CN116732406A - Iron-nickel-cobalt-chromium-boron bulk eutectic high-entropy alloy with network-like dual-phase structure - Google Patents
Iron-nickel-cobalt-chromium-boron bulk eutectic high-entropy alloy with network-like dual-phase structure Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 30
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- 238000003723 Smelting Methods 0.000 claims description 51
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- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical group O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 28
- 229910052786 argon Inorganic materials 0.000 claims description 27
- 238000004140 cleaning Methods 0.000 claims description 26
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- 229910052804 chromium Inorganic materials 0.000 claims description 25
- 239000011521 glass Substances 0.000 claims description 25
- 229910052742 iron Inorganic materials 0.000 claims description 24
- 229910052759 nickel Inorganic materials 0.000 claims description 24
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- 239000007769 metal material Substances 0.000 claims description 6
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- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 4
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Abstract
本发明公开了一种具有网络状双相结构的铁镍钴铬硼系大块共晶高熵合金，所述高熵合金组分以原子百分比表示为[(FeNiCo)1‑yCry]1‑ xBx，0.1≤x≤0.17，0.12≤y≤0.18。本发明通过高熵合金组分设计，采用纯化深过冷的方法综合调控结构，获得具有均匀网络状结构、超过厘米级且具有优异力学性能的铁镍钴铬硼系共晶高熵合金。
The invention discloses an iron-nickel-cobalt-chromium-boron system bulk eutectic high-entropy alloy with a network-like dual-phase structure. The high-entropy alloy composition is expressed in atomic percentage as [(FeNiCo) 1-y Cr y ] 1 ‑ x B x , 0.1≤x≤0.17, 0.12≤y≤0.18. The present invention obtains an iron-nickel-cobalt-chromium-boron system eutectic high-entropy alloy with a uniform network structure, exceeding centimeter level and excellent mechanical properties through the design of high-entropy alloy components and the method of purification and deep supercooling to comprehensively regulate the structure.
Description
技术领域Technical field
本发明属于金属材料领域，具体涉及一种兼具高强度和高塑性且具有网络状双相结构的FeCoNiCrB系共晶高熵合金及其制备方法。The invention belongs to the field of metal materials, and specifically relates to a FeCoNiCrB system eutectic high-entropy alloy with both high strength and high plasticity and a network-like dual-phase structure and a preparation method thereof.
背景技术Background technique
传统合金的设计理念是以1~2种合金元素作为主要元素，添加（或不添加）其他少量一种（或多种）元素作为合金元素来形成合金，而高熵合金突破了传统合金主体元素超过合金成分50%的设计理念。一般至少由五种元素组成，其中每个主元含量都不超过35%，但不低于5%，多种合金元素均作为主要元素形成多主元高熵合金。高熵合金被称为最近几十年来合金化理论三大突破之一，作为一种新型的结构与工程材料，在航空航天、军用、民用仪器仪表等领域具有广泛的应用前景。The design concept of traditional alloys is to use 1 to 2 alloying elements as the main elements, and add (or not add) a small amount of one (or more) other elements as alloying elements to form an alloy. High-entropy alloys break through the main elements of traditional alloys. Design concept with more than 50% alloy composition. It is generally composed of at least five elements, with the content of each principal element not exceeding 35% but not less than 5%. Various alloying elements are used as main elements to form multi-principal high-entropy alloys. High-entropy alloys are known as one of the three major breakthroughs in alloying theory in recent decades. As a new structural and engineering material, they have broad application prospects in aerospace, military, civilian instrumentation and other fields.
