WO2021129802A1 - 一种高强韧铜锌铝形状记忆合金及其制备方法 - Google Patents

一种高强韧铜锌铝形状记忆合金及其制备方法 Download PDF

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WO2021129802A1
WO2021129802A1 PCT/CN2020/139375 CN2020139375W WO2021129802A1 WO 2021129802 A1 WO2021129802 A1 WO 2021129802A1 CN 2020139375 W CN2020139375 W CN 2020139375W WO 2021129802 A1 WO2021129802 A1 WO 2021129802A1
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alloy
preparation
zinc
copper
smelting
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French (fr)
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刘光磊
李绍鸣
万浩
司乃潮
李守祥
孙忠国
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南京龙浩新材料科技有限公司
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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
    • C22C9/01—Alloys based on copper with aluminium as the next major constituent
    • 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
    • C22C1/02—Making non-ferrous alloys by melting
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • 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

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  • the invention relates to the technical field of shape memory alloys, in particular to a high-strength and toughness copper-zinc-aluminum shape memory alloy and a preparation method thereof.
  • Shape memory alloy is a special and novel functional material. Appropriate adjustment of the composition and control of the heat treatment process can make this alloy show three characteristics: (1) shape memory effect; (2) super elasticity; (3) high damping ability. The use of these three characteristics has made shape memory alloys have many applications in industry and has broad application prospects. In the process of solution treatment of copper-based shape memory alloys, the crystal grains are extremely easy to coarsen, resulting in poor ductility and fatigue life. Short, prone to intergranular fracture during use. In order to improve the ductility of copper-based shape memory alloys, suppress grain boundary damage, and increase fatigue life, people have done a lot of work on the grain refinement of copper-zinc-aluminum alloys.
  • the basic principle of grain refinement is to increase the nucleation rate and slow down the growth rate of grains. Therefore, one or more of the copper-based shape memory alloys can be added to the copper-based shape memory alloy with little solubility or can form with certain elements in the alloy.
  • the element of the fine compound promotes the formation of fine equiaxed crystals during the solidification process, or prevents the growth of crystal grains during thermal processing and heat treatment.
  • Chinese patent CN201310345218.6 discloses a composite rare earth modifier that can improve the comprehensive performance of copper-zinc-aluminum memory alloy. By adding 0.2-1.2wt.% of composite rare-earth refiner to the alloy, the copper-zinc-aluminum alloy is improved. Wear resistance, tensile strength, elongation and hardness, but the copper-zinc-aluminum memory alloy prepared by this method has poor cold and hot fatigue properties.
  • the purpose of the present invention is to provide a method for preparing a high-strength and toughness copper-zinc-aluminum shape memory alloy.
  • the preparation method provided by the present invention can significantly improve the cold and hot fatigue properties of the alloy.
  • the invention provides a method for preparing a high-strength and toughness copper-zinc-aluminum shape memory alloy, which comprises the following steps:
  • step (2) Mix and melt the base alloy liquid and Cu-10RE master alloy described in step (1) to obtain a target alloy melt; in terms of mass content, the chemical composition of the Cu-10RE master alloy is: La7-8%, Y2 ⁇ 3%, other rare earth elements are less than 1%, the balance is Cu;
  • step (4) The as-cast alloy billet described in step (4) is subjected to heat preservation treatment and then deformed to obtain a densified alloy billet;
  • step (6) The densified alloy billet described in step (5) is sequentially subjected to cryogenic treatment and aging treatment to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy.
  • the chemical composition of the copper-zinc-aluminum alloy raw material is: Zn 25-26.3%, Al 2.8-3.6%, Mn 0.9-1.1%, Ni 0.8-1.1%, Zr 0.45-0.55%, The remainder is Cu.
  • the chemical composition of the copper-zinc-aluminum alloy raw material is: Zn 25.5-25.8%, Al 3.0-3.3%, Mn 1.0-1.1%, Ni 0.9-1.0%, Zr 0.49-0.52%, The remainder is Cu.
  • the first smelting in step (1) is magnetic levitation vacuum smelting, and the temperature of the first smelting is 1020-1060°C.
  • the content of rare earth elements in the Cu-10RE master alloy is 0.05-0.09% of the mass of the base alloy liquid.
  • the temperature of the mixing and melting in step (2) is 1020-1040°C.
  • the second smelting in step (4) is a magnetic levitation vacuum smelting, and the temperature of the second smelting is 1020-1060°C; the number of the second smelting is 2 to 3 times.
  • the heat preservation treatment in step (5) is performed under vacuum conditions, and the vacuum degree is higher than 10 -2 Pa.
  • the temperature of the heat preservation treatment is 800 to 810°C, and the time is 10 to 12 hours.
  • the deformation amount of the deformation is 50-70%.
  • the density of the densified alloy billet is 6.73 to 6.77 g/cm 3 .
  • the cryogenic treatment in step (6) is liquid nitrogen treatment; the time of the cryogenic treatment is 3 to 5 hours.
  • the aging treatment in step (6) includes a primary aging treatment and a secondary aging treatment in sequence, the temperature of the primary aging treatment is 150-170°C, and the time is 0.3-0.5h; The temperature of the aging treatment is 80 ⁇ 90°C, and the time is 0.5 ⁇ 1h.
