类似的方式替代，但并不会偏离本发明的精神或者超越所附权利要求书所定义的范围。

Claims (7)

  1. 一种抗软化铜合金，其特征在于，所述合金的组成为：Cr：0.1-1.0wt％，Zr：0.01-0.2wt％，Si：0.01-0.10wt％，Fe：≤0.10wt％，其余为铜和不可避免的杂质，该铜合金微观结构含有单质Cr相、Cu5Zr相和Cr3Si相。
  2. 根据权利要求1所述的抗软化铜合金，其特征在于，所述单质Cr相、Cr3Si相，满足如下关系：
    设单质Cr相重量为X，Cr3Si相重量为Y，则：0＜X/Y＜20。
  3. 根据权利要求1所述的抗软化铜合金，其特征在于，该铜合金含有，Mg：0.0001-0.10wt％。
  4. 根据权利要求1或3所述的抗软化铜合金，其特征在于，该铜合金还包括0.01％-2.5wt％的Co，Zn，Mn，Sn，Nb元素的任意一种或多种，其中总和不超过3.5wt％。
  5. 根据权利要求1所述的抗软化铜合金，其特征在于，该铜合金的软化温度≥580℃。
  6. 根据权利要求1至5中任意一项所述的抗软化铜合金的制备方法，其特征在于，包括下述步骤：合金化处理精炼——浇注铸锭——锯锭加热挤压——固溶热处理——拉伸及拉拔——时效热处理——矫直精整；
    其中所述合金化处理和覆盖保护精炼的熔铸温度为1150℃-1350℃；所述热挤压温度为850℃-950℃；所述固溶处理温度为850℃-1000℃，冷却介质为水，冷却速度为10℃/min-150℃/s；冷拉拔加工率为20％-60％；所述的时效热处理温度为420℃-520℃，保温时间为2h-4h。
  7. 权利要求1至5中任意一项所述的抗软化铜合金在接触线与焊接材料上的应用。
PCT/CN2017/000536 2016-09-09 2017-08-18 抗软化铜合金、制备方法及其应用 Ceased WO2018045695A1 (zh)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US16/321,756 US20190161831A1 (en) 2016-09-09 2017-08-18 Softening Resistant Copper Alloy, Preparation Method, and Application Thereof
EP17847871.5A EP3511432B1 (en) 2016-09-09 2017-08-18 Softening resistant copper alloy, preparation method, and application thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201610813189.5 2016-09-09
CN201610813189.5A CN106350698B (zh) 2016-09-09 2016-09-09 抗软化铜合金、制备方法及其应用

Publications (1)

Publication Number Publication Date
WO2018045695A1 true WO2018045695A1 (zh) 2018-03-15

Family

ID=57858375

Family Applications (1)

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

Country Status (4)

Country Link
US (1) US20190161831A1 (zh)
EP (1) EP3511432B1 (zh)
CN (1) CN106350698B (zh)
WO (1) WO2018045695A1 (zh)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114807672A (zh) * 2022-03-23 2022-07-29 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
CN116274955A (zh) * 2023-02-08 2023-06-23 陕西斯瑞新材料股份有限公司 一种火箭发动机燃烧室内衬用的高温铜合金
CN116479283A (zh) * 2023-03-28 2023-07-25 宁波金田铜业(集团)股份有限公司 一种高性能铬青铜棒材及其制备方法

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
CN116083750A (zh) * 2023-03-10 2023-05-09 江西铜业集团有限公司 一种铜合金带材及制备方法、引线框架和连接器

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705125A (en) * 1992-05-08 1998-01-06 Mitsubishi Materials Corporation Wire for electric railways
CN101113499A (zh) * 2006-07-28 2008-01-30 株式会社神户制钢所 具有高强度和高抗软化性的铜合金
CN101386925A (zh) * 2008-09-12 2009-03-18 邢台鑫晖铜业特种线材有限公司 接触线用Cu-Cr-Zr合金制备工艺
CN102471830A (zh) * 2009-09-25 2012-05-23 三菱综合材料株式会社 铜合金滑接导线
CN102534291A (zh) * 2010-12-09 2012-07-04 北京有色金属研究总院 一种高强高导CuCrZr合金及其制备和加工方法
CN106350698A (zh) * 2016-09-09 2017-01-25 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

