WO2024098288A1 - Fe-Co-Ni-Cu-Zn高熵合金及其制备方法 - Google Patents

Fe-Co-Ni-Cu-Zn高熵合金及其制备方法 Download PDF

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WO2024098288A1
WO2024098288A1 PCT/CN2022/130894 CN2022130894W WO2024098288A1 WO 2024098288 A1 WO2024098288 A1 WO 2024098288A1 CN 2022130894 W CN2022130894 W CN 2022130894W WO 2024098288 A1 WO2024098288 A1 WO 2024098288A1
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entropy alloy
high entropy
salt
electrolyte
preparing
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French (fr)
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杨良滔
周杰
张翊
刘青
张志林
吴景龙
梁栋
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Shenzhen Institute of Advanced Technology of CAS
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys

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  • the present application relates to the technical field of material preparation, and in particular to a Fe-Co-Ni-Cu-Zn high entropy alloy and a preparation method thereof.
  • High entropy alloy is a solid solution alloy material composed of five or more metal elements in equiatomic or non-equiatomic ratios. Due to the difference in its structure from traditional alloys, high entropy alloys have the following unique effects: high entropy effect, lattice distortion effect, hysteresis diffusion effect and "cocktail effect", which also enables them to obtain many attractive properties, such as mechanical properties, corrosion resistance, unique electromagnetic properties, etc.
  • the preparation methods of high entropy alloys mainly include physical methods such as arc induction melting, thermal spraying, laser cladding, and mechanical die casting.
  • the existing methods have great difficulty in experimental operation, complex processing routes, and limited control effects.
  • the use of electrochemical deposition for the regulation of high entropy alloys is a low-cost, simple-to-operate preparation method. Compared with other control methods, it can regulate the element ratio and chemical composition of HEA on substrates with complex geometric shapes. It is easy to operate, has low requirements for the processing environment, does not require complex equipment and expensive raw materials, and provides great convenience for engineering applications.
  • electrochemical deposition can easily control the elemental composition, organizational morphology, and performance of high entropy alloys by changing deposition parameters (time, temperature, etc.). Therefore, it is possible to regulate the chemical composition of high entropy alloys by adjusting the electrochemical deposition parameters.
  • One of the purposes of the present application is to provide a method for preparing a Fe-Co-Ni-Cu-Zn high entropy alloy, comprising the following steps:
  • electrolyte is prepared, wherein the electrolyte comprises the following components: soluble iron salt, cobalt salt, nickel salt, copper salt, zinc salt, complexing agent, buffer, reducing agent and additional salt;
  • the adjusted electrolyte is electroplated to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition.
  • the step of preparing the electrolyte specifically includes the following steps:
  • the deionized water is heated and maintained at a temperature of 30°C-90°C, and then a complexing agent, a buffer, an additional salt, a soluble iron salt, a cobalt salt, a nickel salt, a copper salt, and a zinc salt are added and stirred until dissolved, and the electrolyte is obtained after aging for 0.5-10 hours.
  • the soluble iron salt includes ferrous sulfate
  • the cobalt salt includes cobalt sulfate
  • the nickel salt includes nickel sulfate
  • the copper salt includes copper sulfate
  • the zinc salt includes zinc sulfate
  • the complexing agent includes citric acid or trisodium citrate
  • the reducing agent includes sodium hypophosphite or ascorbic acid
  • the buffer includes boric acid
  • the additional salt includes potassium chloride.
  • the ferrous sulfate is 5.0-200.0 g/L
  • the cobalt sulfate is 5.0-180.0 g/L
  • the nickel sulfate is 5.0-150 g/L
  • the potassium chloride is 5.0-100.0 g/L
  • the copper sulfate is 0.1-50.0 g/L
  • the zinc sulfate is 0.2-60.0 g/L
  • the trisodium citrate is 1.0-50.0 g/L
  • the sodium hypophosphite is 0.1-20 g/L
  • the citric acid is 10.0-200.0 g/L
  • the boric acid is 2.0-80.0 g/L.