然而强度/塑性匹配性差的问题普遍存在，这严重阻碍了高熵合金的实际工程应用。一般而言，面心立方（FCC）结构高熵合金具有优异的塑性与加工硬化能力，但是屈服强度低，如FeCoNiCrMn高熵合金的拉伸塑性可达60%，但其抗拉强度却低于500 MPa；而体心立方（BCC）结构高熵合金的强度更高，但塑性差，如AlCoCrFeNiTi0.5高熵合金的压缩强度高达2500 MPa，但几乎没有拉伸塑性。调控组织结构是调控金属性能的重要途径，高强度和高韧性的多相复合结构是当前研究的热点。研究表明，制备双相高熵合金是实现高强度与高塑性匹配的有效途径。采用感应熔炼法可以制备出AlCoCrFeNix大块片层共晶高熵合金，其强塑性较好，断裂塑性可达21%，屈服强度可达600 MPa。但加入非金属元素获得具有均匀网络状结构的大块共晶高熵合金的制备方法仍然未见报道。However, the problem of poor strength/plasticity matching is widespread, which seriously hinders the practical engineering applications of high-entropy alloys. Generally speaking, face-centered cubic (FCC) structure high-entropy alloys have excellent plasticity and work-hardening capabilities, but low yield strength. For example, the tensile plasticity of FeCoNiCrMn high-entropy alloys can reach 60%, but their tensile strength is lower than 500 MPa; while the body-centered cubic (BCC) structure high-entropy alloy has higher strength, but poor plasticity. For example, the compressive strength of AlCoCrFeNiTi 0.5 high-entropy alloy is as high as 2500 MPa, but has almost no tensile plasticity. Controlling the organizational structure is an important way to control the properties of metals, and multiphase composite structures with high strength and toughness are a hot topic in current research. Research shows that the preparation of dual-phase high-entropy alloys is an effective way to achieve matching of high strength and high plasticity. The induction melting method can be used to prepare AlCoCrFeNi However, the preparation method of adding non-metallic elements to obtain bulk eutectic high-entropy alloys with a uniform network structure has not yet been reported.
近年来，快速凝固技术和深冷技术等非平衡凝固技术也被用于合金的结构控制。非平衡凝固技术可以细化晶粒尺寸，与常规凝固相比，非平衡凝固技术过程中形成的树枝状晶粒经历了复杂的变化过程，原有的树枝状形态往往被破坏，导致在特定的过冷区域下实现晶粒细化的发生。其中，熔融包覆法可以有效去除合金熔体中的杂质，促进均匀形核，并获得大的过冷度。如利用氧化硼熔融包覆法可成功制备超细晶均匀网络结构的三元Fe79.5B6.5C14合金，具有良好的强度（达2 GPa）和压缩塑性（17%），但是样品尺寸较小，仅能在毫米级范围获得过冷度，无法实现具有均匀网络状结构的超过厘米级样品。In recent years, non-equilibrium solidification technologies such as rapid solidification technology and cryogenic technology have also been used for structural control of alloys. Non-equilibrium solidification technology can refine the grain size. Compared with conventional solidification, the dendritic grains formed during non-equilibrium solidification technology have undergone a complex change process. The original dendritic morphology is often destroyed, resulting in specific Grain refinement occurs in the supercooling region. Among them, the melt coating method can effectively remove impurities in the alloy melt, promote uniform nucleation, and obtain a large degree of supercooling. For example, the boron oxide melt coating method can be used to successfully prepare a ternary Fe 79.5 B 6.5 C 14 alloy with an ultra-fine grained uniform network structure, which has good strength (up to 2 GPa) and compression plasticity (17%), but the sample size is small. , supercooling can only be obtained in the millimeter range, and samples exceeding centimeter scale with a uniform network structure cannot be achieved.
发明内容Contents of the invention
本发明通过高熵合金组分设计，采用纯化过冷的方法综合调控双相（面心立方相加四方相）网状结构，获得具有高强度、高塑性的FeNiCoCrB系共晶高熵合金。By designing high-entropy alloy components and using purification and supercooling methods, the present invention comprehensively regulates the two-phase (face-centered cubic phase plus tetragonal phase) network structure to obtain a FeNiCoCrB-based eutectic high-entropy alloy with high strength and high plasticity.
为实现上述目的，本发明采取技术方案具体如下：In order to achieve the above objects, the technical solutions adopted by the present invention are as follows:
一种高强高塑共晶高熵合金及其制备方法，所述高熵合金组分以原子百分比表示为[(FeNiCo)1-yCry]1-xBx，0.1≤x≤0.17，0.12≤y≤0.18，由如下步骤制备：A high-strength, high-plastic eutectic high-entropy alloy and its preparation method. The high-entropy alloy composition is expressed in atomic percentage as [(FeNiCo) 1-y Cr y ] 1-x B x , 0.1≤x≤0.17, 0.12 ≤y≤0.18, prepared by the following steps:
步骤1，根据高熵合金成分配置原材料；Step 1: Configure raw materials according to the high-entropy alloy composition;
步骤2，熔炼制备合金锭；Step 2, smelting to prepare alloy ingots;
步骤3，熔融包覆法制备大过冷度共晶高熵合金Step 3. Preparation of large supercooling eutectic high-entropy alloy by melt coating method
将包覆剂放入干净的玻璃管中加热，保证该包覆剂具有较好的流动性；将步骤2得到的合金锭放入熔融的包覆剂中，继续加热至合金液相线温度以上，保温，保温过程中持续抽气；保温结束后将玻璃管取出并充入少量氩气，得到具有大过冷度共晶高熵合金。Put the coating agent into a clean glass tube and heat it to ensure that the coating agent has good fluidity; put the alloy ingot obtained in step 2 into the molten coating agent and continue to heat it until it is above the alloy liquidus temperature. , heat preservation, continuous air extraction during the heat preservation process; after the heat preservation is completed, the glass tube is taken out and filled with a small amount of argon gas to obtain a eutectic high-entropy alloy with a large degree of supercooling.