  • the present invention provides a high-strength and toughness copper-zinc-aluminum shape memory alloy, which is prepared by the preparation method described in any one of the above technical solutions.
  • the present invention provides a method for preparing a high-strength and toughness copper-zinc-aluminum shape memory alloy, which includes the following steps: first smelting the copper-zinc-aluminum alloy raw materials to obtain a base alloy liquid; and combining the base alloy liquid with a Cu-10RE master alloy Mix and melt to obtain the target alloy melt; in terms of mass content, the chemical composition of the Cu-10RE master alloy is: La 7-8%, Y 2-3%, other rare earth elements less than 1%, and the balance is Cu; Casting the target alloy melt to obtain an ingot; performing a second smelting on the ingot to obtain an as-cast alloy billet; deforming the as-cast alloy billet after heat preservation treatment to obtain a densified alloy billet; The densified alloy billet is sequentially subjected to cryogenic treatment and aging treatment to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy.
  • the invention further refines the crystal grains of the alloy through two smelting and cryogenic treatments, and through the coordination of other preparation processes, the copper-zinc-aluminum shape memory alloy obtains better toughness and plasticity, and improves the cold and hot fatigue performance of the alloy;
  • the Cu-10RE master alloy is a refiner.
  • composite rare earth elements can react with harmful impurities on the one hand to produce high melting point products, which float on the surface of the solution when standing, and on the other hand react with other alloy elements to form intergranular These intergranular products act as heterogeneous crystal nuclei in the early stage of alloy solidification, and mechanically hinder the growth of crystal grains in the later stage of solidification, which is beneficial to refine the grains and improve the alloy’s thermal fatigue performance.
  • Figure 1 shows the test results of thermal fatigue performance of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 at 20-300°C;
  • Figure 2 shows the test results of the thermal fatigue performance of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 at 20-400°C;
  • Figure 3 shows the test results of thermal fatigue performance of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 at 20-500°C.
  • the invention provides a method for preparing a high-strength and toughness copper-zinc-aluminum shape memory alloy, which comprises the following steps:
  • step (2) Mix and melt the base alloy liquid and Cu-10RE master alloy described in step (1) to obtain a target alloy melt; in terms of mass content, the chemical composition of the Cu-10RE master alloy is: La7-8%, Y2 ⁇ 3%, other rare earth elements are less than 1%, the balance is Cu;
  • step (4) The as-cast alloy billet described in step (4) is subjected to heat preservation treatment and then deformed to obtain a densified alloy billet;
  • step (6) The densified alloy billet described in step (5) is sequentially subjected to cryogenic treatment and aging treatment to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy.
  • the copper-zinc-aluminum alloy raw material is first smelted to obtain a basic alloy liquid.
  • the chemical composition of the copper-zinc-aluminum alloy raw material is preferably: Zn 25-26.3%, Al 2.8-3.6%, Mn 0.9-1.1%, Ni 0.8-1.1%, Zr 0.45- 0.55%, the balance is Cu and unavoidable impurities.
  • the copper-zinc-aluminum alloy raw materials provided by the present invention include 25-26.3% of Zn, preferably 25.5-25.8%, and 2.8-3.6% of Al, preferably 3.0-3.3% by mass content.
  • the Zn and Al are the matrix elements of the alloy.
  • the copper-zinc-aluminum alloy raw materials provided by the present invention include 0.9-1.1% of Mn, preferably 1.0-1.1%, in terms of mass content.
  • Mn can lower the phase transition temperature and refine the crystal grains.
  • the copper-zinc-aluminum alloy raw materials provided by the present invention include 0.8-1.1% Ni, preferably 0.9-1.0%, in terms of mass content.
  • Ni element can improve the mechanical properties of the alloy.
  • Ni element diffuses slowly in the copper-based alloy, it has little effect on the diffusion rate of other alloy elements. Therefore, the addition of Ni does not affect the martensite of the alloy.
  • the copper-zinc-aluminum alloy raw materials provided by the present invention include Zr 0.45-0.55% by mass content, preferably 0.49-0.52%.
  • Zr can refine the grains, significantly increase the fracture stress and fracture strain of the alloy, and effectively inhibit the generation of intergranular fracture; at the same time, the addition of Zr also increases the recoverable strain of the alloy from 4% To 6%, the shape memory performance of the alloy is improved.
  • the copper-zinc-aluminum alloy raw materials provided by the present invention include the remainder of Cu and unavoidable impurities in addition to the above-mentioned elements.
  • the present invention does not specifically limit the specific source of the copper-zinc-aluminum alloy raw materials, and the alloy raw materials well known to those skilled in the art are used as the copper-zinc-aluminum alloy raw materials that can obtain the target components.
  • the copper-zinc-aluminum alloy raw materials preferably include alloys or pure metals with higher purity than industrial purity, specifically preferably Cu-5Ni, Cu-10Mn, Cu-5Zr, pure Cu, pure Zn and pure Al.
  • the present invention does not specifically limit the ratio of the various alloy raw materials, as long as the final alloy composition can meet the requirements.
  • the first smelting is preferably a magnetic levitation vacuum smelting, which can prevent the interference of impurities in the container and the air.