  • the step of adjusting the deposition potential and the deposition temperature of the electrolyte specifically includes the following steps:
  • a strong acid solution is added to the electrolyte, and the electrodeposition potential of the electrolyte is made to range from 0.5 to 3.5 V, and the deposition temperature is made to range from 30 to 80°C.
  • the strong acid solution includes but is not limited to one of a sulfuric acid solution, a hydrochloric acid solution, and a nitric acid solution, and the concentration of the sulfuric acid solution is 0.1-6 mol/L.
  • the step of electroplating the adjusted electrolyte to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition specifically includes the following steps:
  • An electrode rod is used as an anode and a conductive substrate is used as a cathode. Constant potential electroplating is performed for 0.1-50 minutes to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition.
  • the conductive substrate comprises titanium or copper or silver
  • the electrode rod comprises a millstone rod or lead or titanium or platinum.
  • the conductive substrate further comprises the following steps before use:
  • Polishing was performed with sandpaper, followed by ultrasonic treatment for 10-30 minutes, and then soaking in a 0.5-3 mol/L sulfuric acid solution for 0.5-10 hours, followed by washing with pure water and ethanol, and drying.
  • the second purpose of the present application is to provide a Fe-Co-Ni-Cu-Zn high entropy alloy, which is prepared by the preparation method of the Fe-Co-Ni-Cu-Zn high entropy alloy.
  • the ratio of each metal element in the Fe-Co-Ni-Cu-Zn high entropy alloy is between 1% and 50%.
  • the Fe-Co-Ni-Cu-Zn high entropy alloy and its preparation method provided in the present application include preparing an electrolyte, adjusting the deposition potential and deposition temperature of the electrolyte; electroplating the adjusted electrolyte to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition.
  • the Fe-Co-Ni-Cu-Zn high entropy alloy and its preparation method in the present application apply the electrochemical deposition method to the preparation process of the high entropy alloy to prepare a high entropy alloy with co-deposition of metal elements and good magnetic and electrical properties; at the same time, the above-mentioned preparation method is simple to operate, low-cost and low-energy consumption, and can adjust the alloy structure, which is suitable for industrial and large-scale production of high entropy alloys.
  • FIG1 is a flow chart of the steps of a method for preparing a Fe-Co-Ni-Cu-Zn high entropy alloy provided in an embodiment of the present application.
  • Figure 2 is a SEM image of the regulated Fe-Co-Ni-Cu-Zn high entropy alloy provided in Example 1 of the present application.
  • FIG3 is an EDS image of the regulated Fe-Co-Ni-Cu-Zn high entropy alloy provided in Example 1 of the present application.
  • FIG4 is an energy spectrum image of the Fe-Co-Ni-Cu-Zn high entropy alloy after regulation provided in Example 1 of the present application.
  • Figure 5 is a SEM image of the regulated Fe-Co-Ni-Cu-Zn high entropy alloy provided in Example 2 of the present application.
  • Figure 6 is an EDS image of the regulated Fe-Co-Ni-Cu-Zn high entropy alloy provided in Example 2 of the present application.
  • FIG. 7 is an energy spectrum image of the Fe-Co-Ni-Cu-Zn high entropy alloy after regulation provided in Example 2 of the present application.
  • Figure 8 is a SEM image of the regulated Fe-Co-Ni-Cu-Zn high entropy alloy provided in Example 3 of the present application.
  • FIG9 is an EDS image of the regulated Fe-Co-Ni-Cu-Zn high entropy alloy provided in Example 3 of the present application.
  • FIG10 is an energy spectrum image of the Fe-Co-Ni-Cu-Zn high entropy alloy after regulation provided in Example 3 of the present application.
  • first and second are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, a feature defined as “first” or “second” may explicitly or implicitly include one or more of the features. In the description of this application, the meaning of “plurality” is two or more, unless otherwise clearly and specifically defined.
  • Figure 1 is a step flow chart of a method for preparing a Fe-Co-Ni-Cu-Zn high entropy alloy provided in one embodiment of the present application, including the following steps S110 to S130, and the implementation method of each step is described in detail below.
  • Step S110 preparing an electrolyte, wherein the electrolyte includes the following components: soluble iron salt, cobalt salt, nickel salt, copper salt, zinc salt, complexing agent, buffer, reducing agent and additional salt.
