WO2020155283A1 - 一种高熵合金硼化物陶瓷及其制备方法和应用 - Google Patents

一种高熵合金硼化物陶瓷及其制备方法和应用 Download PDF

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WO2020155283A1
WO2020155283A1 PCT/CN2019/076727 CN2019076727W WO2020155283A1 WO 2020155283 A1 WO2020155283 A1 WO 2020155283A1 CN 2019076727 W CN2019076727 W CN 2019076727W WO 2020155283 A1 WO2020155283 A1 WO 2020155283A1
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entropy alloy
alloy boride
powder
fenicocr
boride
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龙莹
车金涛
黄路江
林华泰
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
    • C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/645—Pressure sintering
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • C04B35/65—Reaction sintering of free metal- or free silicon-containing compositions

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  • the invention belongs to the technical field of boride ceramic materials, and more specifically, relates to a high-entropy alloy boride ceramic (Al y (FeNiCoCr) 1-xy B x , 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) and its preparation Methods and applications.
  • Al y (FeNiCoCr) 1-xy B x 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1
  • the concept of high-entropy series materials was proposed, which consisted of 5 or more elements, and the atomic percentage of each element was between 5% and 35%.
  • the structure was simple, mostly BCC phase, FCC phase or BCC+FCC Two-phase structure.
  • the alloy components are highly disordered and the structure is simple. Most of them are BCC, FCC or BCC+FCC dual-phase structure.
  • the high entropy effect effectively inhibits the production of intermetallic compounds.
  • high-entropy materials have been widely studied by domestic and foreign researchers because of their high strength, high hardness, wear resistance, corrosion resistance and high temperature softening resistance.
  • the reported literature on high-entropy materials is mainly prepared by vacuum melting and casting methods. The size of the blocks prepared is small, and because the materials used, such as nickel, cobalt, chromium, etc., are relatively expensive, the cost of the prepared materials is high. Since Cantor et al. first reported the FeCrNiCoMn alloy with a single structure in 2004, the alloy has received widespread attention. FeCrNiCoMn alloy has a simple fcc solid solution structure, and it can still exist stably after being kept at 1100°C for 6h. The alloy also has very good forging characteristics and low temperature yield strength. Although the alloy has these excellent properties, the alloy is dominated by fcc structure solid solution and has a low hardness, which greatly limits the life and range of its use as a surface material.
  • high-entropy series materials are mainly prepared by arc smelting.
  • the alloy ingots need to be smelted many times. The process is complicated and it is difficult to prepare large-size and complex-shaped samples. Affected by the cooling of the arc smelting water-cooled copper crucible, the ingot is prone to dendrite segregation, composition segregation and the formation of coarse dendrites and columnar crystal structures.
  • Powder metallurgy and surface coating technology provide a new development direction for the research of this type of alloy. Powder metallurgy can effectively avoid component segregation and refine grains.
  • the prepared alloy has good structure and component uniformity;
  • the mechanical alloying method can effectively overcome the problems of the vacuum arc smelting method, and can prepare high-entropy alloys with good chemical homogeneity, fine crystal grains and even nanocrystalline, and can also prepare ceramic high-entropy alloy composite materials.
  • the disadvantage of the mechanical alloy method is that the ball milling process, the ball milling medium, the atmosphere in the spherical tank, and the process control agent may contaminate the raw materials. Therefore, in the process of preparing high-entropy alloy powder and sintering, it is necessary to strictly control and reduce the pollution to the powder. Ball milling causes work hardening and amorphous crystallization, which significantly increases the hardness of the alloy powder after ball milling.
  • Boron is an important alloy element in metal materials. As a solid solution atom, boron can often greatly improve the hardness and wear resistance of the solid solution. Studies have shown that the introduction of boron into the alloy will generate a hard second phase of metal boride, which can significantly improve the mechanical properties of the alloy. The results of studies on boron-containing alloy blocks have shown that boron mainly exists in the form of solid solution and boride precipitates in high-entropy alloys.
  • High-entropy alloy block is prepared by spark plasma sintering, hot pressing sintering, and air pressure sintering to reduce the precipitation of intermetallic compounds, and by changing the content of boron element, to strengthen the hardness and increase the hardness of AlFeNiCoCrB x high-entropy alloy boride block Abrasion resistance.
  • the present invention provides an Al y (FeNiCoCr) 1-xy B x (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) high-entropy alloy boride ceramic.