  • the vacuum degree in the first smelting process is preferably higher than 10 -3 Pa, more preferably 10 -4 Pa; the temperature of the first smelting is preferably 1020-1060°C, more preferably 1030- 1050°C.
  • the present invention mixes and melts the base alloy liquid and the Cu-10RE master alloy to obtain the target alloy melt.
  • the chemical composition of the Cu-10RE master alloy is: La7-8%, Y2-3%, other rare earth elements less than 1%, and the balance is Cu.
  • the content of rare earth elements in the Cu-10RE master alloy is preferably 0.05 to 0.09% of the mass of the base alloy liquid, more preferably 0.06 to 0.08%.
  • the temperature of the mixing and melting is preferably 1020-1040°C, more preferably 1020-1030°C.
  • the method provided by the invention firstly smelts the copper-zinc-aluminum alloy, and then adds the Cu-10RE master alloy, and uses the supercooling effect generated by the addition of rare earth elements to improve the alloy structure, refine the crystal grains, and improve the comprehensive mechanical properties and fatigue properties.
  • the present invention casts the target alloy melt to obtain an ingot.
  • the present invention does not specifically limit the specific casting process, as long as the casting process well known to those skilled in the art can be used.
  • the ingot is preferably a bar with a diameter of 15 mm and a length of 20 mm.
  • the present invention performs the second smelting of the ingot to obtain the as-cast alloy billet.
  • the second smelting is preferably magnetic levitation vacuum smelting, and the vacuum degree in the second smelting process is preferably higher than 10 -3 Pa;
  • the temperature of the second smelting is preferably 1020-1060°C, more preferably The temperature is 1030 to 1050°C;
  • the number of the second melting is preferably 2 to 3 times.
  • the present invention can improve the composition of the alloy to be more uniform by repeating the melting multiple times.
  • the present invention subjects the as-cast alloy billet to heat preservation treatment and then deforms to obtain a densified alloy billet.
  • the heat preservation treatment is preferably carried out under vacuum conditions, and the degree of vacuum is preferably higher than 10 -2 Pa, more preferably 10 -3 Pa; the temperature of the heat preservation treatment is preferably 800 to 810°C; and the time is preferably 10-12h, more preferably 12h.
  • the present invention can promote the further homogenization of alloy composition, improve the structure and improve the overall performance of the alloy through heat preservation treatment. In the present invention, it is preferable to cool in the furnace after the heat preservation treatment, and then perform deformation.
  • the deformation is preferably forging deformation
  • the amount of deformation is preferably 50 to 70%
  • the density of the compacted alloy billet obtained after forging deformation is preferably 6.73 to 6.77 g/cm 3 .
  • the present invention sequentially performs cryogenic treatment and aging treatment on the densified alloy billet to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy.
  • the cryogenic treatment is preferably liquid nitrogen treatment; the time of the cryogenic treatment is preferably 3 to 5 hours, more preferably 5 hours.
  • the invention can improve the structure, refine the crystal grains, and improve the overall performance and thermal fatigue performance of the alloy through cryogenic treatment.
  • the aging treatment preferably includes a primary aging treatment and a secondary aging treatment in sequence, and the temperature of the primary aging treatment is preferably 150-170°C, more preferably 160-170°C; the time is preferably 0.3-0.5h, more preferably 0.5h; the temperature of the secondary aging treatment is preferably 80-90°C, more preferably 90°C; the time is preferably 0.5-1h, more preferably 1h.
  • the invention adopts two-stage aging treatment to strengthen the alloy.
  • the present invention provides a high-strength and toughness copper-zinc-aluminum shape memory alloy, which is prepared by the preparation method described in any one of the above technical solutions.
  • the copper-zinc-aluminum shape memory alloy prepared by the invention has higher toughness and plasticity, and obtains excellent cold and hot fatigue performance. It can be seen from the results of the examples that the high-strength and toughness copper-zinc-aluminum shape memory alloy provided by the present invention has high cold and hot fatigue properties at 20-300°C, 20-400°C and 20-500°C, which is beneficial to improve the shape of copper-zinc-aluminum The service life of memory alloy.
  • the vacuum degree is 10 -2 Pa, and the melting temperature is 1020°C;
  • the densified alloy billet is placed in liquid nitrogen for 3 hours; then a two-stage aging treatment is performed to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy; wherein the two-stage aging treatment specifically includes: first heat preservation in oil at 150°C 0.3h; then keep it in 80°C water for 0.5h.
  • the vacuum degree is 10 -3 Pa, and the melting temperature is 1030°C;
  • the densified alloy billet is placed in liquid nitrogen for 4 hours; then a two-stage aging treatment is performed to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy; wherein the two-stage aging treatment specifically includes: first heat preservation in oil at 160°C 0.3h; then keep it in 90°C water for 0.6h.
  • the specific chemical composition is Zn 26.1%, Al 3.1%, Mn 1.0%, Ni 1.1 %, Zr 0.50%, the balance is Cu and unavoidable impurities. ;
  • the vacuum degree is 10 -2 Pa, and the melting temperature is 1020°C;
  • the densified alloy billet is placed in liquid nitrogen for 3 hours; then a two-stage aging treatment is performed to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy; wherein the two-stage aging treatment specifically includes: first heat preservation in oil at 150°C 0.3h; then keep it in 80°C water for 0.5h.