  • deionized water is heated and maintained at a temperature of 30°C-90°C, and then a complexing agent, a buffer, an additional salt, a soluble iron salt, a cobalt salt, a nickel salt, a copper salt, and a zinc salt are added and stirred until dissolved. After aging for 0.5-10 hours, the electrolyte is obtained.
  • the soluble iron salt includes ferrous sulfate
  • the cobalt salt includes cobalt sulfate
  • the nickel salt includes nickel sulfate
  • the copper salt includes copper sulfate
  • the zinc salt includes zinc sulfate
  • the chelating agent includes citric acid or trisodium citrate
  • the reducing agent includes sodium hypophosphite or ascorbic acid
  • the buffer includes boric acid
  • the additional salt includes potassium chloride.
  • the ferrous sulfate is 5.0-200.0 g/L
  • the cobalt sulfate is 5.0-180.0 g/L
  • the nickel sulfate is 5.0-150 g/L
  • the potassium chloride is 5.0-100.0 g/L
  • the copper sulfate is 0.1-50.0 g/L
  • the zinc sulfate is 0.2-60.0 g/L
  • the trisodium citrate is 1.0-50.0 g/L
  • the sodium hypophosphite is 0.1-20 g/L
  • the citric acid is 10.0-200.0 g/L
  • the boric acid is 2.0-80.0 g/L.
  • Step S120 adjusting the deposition potential and deposition temperature of the electrolyte.
  • the step of adjusting the deposition potential and deposition temperature of the electrolyte specifically includes the following steps: adding a strong acid solution to the electrolyte, and making the electrodeposition potential range of the electrolyte be 0.5-3.5V and the deposition temperature be 30-80°C.
  • the strong acid solution includes but is not limited to one of a sulfuric acid solution, a hydrochloric acid solution, and a nitric acid solution, and the concentration of the sulfuric acid solution is 0.1-6 mol/L.
  • Step S130 electroplating the adjusted electrolyte to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition.
  • the step of electroplating the adjusted electrolyte to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition specifically includes the following steps:
  • An electrode rod is used as an anode and a conductive substrate is used as a cathode. Constant potential electroplating is performed for 0.1-50 minutes to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition.
  • the conductive substrate includes titanium, copper or silver
  • the electrode rod includes a millstone rod, lead, titanium or platinum.
  • the conductive substrate further comprises the following steps before use:
  • Polishing was performed with sandpaper, followed by ultrasonic treatment for 10-30 minutes, and then soaking in a 0.5-3 mol/L sulfuric acid solution for 0.5-10 hours, followed by washing with pure water and ethanol, and drying.
  • the preparation method of the Fe-Co-Ni-Cu-Zn high entropy alloy provided in the above embodiment of the present application is to prepare an electrolyte, adjust the deposition potential and deposition temperature of the electrolyte, and electroplate the adjusted electrolyte to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with adjustable chemical composition.
  • the above preparation method applies the electrochemical deposition method to the preparation process of the high entropy alloy to prepare a high entropy alloy with co-deposition of metal elements and magnetic and good electrical properties; at the same time, the operation is simple, the cost is reduced, the energy consumption is low, and it is suitable for industrial and large-scale production of high entropy alloys.
  • the present application also provides a Fe-Co-Ni-Cu-Zn high entropy alloy, wherein the ratio of each metal element in the Fe-Co-Ni-Cu-Zn high entropy alloy is between 1% and 50%.
  • the preparation method provided in the above embodiments of the present application is not only applicable to the regulation of the chemical components of high entropy alloys composed of the above five elements, but can also be used to regulate other chemical components of high entropy alloys.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • the method for the chemical composition of FeCoNiCuZn high entropy alloy provided in this embodiment 1 has the following specific process:
  • electrolyte 55 g/L ferrous sulfate, 70 g/L cobalt sulfate, 90 g/L nickel sulfate, 1.5 g/L copper sulfate, 3 g/L zinc sulfate, 105 g/L citric acid, 15 g/L trisodium citrate, 1 g/L sodium hypophosphite, 30 g/L boric acid, and 37 g/L potassium chloride were weighed separately and added into 300 ml deionized water heated to 55 degrees Celsius according to the method of claim 6, stirred until dissolved and aged for 4 hours to obtain an electrolyte.