  • the ceramic has high hardness and good wear resistance.
  • Another object of the present invention is to provide a method for preparing the above-mentioned Al y (FeNiCoCr) 1-xy B x high-entropy alloy boride ceramics.
  • the microstructure is a high-entropy material with metal borides dispersed in the FCC solid solution matrix, and by changing the Al y (FeNiCoCr) 1-xy B x high-entropy alloy B element and Al element The mole percentage is used to adjust the volume fraction of the FCC solid solution phase and the metal boride phase to obtain high-entropy boride ceramics with higher hardness and good wear resistance.
  • Another object of the present invention is to provide applications of the above-mentioned high-entropy alloy boride ceramics.
  • a high-entropy alloy boride ceramic the molecular formula of the high-entropy alloy boride ceramic is Al y (FeNiCoCr) 1-xy B x , wherein 0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1, the high-entropy alloy boron
  • the compound is made by ball milling Al, Fe, Ni, Co, Cr and B by mechanochemical method to obtain Al y (FeNiCoCr) 1-xy B x powder; and then at a constant pressure of 10-50Mpa, at a heating rate of 50-200 °C/min, sintering at 800-1500°C (sintering method can be spark plasma sintering, hot pressing sintering or air pressure sintering), and finally made by furnace cooling.
  • the purity of the Al, Fe, Ni, Co, Cr and B powders are all 99.95-99.99 wt.%.
  • the preparation method of the high-entropy alloy boride ceramic includes the following specific steps:
  • the Al, Fe, Ni, Co, Cr, B powders are mixed according to the proportions, mixed and evenly placed in a high-energy ball mill for ball milling, and high-entropy alloy boride powder is obtained after ball milling;
  • the sintering process parameters are: heating rate 50 ⁇ 200°C/min, sintering temperature 800 ⁇ 1500°C and heat preservation, constant pressure 10 ⁇ 50Mpa, and finally cooled with the furnace to obtain high-entropy alloy boride ceramics.
  • the rotation speed of the ball mill in step S1 is 300-1425 rpm
  • the ball-to-material ratio is (2-20):1
  • the time of the ball mill is 5-200 h.
  • the particle size of the high-entropy alloy boride powder in step S1 is 5 to 45 ⁇ m.
  • the sintering time in step S3 is 5-30 min.
  • the present invention has the following beneficial effects:
  • the invention uses mechanochemical method combined with spark plasma sintering (hot press sintering or air pressure sintering) to obtain high-entropy alloy boride ceramics with uniform structure, not easy to segregate, and fine crystal grains, and a microstructure is obtained with FCC solid solution as the matrix and dispersed distribution Fe, Cr boride Al y (FeNiCoCr) 1-xy B x high-entropy alloy boride to strengthen Al y (FeNiCoCr) 1-xy B x (0 ⁇ x ⁇ 1, 0 ⁇ y ⁇ 1) Entropy alloy boride block hardness and improve wear resistance.
  • spark plasma sintering hot press sintering or air pressure sintering
  • 1A and 1B are SEM pictures of Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride powder prepared in Example 1 under different magnifications.
  • Example 2 is the XRD pattern of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1.
  • Example 3 is an SEM photograph of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1.
  • Example 4 is a metallographic micrograph of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1.
  • Example 5 is an SEM photograph of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1 under a 10Kg load of a Vickers hardness tester.
  • Example 6 is an SEM photograph of the wear scar of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1 under a load of 5N and a friction and wear distance of 200 m.
  • Example 7 is the XRD pattern of the Al 0.2 (FeNiCoCr) 0.6 B 0.2 high-entropy alloy boride block prepared in Example 2.
  • Example 8 is an SEM photograph of the wear scar of the Al 0.2 (FeNiCoCr) 0.6 B 0.2 high-entropy alloy boride block prepared in Example 2 under a load of 5N and a friction and wear distance of 200 m.
  • Example 10 is an XRD pattern of the Al 0.5 (FeNiCoCr) 0.5 high-entropy alloy boride block prepared in Example 4.
  • Example 11 is an SEM photograph of the Al 0.5 (FeNiCoCr) 0.5 high-entropy alloy boride block prepared in Example 4.
  • Figure 12 is the hardness change curve of the Al y (FeNiCoCr) 1-xy B x high-entropy alloy boride block prepared in Examples 1-4 under different loads.