  • the vacuum degree is 10 -3 Pa, and the melting temperature is 1030°C;
  • the densified alloy billet is placed in liquid nitrogen for 5 hours; then a two-stage aging treatment is performed to obtain a high-strength and toughness copper-zinc-aluminum shape memory alloy; wherein the two-stage aging treatment specifically includes: first heat preservation in oil at 160°C 0.5h; then keep it in 90°C water for 1h.
  • the preparation method is basically the same as that of Example 1, except that the liquid nitrogen treatment process is omitted.
  • the preparation method is basically the same as that of Example 1, except that the smelting process and the liquid nitrogen treatment process of the ingot are omitted.
  • the copper-zinc-aluminum alloy obtained in Examples 1 to 4 and Comparative Examples 1 to 2 were processed into cold and hot fatigue specimens according to national standards (the specimen size is 40mm ⁇ 20mm ⁇ 5mm, and the warp cutting method is processed into a V with a depth of 3mm Type notch, the other end of the notch has a hole to fix the sample), the cold and hot fatigue test is carried out on the cold and hot fatigue testing machine, respectively at three temperatures of 20 ⁇ 300°C, 20 ⁇ 400°C and 20 ⁇ 500°C Perform a cold and hot fatigue test in the range of 500 cycles, remove the sample every 500 cycles, polish to remove the surface oxide film, measure the surface crack length, use 0.1mm as the crack initiation length, record the number of cycles of crack initiation of the sample, and the test results are as follows: Shown in Figures 1 to 3; among them, Figure 1 is the test results of the cold and hot fatigue performance of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 at 20 to 300°C; Figure 2 is Examples 1 to 4 and Comparative

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Abstract

一种高强韧铜锌铝形状记忆合金及其制备方法，该制备方法是通过两次熔炼和深冷处理进一步细化合金的晶粒，通过其他制备工艺的配合作用，使得铜锌铝形状记忆合金获得了较好的韧塑性，提高了合金的冷热疲劳性能；Cu-10RE中间合金是细化剂，加入复合稀土元素一方面能够与有害杂质反应，生成高熔点产物，静置时浮出溶液表面，另一方面与其他合金元素反应生成晶间产物，这些晶间产物在合金凝固初期起异质晶核作用，在凝固后期则机械阻碍晶粒的长大，有利于细化晶粒，提高合金的冷热疲劳性能。

Description

一种高强韧铜锌铝形状记忆合金及其制备方法
本申请要求于2019年12月25日提交中国专利局、申请号为CN201911355973.6、发明名称为“一种高强韧铜锌铝形状记忆合金及其制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及形状记忆合金技术领域，具体涉及一种高强韧铜锌铝形状记忆合金及其制备方法。