  • Control conditions The strong acid solution provided in the above embodiment was not added, the deposition potential was -1.5 V, and the temperature was 60° C. for control.
  • Deposition preparation A graphite rod is used as the anode and a titanium sheet is used as the cathode.
  • the titanium sheet is polished with sandpaper, then ultrasonically treated for 10 minutes, soaked in 2 mol/L sulfuric acid for 2 hours, and electroplated at a constant potential for 10 minutes to obtain a Fe-Co-Ni-Cu-Zn high entropy alloy with controlled chemical composition. Scanning electron microscopy was used for observation, as shown in Figures 2, 3, and 4; the high entropy alloy is evenly distributed in a granular form, and the content of Co and Cu elements in the chemical composition is relatively high, specifically Co>Cu>Ni>Fe>Zn;
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • the method for the chemical composition of FeCoNiCuZn high entropy alloy provided in this embodiment 2 has the following specific process:
  • Example 2 The difference between Example 2 and Example 1 is that sulfuric acid provided in the above example is added at a concentration of 3 mol/L, the deposition potential is -1.75 V, the temperature is 55°C, and observation is performed using a scanning electron microscope, as shown in Figures 5, 6, and 7.
  • the high entropy alloy is uniformly distributed in the form of a thin film, and the content of Co and Ni elements in the chemical composition is relatively high, specifically Co>Ni>Cu>Fe>Zn.
  • the regulation of organizational morphology and chemical composition is achieved.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • the method for the chemical composition of FeCoNiCuZn high entropy alloy provided in this embodiment 3 has the following specific process:
  • Example 3 The difference between Example 3 and Example 1 is that sulfuric acid provided in the above example is added, the sulfuric acid concentration is 2 mol/L, the deposition potential is -1.5 V, and the temperature is 55°C, as shown in Figures 8, 9, and 10.