优选地，步骤1中，原材料中金属材料的纯度控制在99.0-99.99%，硼的纯度控制在99.0-99.99%。Preferably, in step 1, the purity of the metal material in the raw material is controlled at 99.0-99.99%, and the purity of boron is controlled at 99.0-99.99%.
优选地，步骤1中，配置原材料前对金属材料进行预处理，其过程为：将Fe、Ni、Co、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，超声清洗干净，取出后吹干残留清洗溶剂得到所需金属材料。Preferably, in step 1, the metal material is pretreated before configuring the raw materials. The process is as follows: remove the surface oxide scale from Fe, Ni, Co, and Cr, then put it into a container and add a cleaning solvent, clean it ultrasonically, and take it out. Blow dry the residual cleaning solvent to obtain the required metal material.
优选地，步骤2中，采用高真空感应熔炼法制备初级合金锭，其过程为：将原材料放入纯净的石英管后，移入高真空感应电弧熔炼炉中；然后反复充、抽高纯氩气，降低炉内不利气体含量，在一定电流下进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；Preferably, in step 2, a high vacuum induction melting method is used to prepare primary alloy ingots. The process is as follows: after placing the raw materials into a pure quartz tube, move them into a high vacuum induction arc melting furnace; and then repeatedly filling and pumping high-purity argon gas. , reduce the unfavorable gas content in the furnace, smelt under a certain current, wait until the metal is melted into liquid, and the B element completely enters the melt before stopping the smelting. After the smelting is completed, the primary alloy ingot is obtained;
采用高真空电弧熔炼制备合金锭，其过程为：将初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充、抽高纯氩气，降低炉腔内不利气体含量，对该合金锭进行均匀化电弧熔炼，得到合金锭。High-vacuum arc melting is used to prepare alloy ingots. The process is as follows: put the primary alloy ingots into a high-vacuum arc melting furnace, evacuate, and then repeatedly fill and pump high-purity argon gas to reduce the unfavorable gas content in the furnace cavity. Carry out homogenized arc melting to obtain alloy ingots.
优选地，步骤3中，包覆剂采用三氧化二硼，Preferably, in step 3, the coating agent is diboron trioxide,
优选地，步骤3中，将包覆剂放入干净的玻璃管中加热至900℃。Preferably, in step 3, the coating agent is put into a clean glass tube and heated to 900°C.
优选地，步骤3中，继续加热至1250℃以上，保温2小时。Preferably, in step 3, continue to heat to above 1250°C and keep warm for 2 hours.
与现有技术相比，本发明具有如下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
1、本发明通过多主元素成分（≥5）优化设计，利用高熵效应，采用氧化硼熔融包覆法，极大地降低了异质形核的影响，实现大体积液态合金的深过冷，过冷度可达400摄氏度，同时冷却过程中合金结晶释放潜热发生“再辉”现象，使枝晶重熔，达到细化合金晶粒尺寸的作用，制备出高强高韧的共晶高熵合金。1. By optimizing the design of multiple principal element components (≥5), the present invention utilizes the high entropy effect and adopts the boron oxide melt coating method to greatly reduce the impact of heterogeneous nucleation and achieve deep supercooling of large-volume liquid alloys. The degree of supercooling can reach 400 degrees Celsius. At the same time, the latent heat released by the alloy crystallization during the cooling process causes a "re-glow" phenomenon, which causes the dendrites to remelt, thereby refining the alloy grain size and preparing a high-strength and high-toughness eutectic high-entropy alloy. .
2、本发明的共晶高熵合金将塑性优良的面心立方相与四方结构的硼化物强化相结合，具有均匀网络结构，相比于目前报道的大部分片层结构的高熵合金，该结构更有利于高强度与高塑性匹配。2. The eutectic high-entropy alloy of the present invention combines the face-centered cubic phase with excellent plasticity and the boride reinforcement of the tetragonal structure, and has a uniform network structure. Compared with most of the high-entropy alloys with lamellar structures reported so far, the eutectic high-entropy alloy has The structure is more conducive to matching high strength and high plasticity.