背景技术
形状记忆合金是一种特殊且新颖的功能材料，适当地调整成分和控制热处理过程，可使这种合金出现三大特性：(1)形状记忆效应；(2)超弹性；(3)高阻尼能力。利用这三大特性已使形状记忆合金在工业上得到许多用途，具有广阔的应用前景，铜基形状记忆合金在固溶处理的过程中，晶粒极易粗化，导致其延性差，疲劳寿命短，在使用过程中易发生沿晶断裂。为了改善铜基形状记忆合金的延性，抑制晶界破坏，提高疲劳寿命，人们在铜锌铝合金晶粒细化方面做了大量的工作。晶粒细化的基本原理就是增大形核率，减缓晶粒长大速度，因此，可以在铜基形状记忆合金中添加一种或几种溶解度很小的或者能和合金中某些元素形成微细化合物的元素，在凝固过程中促进细小等轴晶形成，或在热加工和热处理过程中阻止晶粒长大。
中国专利CN201310345218.6公开了一种能提高铜锌铝记忆合金综合性能的复合稀土变质剂，通过在合金中加入0.2～1.2wt.％的复合稀土细化变质剂，提高了铜锌铝合金的耐磨性、抗拉强度、伸长率和硬度，但该方法制备的铜锌铝记忆合金的冷热疲劳性能欠佳。
发明内容
本发明的目的在于提供一种高强韧铜锌铝形状记忆合金的制备方法，采用本发明提供的制备方法能够显著提高合金的冷热疲劳性能。
为了实现上述发明目的，本发明提供以下技术方案：
本发明提供了一种高强韧铜锌铝形状记忆合金的制备方法，包括以下步骤：
(1)将铜锌铝合金原料进行第一熔炼，得到基础合金液；
(2)将步骤(1)所述基础合金液与Cu-10RE中间合金混合熔化，得到目标合金熔体；按质量含量计，所述Cu-10RE中间合金的化学成分为：La7～8％，Y2～3％，其他稀土元素小于1％，余量为Cu；
(3)将步骤(2)所述目标合金熔体进行铸造，得到铸锭；
(4)将步骤(3)所述铸锭进行第二熔炼，得到铸态合金坯；
(5)将步骤(4)所述铸态合金坯进行保温处理后变形，得到致密化合金坯；
(6)将步骤(5)所述致密化合金坯依次进行深冷处理和时效处理，得到高强韧铜锌铝形状记忆合金。
优选地，按质量含量计，所述铜锌铝合金原料的化学成分为：Zn 25～26.3％，Al 2.8～3.6％，Mn 0.9～1.1％，Ni 0.8～1.1％，Zr 0.45～0.55％，余量为Cu。
优选地，按质量含量计，所述铜锌铝合金原料的化学成分为：Zn 25.5～25.8％，Al 3.0～3.3％，Mn 1.0～1.1％，Ni 0.9～1.0％，Zr 0.49～0.52％，余量为Cu。
优选地，步骤(1)所述第一熔炼为磁悬浮真空熔炼，所述第一熔炼的温度为1020～1060℃。
优选地，所述Cu-10RE中间合金中稀土元素的含量为基础合金液质量的0.05～0.09％。
优选地，步骤(2)所述混合熔化的温度为1020～1040℃。
优选地，步骤(4)所述第二熔炼为磁悬浮真空熔炼，所述第二熔炼的温度为1020～1060℃；所述第二熔炼的次数为2～3次。
优选地，步骤(5)所述保温处理在真空条件下进行，真空度高于10 -2Pa。
优选地，所述保温处理的温度为800～810℃，时间为10～12h。
优选地，所述变形的变形量为50～70％。
优选地，所述致密化合金坯的密度为6.73～6.77g/cm 3。
优选地，步骤(6)所述深冷处理为液氮处理；所述深冷处理的时间为3～5h。
优选地，步骤(6)所述时效处理包括依次进行的一级时效处理和二级时效处理，所述一级时效处理的温度为150～170℃，时间为0.3～0.5h；所述二级时效处理的温度为80～90℃，时间为0.5～1h。
本发明提供了一种高强韧铜锌铝形状记忆合金，采用上述技术方案任一项所述制备方法制备得到。
本发明提供了一种高强韧铜锌铝形状记忆合金的制备方法，包括以下步骤：将铜锌铝合金原料进行第一熔炼，得到基础合金液；将所述基础合金液与Cu-10RE中间合金混合熔化，得到目标合金熔体；按质量含量计，所述Cu-10RE中间合金的化学成分为：La 7～8％，Y 2～3％，其他稀土元素小于1％，余量为Cu；将所述目标合金熔体进行铸造，得到铸锭；将所述铸锭进行第二熔炼，得到铸态合金坯；将所述铸态合金坯进保温处理后变形，得到致密化合金坯；将所述致密化合金坯依次进行深冷处理和时效处理，得到高强韧铜锌铝形状记忆合金。本发明通过两次熔炼和深冷处理进一步细化合金的晶粒，通过其他制备工艺的配合作用，使得铜锌铝形状记忆合金获得了较好的韧塑性，提高了合金的冷热疲劳性能；在本发明中，Cu-10RE中间合金是细化剂，加入复合稀土元素一方面能够与有害杂质反应，生成高熔点产物，静置时浮出溶液表面，另一方面与其他合金元素反应生成晶间产物，这些晶间产物在合金凝固初期起异质晶核作用，在凝固后期则机械阻碍晶粒的长大，有利于细化晶粒，提高合金的冷热疲劳性能。
说明书附图
图1为实施例1～4、对比例1和对比例2在20～300℃的冷热疲劳性能测试结果；
图2为实施例1～4、对比例1和对比例2在20～400℃的冷热疲劳性能测试结果；
图3为实施例1～4、对比例1和对比例2在20～500℃的冷热疲劳性能测试结果。
具体实施方式
本发明提供了一种高强韧铜锌铝形状记忆合金的制备方法，包括以下步骤：