  • the high entropy alloy is evenly distributed in the form of stone-like particles, and the chemical composition has a high content of Co and Ni elements, specifically Ni>Co>Cu>Fe>Zn.
  • the regulation of organizational morphology and chemical composition is achieved.

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Abstract

一种Fe-Co-Ni-Cu-Zn高熵合金及其制备方法，包括配置电解液，对所述电解液的沉积电位及沉积温度进行调节;对调节后的所述电解液进行电镀处理，得到化学成分可调控的 Fe-Co-Ni-Cu-Zn 高熵合金。所述Fe-Co-Ni-Cu-Zn 高熵合金及其制备方法，将电化学沉积方法应用于高熵合金的制备过程，制备出金属元素共沉积，具有磁学和良好电学性能的高熵合金；同时，上述制备方法操作简便，低成本和低能耗可以调控合金组织的方法，适用与高熵合金的工业与规模化生产。

Description

Fe-Co-Ni-Cu-Zn高熵合金及其制备方法 技术领域
本申请涉及材料制备技术领域，特别涉及一种Fe-Co-Ni-Cu-Zn高熵合金及其制备方法。
背景技术
高熵合金是由五种及五种以上的等原子或非等原子比的金属元素组成的固溶体合金材料，高熵合金因其结构与传统合金的差异性，有以下几个独特效应：高熵效应、晶格畸变效应、迟滞扩散效应和“鸡尾酒效应”，也使其获得了许多吸引人的性能，如力学性能、抗腐蚀性能、独特的电磁学性能等。
目前高熵合金制备方法主要包括电弧感应熔炼、热喷涂、激光熔覆、机械压铸等物理方法，现有方法实验操作过程难度大，加工路线复杂，调控效果有限。使用电化学沉积进行高熵合金的调控是一种成本低，操作简单的制备方法，相比于其它调控方法，其可以在复杂几何形状的基底进行调控HEA的元素比例与化学成分，操作简便，加工环境要求低，不需要复杂的设备和昂贵的原料，为工程应用提供了极大的便利。此外，电化学沉积通过改变沉积参数(时间、温度等)，能容易地控制高熵合金的元素组成、组织形貌和性能等。因此，通过电化学沉积参数的调节为调控高熵合金化学成分提供了可能。
但现有方法实验周期长，操作过程难度大，生产成本高，加工路线复杂，加工环境要求高，调控效果有限。
发明内容
鉴于此，有必要针对现有技术中存在的缺陷提供一种易操作且调控高熵合金化学成分较佳的Fe-Co-Ni-Cu-Zn高熵合金及其制备方法。
为解决上述问题，本申请采用下述技术方案：
本申请的目的之一，提供了一种Fe-Co-Ni-Cu-Zn高熵合金的制备方法，包括下述步骤：
配置电解液，所述电解液包括以下组分可溶性铁盐、钴盐、镍盐、铜盐、锌盐、络合剂、缓冲剂、还原剂及附加盐；
对所述电解液的沉积电位及沉积温度进行调节；
对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金。
在其中一些实施例中，在配置电解液的步骤中，具体包括下述步骤：
将去离子水加热并维持温度至30℃-90℃，再加入络合剂、缓冲剂、附加盐、可溶性铁盐、钴盐、镍盐、铜盐、锌盐搅拌至溶解，陈化0.5-10h后，得到所述电解液。
在其中一些实施例中，所述的可溶性铁盐包括硫酸亚铁，所述钴盐包括硫酸钴，所述镍盐包括硫酸镍，所述铜盐包括硫酸铜，所述锌盐包括硫酸锌，所述络合剂包括柠檬酸或柠檬酸三钠，所述还原剂包括次亚磷酸钠或抗坏血酸， 所述缓冲剂包括硼酸，所述附加盐包括氯化钾。
在其中一些实施例中，所述硫酸亚铁为5.0-200.0g/L、所述硫酸钴为5.0-180.0g/L、所述硫酸镍为5.0-150g/L、所述氯化钾为5.0-100.0g/L、所述硫酸铜为0.1-50.0g/L、所述硫酸锌为0.2-60.0g/L、所述柠檬酸三钠为1.0-50.0g/L、所述次亚磷酸钠为0.1-20g/L、所述柠檬酸为10.0-200.0g/L、所述硼酸为2.0-80.0g/L。
在其中一些实施例中，在对所述电解液的沉积电位及沉积温度进行调节的步骤中，具体包括下述步骤：
在所述电解液中加入强酸性溶液，并使得所述电解液的电沉积电位范围为0.5-3.5V，沉积温度为30-80℃。
在其中一些实施例中，所述的强酸性溶液包括但不限于为硫酸溶液、盐酸溶液、硝酸溶液中的一种，所述硫酸溶液的浓度0.1-6mol/L。
在其中一些实施例中，在对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金的步骤中，具体包括下述步骤：