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103382535B (zh) * 2013-07-10 2015-09-02 河南科技大学 一种高强、高导电、高延伸性铜合金及其制备方法
CN104342575B (zh) * 2014-10-11 2017-01-18 烟台万隆真空冶金股份有限公司 一种电气化铁路铬锆铜接触线及其加工工艺
JP6693092B2 (ja) * 2015-11-09 2020-05-13 三菱マテリアル株式会社 銅合金素材

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5705125A (en) * 1992-05-08 1998-01-06 Mitsubishi Materials Corporation Wire for electric railways
CN101113499A (zh) * 2006-07-28 2008-01-30 株式会社神户制钢所 具有高强度和高抗软化性的铜合金
CN101386925A (zh) * 2008-09-12 2009-03-18 邢台鑫晖铜业特种线材有限公司 接触线用Cu-Cr-Zr合金制备工艺
CN102471830A (zh) * 2009-09-25 2012-05-23 三菱综合材料株式会社 铜合金滑接导线
CN102534291A (zh) * 2010-12-09 2012-07-04 北京有色金属研究总院 一种高强高导CuCrZr合金及其制备和加工方法
CN106350698A (zh) * 2016-09-09 2017-01-25 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

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HU , JINLI: "Microstructure and Properties of Cu-0.4%Cr-0.12%Zr-0.01%Si Alloy with High Strength and Conductivity", DISSERTATION, 31 August 2010 (2010-08-31), pages 1 - 80, XP009515753 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114807672A (zh) * 2022-03-23 2022-07-29 中南大学 Cu-Zn-Cr-Zr-Fe-Si系合金及其制备方法
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
CN116274955A (zh) * 2023-02-08 2023-06-23 陕西斯瑞新材料股份有限公司 一种火箭发动机燃烧室内衬用的高温铜合金
CN116479283A (zh) * 2023-03-28 2023-07-25 宁波金田铜业(集团)股份有限公司 一种高性能铬青铜棒材及其制备方法

Also Published As

Publication number Publication date
CN106350698A (zh) 2017-01-25
EP3511432A4 (en) 2019-07-17
US20190161831A1 (en) 2019-05-30
CN106350698B (zh) 2018-03-27
EP3511432A1 (en) 2019-07-17
EP3511432B1 (en) 2021-07-21

Similar Documents

Publication Publication Date Title
WO2018045695A1 (zh) 抗软化铜合金、制备方法及其应用
CN103966475B (zh) 一种铜铬钛合金接触线及其制备方法
CN104278171B (zh) 一种CuTi系弹性铜合金及其制备方法
JP2501275B2 (ja) 導電性および強度を兼備した銅合金
CN109022896A (zh) 一种具有电磁波屏蔽性能的高强高导耐热Cu-Fe-Y-Mg合金材料及其制备方法
CN101984107B (zh) CuNiSiAl系弹性铜合金的制备方法
CN104946936A (zh) 一种架空导线用高导电率稀土硬铝单丝材料
CN109266901B (zh) 一种Cu15Ni8Sn高强耐磨合金杆/丝的制备方法
CN110863120B (zh) 一种引线框架用铜合金及其制备方法
CN114657403B (zh) 一种高导耐热耐损伤铝合金导体材料的制备方法
CN111826550A (zh) 一种中等强度耐硝酸腐蚀钛合金
WO2020228503A1 (zh) 一种高强高导 Cu-Ag-Sc 合金及其制备方法
JP5802150B2 (ja) 銅合金
CN101333610A (zh) 超高强、高导电CuNiSi系弹性铜合金及其制备方法
CN107587004B (zh) 一种Al-Ni-Cu-Fe-Yb-Sc合金导体材料及其制备方法
CN102952962B (zh) Cu-Fe复合材料及其制备方法
CN105154709B (zh) 高铬铜合金材料及其制备方法
CN111001964A (zh) 一种石化装备用耐高温腐蚀镍基实心焊丝制备方法及焊接工艺
CN115464406B (zh) 一种高强高导CuCr铜中间合金及其制备方法
CN102492869B (zh) 一种铜锆铋合金及其制备方法
CN118421993A (zh) 一种改善Cu-Cr-Zr系合金硬度和导电率的制备工艺
CN100434553C (zh) 一种高温固溶强化耐热钛合金
CN103827329A (zh) 电线用导体
CN101693959A (zh) Cu-Fe-Ag-P原位复合材料及其制备方法
JP5252722B2 (ja) 高強度・高導電性銅合金及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17847871

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2017847871

Country of ref document: EP

Effective date: 20190409