(1)将铜锌铝合金原料进行第一熔炼，得到基础合金液；
(2)将步骤(1)所述基础合金液与Cu-10RE中间合金混合熔化，得到目标合金熔体；按质量含量计，所述Cu-10RE中间合金的化学成分为：La7～8％，Y2～3％，其他稀土元素小于1％，余量为Cu；
(3)将步骤(2)所述目标合金熔体进行铸造，得到铸锭；
(4)将步骤(3)所述铸锭进行第二熔炼，得到铸态合金坯；
(5)将步骤(4)所述铸态合金坯进保温处理后变形，得到致密化合金坯；
(6)将步骤(5)所述致密化合金坯依次进行深冷处理和时效处理，得到高强韧铜锌铝形状记忆合金。
本发明将铜锌铝合金原料进行第一熔炼，得到基础合金液。在本发明中，按质量含量计，所述铜锌铝合金原料的化学成分优选为：Zn 25～26.3％，Al 2.8～3.6％，Mn 0.9～1.1％，Ni 0.8～1.1％，Zr 0.45～0.55％，余量为Cu及不可避免杂质。
本发明提供的铜锌铝合金原料，按质量含量计，包括Zn 25～26.3％，优选为25.5～25.8％；包括Al 2.8～3.6％，优选为3.0～3.3％。在本发明中，所述Zn和Al为合金的基体元素。
本发明提供的铜锌铝合金原料，按质量含量计，包括Mn0.9～1.1％，优选为1.0～1.1％。在本发明中，Mn可以降低相变温度，细化晶粒。
本发明提供的铜锌铝合金原料，按质量含量计，包括Ni0.8～1.1％，优选为0.9～1.0％。在本发明中，Ni元素可以提高合金的机械性能，同时由于Ni元素在铜基合金中扩散缓慢，对其他合金元素的扩散速度影响不大，所以，Ni的加入并不影响合金的马氏体界面推移过程中合金的有序度、空位浓度和合金元素浓度。
本发明提供的铜锌铝合金原料，按质量含量计，包括Zr 0.45～0.55％，优选为0.49～0.52％。在本发明中，Zr可以细化晶粒，显著提高了合金的 断裂应力和断裂应变，并有效地抑制了沿晶断裂的产生；同时Zr的加入还使合金的可恢复应变量从4％提高到6％，改善了合金的形状记忆性能。
本发明提供的铜锌铝合金原料，按质量含量计，除上述元素外，包括余量的Cu和不可避免的杂质。
本发明对所述铜锌铝合金原料的具体来源没有特殊的限定，采用本领域技术人员所熟知的合金原料以能得到目标组分的铜锌铝合金原料为准。在本发明中，所述铜锌铝合金原料优选包括合金或纯度高于工业纯的纯金属，具体优选为Cu-5Ni、Cu-10Mn、Cu-5Zr、纯Cu、纯Zn和纯Al。本发明对所述各种合金原料的比例没有特殊的限定，能够使最终合金成分满足要求即可。
在本发明中，所述第一熔炼优选为磁悬浮真空熔炼，能够防止容器及空气中的杂质干扰。在本发明中，所述第一熔炼过程中的真空度优选高于10 -3Pa，更优选为10 -4Pa；所述第一熔炼的温度优选为1020～1060℃，更优选为1030～1050℃。本发明优选在所述熔炼过程中进行搅拌，提高熔体的均匀性。
得到基础合金液后，本发明将所述基础合金液与Cu-10RE中间合金混合熔化，得到目标合金熔体。在本发明中，按质量含量计，所述Cu-10RE中间合金的化学成分为：La7～8％，Y2～3％，其他稀土元素小于1％，余量为Cu。在本发明中，所述Cu-10RE中间合金中稀土元素的含量优选为基础合金液质量的0.05～0.09％，更优选为0.06～0.08％。在本发明中，所述混合熔化的温度优选为1020～1040℃，更优选为1020～1030℃。本发明提供的方法先熔炼铜锌铝合金，再加入Cu-10RE中间合金，利用稀土元素添加所产生的过冷效应，改善合金组织，细化晶粒，提高综合力学性能和疲劳性能。
得到目标合金熔体后，本发明将所述目标合金熔体进行铸造，得到铸锭。本发明对所述铸造的具体工艺没有特殊的限定，采用本领域技术人员所熟知的铸造工艺即可。在本发明中，所述铸锭优选直径为15mm，长为20mm的棒材。本发明优选在铸造之前，先将所述目标合金熔体进行扒渣和过滤，去除合金液中的杂质。
得到铸锭后，本发明将所述铸锭进行第二熔炼，得到铸态合金坯。在 本发明中，所述第二熔炼优选为磁悬浮真空熔炼，所述第二熔炼过程中的真空度优选高于10 -3Pa；所述第二熔炼的温度优选为1020～1060℃，更优选为1030～1050℃；所述第二熔炼的次数优选为2～3次，本发明通过多次反复熔炼，能够提高使合金的成分更加均匀。
得到铸态合金坯后，本发明将所述铸态合金坯进行保温处理后变形，得到致密化合金坯。在本发明中，所述保温处理优选在真空条件下进行，真空度优选高于10 -2Pa，更优选为10 -3Pa；所述保温处理的温度优选为800～810℃；时间优选为10～12h，更优选为12h。本发明通过保温处理能够促进合金成分进一步均匀化，改善组织，提高合金综合性能。本发明优选在保温处理后随炉冷却，然后再进行变形。
在本发明中，所述变形优选为锻造变形，变形量优选为50～70％，锻造变形后所得致密化合金坯的密度优选为6.73～6.77g/cm 3。
得到致密化合金坯后，本发明将所述致密化合金坯依次进行深冷处理和时效处理，得到高强韧铜锌铝形状记忆合金。在本发明中，所述深冷处理优选为液氮处理；所述深冷处理的时间优选为3～5h，更优选为5h。本发明通过深冷处理能够改善组织，细化晶粒，改善合金的综合性能和冷热疲劳性能。