用电极棒为阳极，导电基底作为阴极，使用恒电位电镀0.1-50min，即得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金。
在其中一些实施例中，所述导电基底包括钛或铜或银，所述电极棒包括石磨棒或铅或钛或铂。
在其中一些实施例中，所述导电基底在使用之前还包括下述步骤：
采用砂纸进行抛光处理，再进行超声处理10-30min，然后使用浓度为 0.5-3mol/L硫酸溶液浸泡处理0.5-10h，再依次用纯水、乙醇冲洗，烘干。
本申请的目的之二，提供了一种Fe-Co-Ni-Cu-Zn高熵合金，由所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法制备得到。
在其中一些实施例中，所述的Fe-Co-Ni-Cu-Zn高熵合金各金属元素的比例在1％～50％之间。
本申请采用上述技术方案，其有益效果如下：
本申请提供的Fe-Co-Ni-Cu-Zn高熵合金及其制备方法，包括配置电解液，对所述电解液的沉积电位及沉积温度进行调节；对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金，本申请上述Fe-Co-Ni-Cu-Zn高熵合金及其制备方法，将电化学沉积方法应用于高熵合金的制备过程，制备出金属元素共沉积，具有磁学和良好电学性能的高熵合金；同时，上述制备方法操作简便，低成本和低能耗可以调控合金组织的方法，适用与高熵合金的工业与规模化生产。
附图说明
为了更清楚地说明本申请实施例的技术方案，下面将对本申请实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面所描述的附图仅仅是本申请的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1为本申请实施例提供的Fe-Co-Ni-Cu-Zn高熵合金的制备方法的步骤流程图。
图2为申请本实施例1提供的调控后Fe-Co-Ni-Cu-Zn高熵合金SEM图像。
图3为申请本实施例1提供的调控后Fe-Co-Ni-Cu-Zn高熵合金EDS图像。
图4为申请本实施例1提供的调控后Fe-Co-Ni-Cu-Zn高熵合金能谱图像。
图5为申请本实施例2提供的调控后Fe-Co-Ni-Cu-Zn高熵合金SEM图像。
图6为申请本实施例2提供的调控后Fe-Co-Ni-Cu-Zn高熵合金EDS图像。
图7为申请本实施例2提供的调控后Fe-Co-Ni-Cu-Zn高熵合金能谱图像。
图8为申请本实施例3提供的调控后Fe-Co-Ni-Cu-Zn高熵合金SEM图像。
图9为申请本实施例3提供的调控后Fe-Co-Ni-Cu-Zn高熵合金EDS图像。
图10为申请本实施例3提供的调控后Fe-Co-Ni-Cu-Zn高熵合金能谱图像。
具体实施方式
下面详细描述本申请的实施例，所述实施例的示例在附图中示出，其中自始至终相同或类似的标号表示相同或类似的元件或具有相同或类似功能的元件。下面通过参考附图描述的实施例是示例性的，旨在用于解释本申请，而不能理解为对本申请的限制。
在本申请的描述中，需要理解的是，术语“上”、“下”、“水平”、“内”、“外”等指示的方位或位置关系为基于附图所示的方位或位置关系，仅是为了便于描述本申请和简化描述，而不是指示或暗示所指的装置或元件必须具有特定的方 位、以特定的方位构造和操作，因此不能理解为对本申请的限制。
此外，术语“第一”、“第二”仅用于描述目的，而不能理解为指示或暗示相对重要性或者隐含指明所指示的技术特征的数量。由此，限定有“第一”、“第二”的特征可以明示或者隐含地包括一个或者更多个该特征。在本申请的描述中，“多个”的含义是两个或两个以上，除非另有明确具体的限定。
为了使本申请的目的、技术方案及优点更加清楚明白，以下结合附图及实施例，对本申请进行进一步详细说明。
请参阅图1，本申请一实施例提供的一种Fe-Co-Ni-Cu-Zn高熵合金的制备方法的步骤流程图，包括下述步骤S110至步骤S130，以下详细说明各个步骤的实现方式。
步骤S110：配置电解液，所述电解液包括以下组分可溶性铁盐、钴盐、镍盐、铜盐、锌盐、络合剂、缓冲剂、还原剂及附加盐。
在本实施例中，将去离子水加热并维持温度至30℃-90℃，再加入络合剂、缓冲剂、附加盐、可溶性铁盐、钴盐、镍盐、铜盐、锌盐搅拌至溶解，陈化0.5-10h后，得到所述电解液。
在本实施例中，所述的可溶性铁盐包括硫酸亚铁，所述钴盐包括硫酸钴，所述镍盐包括硫酸镍，所述铜盐包括硫酸铜，所述锌盐包括硫酸锌，所述络合剂包括柠檬酸或柠檬酸三钠，所述还原剂包括次亚磷酸钠或抗坏血酸，所述缓冲剂包括硼酸，所述附加盐包括氯化钾。