3、本发明的共晶高熵合金，可通过成分调控强塑性：3. The eutectic high-entropy alloy of the present invention can control strong plasticity through composition:
（1）通过调整Cr的含量，得到如下性能共晶高熵合金，Cr18B17具有1248 MPa的屈服强度，1519 MPa的断裂强度，压缩塑性为16.2%； Cr15B17屈服强度增加至1332 MPa，断裂强度1902 MPa，压缩塑性为25%；Cr14B17屈服强度继续1384 MPa，断裂强度为1639 MPa，压缩塑性2.9%；Cr12B17屈服强度为1190 MPa，断裂强度为1453 MPa，压缩塑性3%。(1) By adjusting the Cr content, the following performance eutectic high-entropy alloy is obtained. Cr18B17 has a yield strength of 1248 MPa, a fracture strength of 1519 MPa, and a compression plasticity of 16.2%; Cr15B17 yield strength increases to 1332 MPa, and the fracture strength is 1902 MPa. , the compression plasticity is 25%; the yield strength of Cr14B17 continues to be 1384 MPa, the fracture strength is 1639 MPa, and the compression plasticity is 2.9%; the yield strength of Cr12B17 is 1190 MPa, the fracture strength is 1453 MPa, and the compression plasticity is 3%.
（2）通过调整B含量，获得如下性能共晶高熵合金：Cr15B16屈服强度为1247 MPa，断裂强度为1704 MPa，压缩塑性为19.2%，Cr15B15屈服强度为1159 MPa，断裂强度为2254MPa，压缩塑性为55%以上；Cr15B14屈服强度为1330 MPa，由于压缩过程中高径比持续降低，压缩塑性超过80%；Cr15B13屈服强度为1248 MPa，压缩过程中高径比持续降低，压缩塑性超过80%；Cr15B12屈服强度为1235 MPa，压缩过程中高径比持续降低，压缩塑性超过80%，经过轧制退火处理后拉伸塑性超过12%，拉伸断裂强度超过600 MPa；Cr15B10屈服强度为1132MPa，压缩过程中高径比持续降低，压缩塑性超过80%。(2) By adjusting the B content, the following properties of the eutectic high-entropy alloy are obtained: Cr15B16 yield strength is 1247 MPa, fracture strength is 1704 MPa, compression plasticity is 19.2%, Cr15B15 yield strength is 1159 MPa, fracture strength is 2254MPa, compression plasticity is more than 55%; Cr15B14 yield strength is 1330 MPa, due to the continuous reduction of the aspect ratio during the compression process, the compression plasticity exceeds 80%; Cr15B13 yield strength is 1248 MPa, the aspect ratio continues to decrease during the compression process, the compression plasticity exceeds 80%; Cr15B12 yield The strength is 1235 MPa, the aspect ratio continues to decrease during compression, the compression plasticity exceeds 80%, the tensile plasticity exceeds 12% after rolling annealing, and the tensile fracture strength exceeds 600 MPa; the yield strength of Cr15B10 is 1132MPa, and the aspect ratio during compression exceeds 80%. The ratio continues to decrease, and the compression plasticity exceeds 80%.
4、 本发明所述合金锭制备方法及玻璃熔融包覆法，可克服现有技术只能制备小样品的局限性，可以制备一百克以上大样品，样品尺寸可达到厘米级，为未来该方法和该高熵合金工业化应用提供了良好基础。4. The alloy ingot preparation method and the glass melt coating method of the present invention can overcome the limitation that the existing technology can only prepare small samples, and can prepare large samples of more than one hundred grams, and the sample size can reach centimeter level, which provides a good foundation for the future. This method provides a good foundation for the industrial application of this high-entropy alloy.
5、在合金设计过程中充分考虑了Cr、Co等元素的耐氧化、耐腐蚀性能，进一步提高了合金的综合性能。5. In the alloy design process, the oxidation resistance and corrosion resistance of elements such as Cr and Co are fully considered, further improving the overall performance of the alloy.
附图说明Description of drawings
图1是本发明所述玻璃熔融包覆法制备过程中大块Cr15B15共晶高熵合金的“再辉”过程及样品实物图。Figure 1 is a "re-glow" process of a large piece of Cr15B15 eutectic high-entropy alloy during the preparation process of the glass melt coating method of the present invention and a picture of the actual sample.