在本发明中，所述时效处理优选包括依次进行的一级时效处理和二级时效处理，所述一级时效处理的温度优选为150～170℃，更优选为160～170℃；时间优选为0.3～0.5h，更优选为0.5h；所述二级时效处理的温度优选为80～90℃，更优选为90℃；时间优选为0.5～1h，更优选为1h。本发明采用两级时效处理能够强化合金。
本发明提供了一种高强韧铜锌铝形状记忆合金，采用上述技术方案任一项所述制备方法制备得到。本发明制备的铜锌铝形状记忆合金具有较高的韧塑性，获得了优异的冷热疲劳性能。由实施例结果可知，本发明提供的高强韧铜锌铝形状记忆合金在20～300℃、20～400℃和20～500℃均具有较高的冷热疲劳性能，有利于提高铜锌铝形状记忆合金的使用寿命。
下面将结合本发明中的实施例，对本发明中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创 造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。
实施例1
将Cu-5Ni、Cu-10Mn、Cu-5Zr、纯Cu、纯Zn和纯Al进行混合，得到铜锌铝合金原料，具体的化学成分为Zn 25.8％，Al 3.2％，Mn 0.9％，Ni 1.0％，Zr 0.46％，余量为Cu及不可避免杂质；
将所述铜锌铝合金原料置于磁悬浮真空熔炼设备中，真空度为10 -2Pa，在1050℃条件下融化后搅拌均匀，得到基础合金液；
将所述基础合金液降温至1030℃，加入Cu-10RE中间合金，待Cu-10RE中间合金熔化后搅拌均匀，得到目标合金熔体；
对所述目标合金熔体进行扒渣、过滤后进行铸造得到铸锭；
利用磁悬浮真空熔炼设备将所述铸锭反复熔炼2～3次，得到铸态合金坯，真空度为10 -2Pa，熔炼温度为1020℃；
将所述铸态合金坯置于800℃的真空热处理设备中保温12h后随炉冷却；然后进行锻造处理，得到致密化合金坯；
将所述致密化合金坯置于液氮中处理3h；然后进行两级时效处理得到高强韧铜锌铝形状记忆合金；其中，所述两级时效处理具体为：先在150℃的油中保温0.3h；然后在80℃的水中保温0.5h。
实施例2
将Cu-5Ni、Cu-10Mn、Cu-5Zr、纯Cu、纯Zn和纯Al进行混合，得到铜锌铝合金原料，具体的化学成分为Zn 25.3％，Al 3.5％，Mn 1.0％，Ni 0.9％，Zr 0.49％，余量为Cu及不可避免杂质。；
将所述铜锌铝合金原料置于磁悬浮真空熔炼设备中，真空度为10 -3Pa，在1050℃条件下融化后搅拌均匀，得到基础合金液；
将所述基础合金液降温至1030℃，加入Cu-10RE中间合金，待Cu-10RE中间合金熔化后搅拌均匀，得到目标合金熔体；
对所述目标合金熔体进行扒渣、过滤后进行铸造得到铸锭；
利用磁悬浮真空熔炼设备将所述铸锭反复熔炼2～3次，得到铸态合金坯，真空度为10 -3Pa，熔炼温度为1030℃；
将所述铸态合金坯置于800℃的真空热处理设备中保温12h后随炉冷却；然后进行锻造处理，得到致密化合金坯；
将所述致密化合金坯置于液氮中处理4h；然后进行两级时效处理得到高强韧铜锌铝形状记忆合金；其中，所述两级时效处理具体为：先在160℃的油中保温0.3h；然后在90℃的水中保温0.6h。
实施例3
将Cu-5Ni、Cu-10Mn、Cu-5Zr、纯Cu、纯Zn和纯Al进行混合，得到铜锌铝合金原料，具体的化学成分为Zn 26.1％，Al 3.1％，Mn 1.0％，Ni 1.1％，Zr 0.50％，余量为Cu及不可避免杂质。；
将所述铜锌铝合金原料置于磁悬浮真空熔炼设备中，真空度为10 -3Pa，在1050℃条件下融化后搅拌均匀，得到基础合金液；
将所述基础合金液降温至1040℃，加入Cu-10RE中间合金，待Cu-10RE中间合金熔化后搅拌均匀，得到目标合金熔体；
对所述目标合金熔体进行扒渣、过滤后进行铸造得到铸锭；
利用磁悬浮真空熔炼设备将所述铸锭反复熔炼2次，得到铸态合金坯，真空度为10 -2Pa，熔炼温度为1020℃；
将所述铸态合金坯置于800℃的真空热处理设备中保温10h后随炉冷却；然后进行锻造处理，得到致密化合金坯；
将所述致密化合金坯置于液氮中处理3h；然后进行两级时效处理得到高强韧铜锌铝形状记忆合金；其中，所述两级时效处理具体为：先在150℃的油中保温0.3h；然后在80℃的水中保温0.5h。
实施例4
将Cu-5Ni、Cu-10Mn、Cu-5Zr、纯Cu、纯Zn和纯Al进行混合，得到铜锌铝合金原料，具体的化学成分为Zn 25.9％，Al 3.2％，Mn 0.9％，Ni 1.1％，Zr 0.52％，余量为Cu及不可避免杂质。；
将所述铜锌铝合金原料置于磁悬浮真空熔炼设备中，真空度为10 -3Pa，在1040℃条件下融化后搅拌均匀，得到基础合金液；
将所述基础合金液降温至1030℃，加入Cu-10RE中间合金，待Cu-10RE中间合金熔化后搅拌均匀，得到目标合金熔体；
对所述目标合金熔体进行扒渣、过滤后进行铸造得到铸锭；
利用磁悬浮真空熔炼设备将所述铸锭反复熔炼2～3次，得到铸态合金坯，真空度为10 -3Pa，熔炼温度为1030℃；