在本实施例中，所述硫酸亚铁为5.0-200.0g/L、所述硫酸钴为5.0-180.0g/L、 所述硫酸镍为5.0-150g/L、所述氯化钾为5.0-100.0g/L、所述硫酸铜为0.1-50.0g/L、所述硫酸锌为0.2-60.0g/L、所述柠檬酸三钠为1.0-50.0g/L、所述次亚磷酸钠为0.1-20g/L、所述柠檬酸为10.0-200.0g/L、所述硼酸为2.0-80.0g/L。
步骤S120：对所述电解液的沉积电位及沉积温度进行调节。
在本实施例中，在对所述电解液的沉积电位及沉积温度进行调节的步骤中，具体包括下述步骤：在所述电解液中加入强酸性溶液，并使得所述电解液的电沉积电位范围为0.5-3.5V，沉积温度为30-80℃。
在本实施例中，所述的强酸性溶液包括但不限于为硫酸溶液、盐酸溶液、硝酸溶液中的一种，所述硫酸溶液的浓度0.1-6mol/L。
步骤S130：对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金。
在本实施例中，在对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金的步骤中，具体包括下述步骤：
用电极棒为阳极，导电基底作为阴极，使用恒电位电镀0.1-50min，即得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金。
在本实施例中，所述导电基底包括钛或铜或银，所述电极棒包括石磨棒或铅或钛或铂。
在本实施例中，所述导电基底在使用之前还包括下述步骤：
采用砂纸进行抛光处理，再进行超声处理10-30min，然后使用浓度为 0.5-3mol/L硫酸溶液浸泡处理0.5-10h，再依次用纯水、乙醇冲洗，烘干。
本申请上述实施例提供的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，通过配置电解液，对所述电解液的沉积电位及沉积温度进行调节，对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金，上述制备方法，将电化学沉积方法应用于高熵合金的制备过程，制备出金属元素共沉积，具有磁学和良好电学性能的高熵合金；同时，操作简便，成本降低、低能耗，适用与高熵合金的工业与规模化生产。
本申请还提供了一种Fe-Co-Ni-Cu-Zn高熵合金，所述的Fe-Co-Ni-Cu-Zn高熵合金各金属元素的比例在1％～50％之间。
可以理解，本申请上述实施例提供的制备方法不仅适用于上述5种元素组成的高熵合金化学组分调控，还可以对其他的高熵合金化学组分进行调控。
以下结合具体实施例对本申请上述技术方案进行详细说明。
实施例1：
本实施例1提供的FeCoNiCuZn高熵合金化学成分的方法，具体过程如下：
电解液的制备：分别称取55g/L硫酸亚铁、70g/L硫酸钴、90g/L硫酸镍、1.5g/L硫酸铜、3g/L硫酸锌，105g/L柠檬酸、15g/L柠檬酸三钠，1g/L次亚磷酸钠，30g/L硼酸，37g/L氯化钾按照权利要求6所述方法添加进加热至55摄氏度的300ml去离子水中，搅拌至溶解并陈化4h，得到电解液。
调控条件控制：未添加上述实施例提供的强酸性溶液，沉积电位为-1.5V， 温度60℃进行调控。
沉积制备：采用石墨棒为阳极，钛片作为阴极，钛片使用砂纸进行抛光处理，再超声处理10min，使用浓度为2mol/L硫酸浸泡处理2h，使用恒电位进行电镀10min，即得到化学成分调控好的Fe-Co-Ni-Cu-Zn高熵合金。使用扫描电镜进行观测，如图2、3、4所示；该高熵合金以颗粒型形态均匀分布，化学组成成分中Co、Cu元素含量较高，具体为Co>Cu>Ni>Fe>Zn；
实施例2：
本实施例2提供的FeCoNiCuZn高熵合金化学成分的方法，具体过程如下：
本实施例2与实施例1，不同之处在于，添加上述实施例提供的硫酸，浓度为3mol/L，沉积电位为-1.75V，温度为55℃，使用扫描电镜进行观测，如图5、6、7所示。该高熵合金以薄膜形态均匀分布，化学组成成分中Co、Ni元素含量较高，具体为Co>Ni>Cu>Fe>Zn。与实施例1、3相比较实现了组织形态和化学成分上的调控。
实施例3：
本实施例3提供的FeCoNiCuZn高熵合金化学成分的方法，具体过程如下：
本实施例3与实施例1，不同之处在于，添加上述实施例提供的硫酸，硫酸浓度为2mol/L，沉积电位为-1.5V，温度为55℃，如图8、9、10所示。该高熵合金以石状颗粒形态均匀分布，化学组成成分Co、Ni元素含量较高，具体为Ni>Co>Cu>Fe>Zn。与实施例1、2相比较实现了组织形态和化学成分上的调控。
可以理解，以上所述实施例的各技术特征可以进行任意的组合，为使描述简洁，未对上述实施例中的各个技术特征所有可能的组合都进行描述，然而，只要这些技术特征的组合不存在矛盾，都应当认为是本说明书记载的范围。