图2是本发明所述的具有“再辉”现象的FeNiCoCrB系共晶高熵合金的扫描电镜照片，其中（a）（c）为Cr15B12和（b）（d）为Cr15B15共晶高熵合金。Figure 2 is a scanning electron microscope photo of the FeNiCoCrB system eutectic high-entropy alloy with "re-glow" phenomenon according to the present invention, in which (a) (c) is Cr15B12 and (b) (d) is Cr15B15 eutectic high-entropy alloy. .
图3是本发明所述的具有“再辉”的FeNiCoCrB系共晶高熵合金同步辐射图谱，其中（a）为Cr15B12和（b）为Cr15B15共晶高熵合金。Figure 3 is the synchrotron radiation spectrum of the FeNiCoCrB system eutectic high-entropy alloy with "re-glow" according to the present invention, in which (a) is Cr15B12 and (b) is Cr15B15 eutectic high-entropy alloy.
图4 是共晶高熵合金[(FeNiCo)0.85Cr0.15]0.85B0.15合金锭压缩力学性能曲线Figure 4 is the compression mechanical properties curve of eutectic high-entropy alloy [(FeNiCo) 0.85 Cr 0.15 ] 0.85 B 0.15 alloy ingot
图5 是本发明所述的具有“再辉”的FeNiCoCrB系共晶高熵合金压缩应力应变曲线。Figure 5 is the compressive stress-strain curve of the FeNiCoCrB eutectic high-entropy alloy with "re-glow" according to the present invention.
图6 是本发明所述的具有“再辉”的FeNiCoCrB系共晶高熵合金样品压缩应力应变曲线。Figure 6 is the compressive stress strain curve of the FeNiCoCrB system eutectic high-entropy alloy sample with "re-glow" according to the present invention.
图7 是本发明所述室温轧制950℃退火后的FeNiCoCrB系共晶高熵合金样品拉伸应力应变曲线。Figure 7 is the tensile stress strain curve of the FeNiCoCrB eutectic high-entropy alloy sample after room temperature rolling and annealing at 950°C according to the present invention.
具体实施方式Detailed ways
以下通过附图以及具体实施方式对本发明内容进行详细描述，以使本领域内的技术人员能够更好的理解并实施本发明。以下所举实例不能作为对本发明的限定。The following describes the present invention in detail through the drawings and specific embodiments, so that those skilled in the art can better understand and implement the present invention. The following examples are not intended to limit the invention.
含有非金属元素的共晶高熵合金，所设计成分对应的熔体往往含有丰富的局域有序结构，在冷却过程中有助于阻碍结晶过程，从而更易于获得大的过冷度。基于高熵效应设计合理的共晶高熵合金成分，应用熔融包覆深过冷技术，有助于突破样品尺寸限制，使高熵合金在超过厘米量级获得大过冷度，制备出晶粒细化、网络状组织结构均匀，综合力学性能优异的高熵合金，进而满足人们对材料高强度、高韧性的需求。For eutectic high-entropy alloys containing non-metallic elements, the melt corresponding to the designed composition often contains rich local ordered structures, which helps to hinder the crystallization process during the cooling process, making it easier to obtain a large degree of supercooling. Reasonable design of eutectic high-entropy alloy components based on the high-entropy effect and application of melt-coating deep supercooling technology can help break through sample size limitations, enable high-entropy alloys to obtain large undercooling on the order of more than centimeters, and prepare grains It is a high-entropy alloy with a refined and uniform network structure and excellent comprehensive mechanical properties, thereby meeting people's demand for high strength and high toughness materials.
本发明采用熔融包覆深过冷技术即熔融玻璃净化法，一方面，通过熔融玻璃的界面化学作用以及高粘度所带来吸附作用，吸附熔体中所存在的杂质，使得中的异质核心转移到了熔融玻璃中，从而大大的降低了异质形核的作用；另一方面，熔融玻璃包裹在金属表面，不仅可以避免熔融的金属接触试管内壁产生异质形核，还可以缓冲外界随机振动进而减少其对结晶过程的干扰，同时也起到防止金属氧化的作用。优选地，可以使用三氧化二硼作为净化剂。利用以下步骤的制备方法获得具有大过冷度的共晶高熵合金。The present invention adopts the melt coating deep supercooling technology, that is, the molten glass purification method. On the one hand, through the interfacial chemical action of the molten glass and the adsorption effect brought by the high viscosity, the impurities present in the melt are adsorbed, making the heterogeneous core in the It is transferred to the molten glass, thereby greatly reducing the effect of heterogeneous nucleation; on the other hand, the molten glass is wrapped on the metal surface, which not only prevents the molten metal from contacting the inner wall of the test tube to generate heterogeneous nucleation, but also buffers random external vibrations. This reduces its interference with the crystallization process and also prevents metal oxidation. Preferably, diboron trioxide can be used as a purifying agent. The preparation method of the following steps is used to obtain a eutectic high-entropy alloy with a large degree of supercooling.