将所述铸态合金坯置于800℃的真空热处理设备中保温12h后随炉冷却；然后进行锻造处理，得到致密化合金坯；
将所述致密化合金坯置于液氮中处理5h；然后进行两级时效处理得到高强韧铜锌铝形状记忆合金；其中，所述两级时效处理具体为：先在160℃的油中保温0.5h；然后在90℃的水中保温1h。
对比例1
与实施例1的制备方法基本相同，不同之处仅在于省略了液氮处理过程。
对比例2
与实施例1的制备方法基本相同，不同之处仅在于省略了铸锭的熔炼过程和液氮处理过程。
效果例
将实施例1～4和对比例1～2得到的铜锌铝合金按国家标准加工出冷热疲劳试样(试样尺寸为40mm×20mm×5mm，经线切割方法加工成带有3mm深的V型缺口，缺口的另一端有一个孔，以用来固定试样)，冷热疲劳试验在冷热疲劳试验机上进行，分别在20～300℃、20～400℃和20～500℃三种温度范围下进行冷热疲劳试验，每循环500次取下试样，抛光去除表面氧化膜，测量表面裂纹长度，以0.1mm作为裂纹萌生长度，记下试样裂纹萌生循环次数，所得测试结果分别如图1～3所示；其中，图1为实施例1～4、对比例1和对比例2在20～300℃的冷热疲劳性能测试结果；图2为实施例1～4、对比例1和对比例2在20～400℃的冷热疲劳性能测试结果；图3为实施例1～4、对比例1和对比例2在20～500℃的冷热疲劳性能测试结果。
由图1～3可以看到，经过磁悬浮真空熔炼反复熔炼和液氮深冷处理后，使得铜锌铝合金获得了很好的韧塑性的配合，获得了更好的热疲劳性能。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发 明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (14)

  1. 一种高强韧铜锌铝形状记忆合金的制备方法，其特征在于，包括以下步骤：
    (1)将铜锌铝合金原料进行第一熔炼，得到基础合金液；
    (2)将步骤(1)所述基础合金液与Cu-10RE中间合金混合熔化，得到目标合金熔体；按质量含量计，所述Cu-10RE中间合金的化学成分为：La 7～8％，Y 2～3％，其他稀土元素小于1％，余量为Cu；
    (3)将步骤(2)所述目标合金熔体进行铸造，得到铸锭；
    (4)将步骤(3)所述铸锭进行第二熔炼，得到铸态合金坯；
    (5)将步骤(4)所述铸态合金坯进行保温处理后变形，得到致密化合金坯；
    (6)将步骤(5)所述致密化合金坯依次进行深冷处理和时效处理，得到高强韧铜锌铝形状记忆合金。
  2. 根据权利要求1所述的制备方法，其特征在于，按质量含量计，所述铜锌铝合金原料的化学成分为：Zn 25～26.3％，Al 2.8～3.6％，Mn 0.9～1.1％，Ni 0.8～1.1％，Zr 0.45～0.55％，余量为Cu。
  3. 根据权利要求2所述的制备方法，其特征在于，按质量含量计，所述铜锌铝合金原料的化学成分为：Zn 25.5～25.8％，Al 3.0～3.3％，Mn 1.0～1.1％，Ni 0.9～1.0％，Zr 0.49～0.52％，余量为Cu。
  4. 根据权利要求1～3任意一项所述的制备方法，其特征在于，步骤(1)所述第一熔炼为磁悬浮真空熔炼，所述第一熔炼的温度为1020～1060℃。
  5. 根据权利要求1所述的制备方法，其特征在于，所述Cu-10RE中间合金中稀土元素的含量为基础合金液质量的0.05～0.09％。
  6. 根据权利要求1或5所述的制备方法，其特征在于，步骤(2)所述混合熔化的温度为1020～1040℃。
  7. 根据权利要求1～3任意一项所述的制备方法，其特征在于，步骤(4)所述第二熔炼为磁悬浮真空熔炼，所述第二熔炼的温度为1020～1060℃；所述第二熔炼的次数为2～3次。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤(5)所述保温处理在真空条件下进行，真空度高于10 -2Pa。
  9. 根据权利要求1或8所述的制备方法，其特征在于，所述保温处理的温度为800～810℃，时间为10～12h。
  10. 根据权利要求1所述的制备方法，其特征在于，所述变形的变形量为50～70％。
  11. 根据权利要求1所述的制备方法，其特征在于，所述致密化合金坯的密度为6.73～6.77g/cm 3。
  12. 根据权利要求1所述的制备方法，其特征在于，步骤(6)所述深冷处理为液氮处理；所述深冷处理的时间为3～5h。
  13. 根据权利要求1所述的制备方法，其特征在于，步骤(6)所述时效处理包括依次进行的一级时效处理和二级时效处理，所述一级时效处理的温度为150～170℃，时间为0.3～0.5h；所述二级时效处理的温度为80～90℃，时间为0.5～1h。
  14. 一种高强韧铜锌铝形状记忆合金，其特征在于，采用权利要求1～13任一项所述制备方法制备得到。
PCT/CN2020/139375 2019-12-25 2020-12-25 一种高强韧铜锌铝形状记忆合金及其制备方法 WO2021129802A1 (zh)

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