以上仅为本申请的较佳实施例而已，仅具体描述了本申请的技术原理，这些描述只是为了解释本申请的原理，不能以任何方式解释为对本申请保护范围的限制。基于此处解释，凡在本申请的精神和原则之内所作的任何修改、等同替换和改进，及本领域的技术人员不需要付出创造性的劳动即可联想到本申请的其他具体实施方式，均应包含在本申请的保护范围之内。

Claims (11)

  1. 一种Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，包括下述步骤：
    配置电解液，所述电解液包括以下组分可溶性铁盐、钴盐、镍盐、铜盐、锌盐、络合剂、缓冲剂、还原剂及附加盐；
    对所述电解液的沉积电位及沉积温度进行调节；
    对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金。
  2. 如权利要求1所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，在配置电解液的步骤中，具体包括下述步骤：
    将去离子水加热并维持温度至30℃-90℃，再加入络合剂、缓冲剂、附加盐、可溶性铁盐、钴盐、镍盐、铜盐、锌盐搅拌至溶解，陈化0.5-10h后，得到所述电解液。
  3. 如权利要求1或2所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，所述的可溶性铁盐包括硫酸亚铁，所述钴盐包括硫酸钴，所述镍盐包括硫酸镍，所述铜盐包括硫酸铜，所述锌盐包括硫酸锌，所述络合剂包括柠檬酸或柠檬酸三钠，所述还原剂包括次亚磷酸钠或抗坏血酸，所述缓冲剂包括硼酸，所述附加盐包括氯化钾。
  4. 如权利要求3所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，所述硫酸亚铁为5.0-200.0g/L、所述硫酸钴为5.0-180.0g/L、所述硫酸镍为 5.0-150g/L、所述氯化钾为5.0-100.0g/L、所述硫酸铜为0.1-50.0g/L、所述硫酸锌为0.2-60.0g/L、所述柠檬酸三钠为1.0-50.0g/L、所述次亚磷酸钠为0.1-20g/L、所述柠檬酸为10.0-200.0g/L、所述硼酸为2.0-80.0g/L。
  5. 如权利要求1所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，在对所述电解液的沉积电位及沉积温度进行调节的步骤中，具体包括下述步骤：
    在所述电解液中加入强酸性溶液，并使得所述电解液的电沉积电位范围为0.5-3.5V，沉积温度为30-80℃。
  6. 如权利要求5所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，所述的强酸性溶液包括但不限于为硫酸溶液、盐酸溶液、硝酸溶液中的一种，所述硫酸溶液的浓度0.1-6mol/L。
  7. 如权利要求1所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，在对调节后的所述电解液进行电镀处理，得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金的步骤中，具体包括下述步骤：
    用电极棒为阳极，导电基底作为阴极，使用恒电位电镀0.1-50min，即得到化学成分可调控的Fe-Co-Ni-Cu-Zn高熵合金。
  8. 如权利要求7所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，所述导电基底包括钛或铜或银，所述电极棒包括石磨棒或铅或钛或铂。
  9. 如权利要求8所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法，其特征在于，所述导电基底在使用之前还包括下述步骤：
    采用砂纸进行抛光处理，再进行超声处理10-30min，然后使用浓度为0.5-3mol/L硫酸溶液浸泡处理0.5-10h，再依次用纯水、乙醇冲洗，烘干。
  10. 一种Fe-Co-Ni-Cu-Zn高熵合金，其特征在于，由权利要求1至9任一项所述的Fe-Co-Ni-Cu-Zn高熵合金的制备方法制备得到。
  11. 如权利要求10所述的Fe-Co-Ni-Cu-Zn高熵合金，其特征在于，所述的Fe-Co-Ni-Cu-Zn高熵合金各金属元素的比例在1％～50％之间。
PCT/CN2022/130894 2022-11-09 2022-11-09 Fe-Co-Ni-Cu-Zn高熵合金及其制备方法 Ceased WO2024098288A1 (zh)

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