本发明所述的一种高强高塑共晶高熵合金，所述高熵合金组分以原子百分比表示为[(FeNiCo)1-yCry]1-xBx，0.1≤x≤0.17，0.12≤y≤0.18，为方便描述，后续将不同元素比例高熵合金基于x和y值简称称为CryBx，如将x=0.15，y=0.15简称为Cr15B15共晶高熵合金，x=0.12，y=0.15称为Cr15B12共晶高熵合金。The present invention is a high-strength, high-plastic eutectic high-entropy alloy. The high-entropy alloy composition is expressed in atomic percentage as [(FeNiCo) 1-y Cr y ] 1-x B x , 0.1≤x≤0.17, 0.12≤y≤0.18. For the convenience of description, the high-entropy alloys with different element ratios will be referred to as CryBx based on the x and y values. For example, x=0.15, y=0.15 will be referred to as Cr15B15 eutectic high-entropy alloy, x=0.12, y=0.15 is called Cr15B12 eutectic high-entropy alloy.
实施例1Example 1
一种共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.85B0.15，其中各元素的比例为原子百分比A eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.85 B 0.15 , in which the proportion of each element is atomic percentage.
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤（1）所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step (1) into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction If the gas content in the smelting environment is unfavorable, set the working current to 35A for smelting. Stop the smelting after all the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级该合金锭进行均匀化熔炼，得到合金锭。将合金锭切成高径比为1：1.5的棒状试样进行压缩实验，压缩力学性能曲线如图4所示，该合金锭强度为2350MPa，无塑性变形。High vacuum arc melting: Put the alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate it, then repeatedly charge and pump high-purity argon gas, wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and set the working current It is 130A, and the primary alloy ingot is homogenized and smelted to obtain an alloy ingot. The alloy ingot was cut into rod-shaped specimens with a height-to-diameter ratio of 1:1.5 for compression experiments. The compression mechanical performance curve is shown in Figure 4. The alloy ingot has a strength of 2350MPa and no plastic deformation.
实施例2Example 2
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.18]0.83B0.17，记为Cr18B17，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.18 ] 0.83 B 0.17 , recorded as Cr18B17, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图5中Cr18B17曲线，该样品屈服强度为1248MPa，断裂强度为1519MPa，塑性16.2%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with an aspect ratio of 1:1.5 for compression experiments, and the Cr18B17 curve in Figure 5 was obtained. The sample has a yield strength of 1248MPa, a fracture strength of 1519MPa, and a plasticity of 16.2%.
实施例3Example 3
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.83B0.17，记为Cr15B17，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.83 B 0.17 , recorded as Cr15B17, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图5中Cr15B17曲线，该样品屈服强度为1332MPa，断裂强度为1902MPa，塑性25%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with an aspect ratio of 1:1.5 for compression experiments, and the Cr15B17 curve in Figure 5 was obtained. The sample has a yield strength of 1332MPa, a fracture strength of 1902MPa, and a plasticity of 25%.
实施例4Example 4
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.14]0.83B0.17，记为Cr14B17，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.14 ] 0.83 B 0.17 , recorded as Cr14B17, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图5中Cr14B17曲线，该样品屈服强度为1384MPa，断裂强度为1639MPa，塑性2.9%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with a height-to-diameter ratio of 1:1.5 for compression experiments, and the Cr14B17 curve in Figure 5 was obtained. The sample has a yield strength of 1384MPa, a fracture strength of 1639MPa, and a plasticity of 2.9%.
实施例5Example 5
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.12]0.83B0.17，记为Cr12B17，其中各元素的比例为原子百分比。包括以下步骤：A high-strength, high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.12 ] 0.83 B 0.17 , recorded as Cr12B17, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图5中Cr12B17曲线，该样品屈服强度为1190MPa，断裂强度为1453MPa，塑性3%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with an aspect ratio of 1:1.5 for compression experiments, and the Cr12B17 curve in Figure 5 was obtained. The sample has a yield strength of 1190MPa, a fracture strength of 1453MPa, and a plasticity of 3%.
实施例6Example 6
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.84B0.16，记为Cr15B16，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.84 B 0.16 , recorded as Cr15B16, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图6中Cr15B16曲线，该样品屈服强度为1545MPa，断裂强度为1704MPa，塑性19.2%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with an aspect ratio of 1:1.5 for compression experiments, and the Cr15B16 curve in Figure 6 was obtained. The yield strength of the sample was 1545MPa, the fracture strength was 1704MPa, and the plasticity was 19.2%.
实施例7Example 7
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.85B0.15，记为Cr15B15，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.85 B 0.15 , recorded as Cr15B15, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。该共晶高熵合金冷却过程“再辉”现象及冷却至室温的样品如图1所示。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图6中Cr15B15曲线，该样品屈服强度为1492MPa，断裂强度为2254MPa，压缩塑性超过55%。Cr15B15扫描电镜图如图2（c）（d）所示，两相成网络状分布。Cr15B15同步辐射数据如图3（b）所示，由面心立方相和四方相构成。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The "re-glow" phenomenon during the cooling process of the eutectic high-entropy alloy and the sample cooled to room temperature are shown in Figure 1. The eutectic high-entropy alloy was cut into rod-shaped samples with an aspect ratio of 1:1.5 for compression experiments, and the Cr15B15 curve in Figure 6 was obtained. The yield strength of the sample was 1492MPa, the fracture strength was 2254MPa, and the compression plasticity exceeded 55%. The SEM images of Cr15B15 are shown in Figure 2(c)(d). The two phases are distributed in a network. Cr15B15 synchrotron radiation data is shown in Figure 3(b), which is composed of face-centered cubic phase and tetragonal phase.
实施例8Example 8
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.86B0.14，记为Cr15B14，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.86 B 0.14 , recorded as Cr15B14, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图6中Cr15B14曲线，该样品屈服强度为1330MPa，压缩过程中高径比持续降低，压缩塑性超过80%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with a height-to-diameter ratio of 1:1.5 for compression experiments, and the Cr15B14 curve in Figure 6 was obtained. The yield strength of the sample was 1330MPa. During the compression process, the height-to-diameter ratio continued to decrease, and the compression plasticity exceeded 80%. .
实施例9Example 9
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.87B0.13，记为Cr15B13，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.87 B 0.13 , recorded as Cr15B13, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图6中Cr15B13曲线，该样品屈服强度为1248MPa，压缩过程中高径比持续降低，压缩塑性超过80%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with a height-to-diameter ratio of 1:1.5 for compression experiments, and the Cr15B13 curve in Figure 6 was obtained. The yield strength of the sample was 1248MPa. During the compression process, the height-to-diameter ratio continued to decrease, and the compression plasticity exceeded 80%. .
实施例10Example 10
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.88B0.12，记为Cr15B12，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.88 B 0.12 , recorded as Cr15B12, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图6中Cr15B10曲线，该样品屈服强度为1235MPa，压缩过程中高径比持续降低，压缩塑性超过80%。Cr15B12扫描电镜图如图2（a）（b）所示，两相成网络状分布。Cr15B15同步辐射数据如图3（a）所示，由面心立方相和四方相构成。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with a height-to-diameter ratio of 1:1.5 for compression experiments, and the Cr15B10 curve in Figure 6 was obtained. The yield strength of the sample was 1235MPa. During the compression process, the height-to-diameter ratio continued to decrease, and the compression plasticity exceeded 80%. . The SEM images of Cr15B12 are shown in Figure 2(a)(b). The two phases are distributed in a network. Cr15B15 synchrotron radiation data is shown in Figure 3(a), which is composed of face-centered cubic phase and tetragonal phase.
步骤4、轧制退火处理Step 4. Rolling annealing treatment
将步骤三得到的共晶高熵合金样品进行室温轧制；轧制后的样品在950摄氏度下退火10小时得到所述高熵合金样品，然后进行拉伸实验，得到图7拉伸性能曲线，拉伸断裂强度为600MPa，塑性为12%。The eutectic high-entropy alloy sample obtained in step 3 is rolled at room temperature; the rolled sample is annealed at 950 degrees Celsius for 10 hours to obtain the high-entropy alloy sample, and then a tensile experiment is performed to obtain the tensile performance curve shown in Figure 7. The tensile breaking strength is 600MPa and the plasticity is 12%.
实施例11Example 11
一种高强高韧共晶高熵合金，该高熵合金的组成为[(FeNiCo)0.85Cr0.15]0.89B0.10，记为Cr15B10，其中各元素的比例为原子百分比。包括以下步骤：A high-strength and high-toughness eutectic high-entropy alloy. The composition of the high-entropy alloy is [(FeNiCo) 0.85 Cr 0.15 ] 0.89 B 0.10 , recorded as Cr15B10, in which the proportion of each element is atomic percentage. Includes the following steps:
步骤1，根据高熵合金成分配置原材料。Step 1: Configure raw materials according to the high-entropy alloy composition.
超声清洗：将Co、Fe、Ni、Cr去除表面氧化皮，然后放入容器中并加入清洗溶剂，利用超声清洗干净，取出后吹干残留清洗溶剂得到所需四种金属原料。Ultrasonic cleaning: Remove the surface oxide scale from Co, Fe, Ni, and Cr, then put it into a container and add cleaning solvent. Use ultrasonic cleaning to clean it. After taking it out, blow dry the remaining cleaning solvent to obtain the four required metal raw materials.
配料：根据所述共晶高熵合金的摩尔百分比精确称量步骤（1）所得到的Co、Fe、Ni、Cr四种金属以及B原料。Ingredients: Accurately weigh the four metals Co, Fe, Ni, Cr and B raw material obtained in step (1) according to the mole percentage of the eutectic high-entropy alloy.
步骤2，熔炼制备合金锭。Step 2: Prepare alloy ingots by smelting.
高真空感应熔炼：将步骤1所得到的五种元素放入纯净的石英管中，然后放入高真空感应电弧熔炼炉中；然后反复充抽高纯氩气，多次洗气降低感应熔炼环境不利气体含量，将工作电流设置为35A进行熔炼，待金属均熔化成液体， B元素完全进入熔体中后再停止熔炼，熔炼完后得到初级合金锭；High vacuum induction melting: Put the five elements obtained in step 1 into a pure quartz tube, and then put it into a high vacuum induction arc melting furnace; then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the induction melting environment If the gas content is unfavorable, set the working current to 35A for smelting. Stop the smelting after the metal has melted into liquid and the B element has completely entered the melt. After smelting, the primary alloy ingot is obtained;
高真空电弧熔炼：将高真空感应熔炼得到的初级合金锭放入高真空电弧熔炼炉，抽真空，然后反复充抽高纯氩气，多次洗气降低炉腔内不利气体含量，将工作电流设为130A，对初级合金锭进行均匀化熔炼，得到合金锭。High vacuum arc melting: Put the primary alloy ingot obtained by high vacuum induction melting into the high vacuum arc melting furnace, evacuate, and then repeatedly charge and pump high-purity argon gas, and wash the gas multiple times to reduce the unfavorable gas content in the furnace cavity, and reduce the working current Set to 130A, homogenize the primary alloy ingot and obtain the alloy ingot.
步骤3，熔融包覆法制备网络结构共晶高熵合金。Step 3: Prepare network structure eutectic high-entropy alloy by melt coating method.
将包覆剂三氧化二硼放入干净的玻璃管中加热至900℃；将步骤2得到的合金锭放入熔融的包覆剂中加热至1250℃，保温2小时，保温过程中持续抽气；保温结束后将玻璃管取出，在空气中冷却至室温，在空气中冷却过程中会发生“再辉”现象，得到所述具有网络结构的共晶高熵合金。将该共晶高熵合金切成高径比为1:1.5的棒状样品进行压缩实验，得到图6中Cr15B10曲线，该样品屈服强度为1132MPa，压缩过程中高径比持续降低，压缩塑性超过80%。Put the coating agent diboron trioxide into a clean glass tube and heat it to 900°C; put the alloy ingot obtained in step 2 into the molten coating agent and heat it to 1250°C, keep it warm for 2 hours, and continue to pump air during the insulation process. ; After the heat preservation is completed, the glass tube is taken out and cooled to room temperature in the air. During the cooling process in the air, a "re-glow" phenomenon occurs, and the eutectic high-entropy alloy with a network structure is obtained. The eutectic high-entropy alloy was cut into rod-shaped samples with a height-to-diameter ratio of 1:1.5 for compression experiments, and the Cr15B10 curve in Figure 6 was obtained. The yield strength of the sample was 1132MPa. During the compression process, the height-to-diameter ratio continued to decrease, and the compression plasticity exceeded 80%. .
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