  • Example 13 is an SEM photograph of the wear scar of the Al 0.5 (FeNiCoCr) 0.5 high-entropy alloy boride block prepared in Example 4 under a load of 5N and a friction and wear distance of 200 m.
  • the powder preparation process is protected by argon in the whole process, and a high-energy ball mill model of 8000M from SPEX of the United States is used for powder synthesis.
  • a high-energy ball mill model of 8000M from SPEX of the United States is used for powder synthesis.
  • the high-entropy alloy boride powder after ball milling is put into the spark plasma sintering mold for sintering.
  • the sintering process parameters are: heating rate 100°C/min, sintering temperature 1100°C, holding time 10min, constant pressure 30Mpa, to obtain Al 1 /3 (FeNiCoCr) 1/3 B 1/3 ceramic.
  • Fig. 1 is SEM pictures of Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride powder prepared in Example 1 under different magnifications. Among them, 1A is 500 times magnification, and 1B is 4000 times magnification. It can be seen from Figure 1 that the particle morphology of the powder after ball milling is spherical or approximately spherical with uniform particle size, with a particle size range of 5 to 45 ⁇ m. 2 is the XRD pattern of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1. It can be seen from Figure 2 that borides are formed.
  • Figure 3 is an SEM photograph of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in this embodiment.
  • (a) is the SEM image of Al 1/3 (FeNiCoCr) 1/3 B 1/3 cross-section
  • (b) is the SEM image of the corroded surface of Al 1/3 (FeNiCoCr) 1/3 B 1/3
  • the etching solution is configured
  • Example 5 is an SEM photograph of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1 under a 10Kg load of a Vickers hardness tester.
  • 6 is an SEM photograph of the wear scar of the Al 1/3 (FeNiCoCr) 1/3 B 1/3 high-entropy alloy boride block prepared in Example 1 under a load of 5N and a friction and wear distance of 200 m.
  • the Vickers hardness under a load of 20Kg is 1195.2Hv; the fracture toughness measured by the indentation method is 4.42Mpa ⁇ m 1/2 .
  • ball milling is carried out for 60 hours according to the design process parameters of the ball mill.
  • the particle morphology is spherical or nearly spherical with uniform particle size, and the particle size ranges from 5 to 45 ⁇ m.
  • the ball-milled high-entropy alloy boride powder is put into a spark plasma sintering mold for sintering.
  • the sintering process parameters are: heating rate 100°C/min, sintering temperature 1100°C, holding time 10min, constant pressure 30Mpa, to obtain Al 0.2 (FeNiCoCr) 0.6 B 0.2 ceramic.
  • FIG. 7 is the XRD pattern of the Al 0.2 (FeNiCoCr) 0.6 B 0.2 high-entropy alloy boride block prepared in Example 2. As shown in Figure 7, the amount of boride generated is small; Figure 8 is the SEM photo of the wear scar of the Al 0.2 (FeNiCoCr) 0.6 B 0.2 high-entropy alloy boride block prepared in Example 2 under a load of 5N and a friction and wear distance of 200m . After sintering, the Vickers hardness of the block under a load of 20Kg is 804.1Hv; the fracture toughness measured by the indentation method is 5.13Mpa ⁇ m 1/2 .
  • the particle morphology is spherical or nearly spherical with uniform particle size, and the particle size ranges from 5 to 45 ⁇ m.
  • the ball-milled high-entropy alloy boride powder is put into a spark plasma sintering mold for sintering.
  • the sintering process parameters are: heating rate 100°C/min, sintering temperature 1100°C, holding time 10min, constant pressure 30Mpa, and Al 0.25 is obtained.
  • 9 is an XRD pattern of the Al 0.25 (FeNiCoCr) 0.25 B 0.25 high-entropy alloy boride block prepared in Example 3.
  • the amount of boride is large; the Vickers hardness of the block after sintering is 1044.0Hv under a load of 20Kg; the fracture toughness measured by the indentation method is 5.13Mpa ⁇ m 1/2 .
  • ball milling is carried out for 60 hours according to the design process parameters of the ball mill.
  • the SEM image of the powder after ball milling is shown in the figure.
  • the particle morphology is spherical or nearly spherical with uniform particle size, and the particle size ranges from 5-45 ⁇ m.
  • the sintering process parameters are: heating rate 100°C/min, sintering temperature 1100°C, holding time 10min, constant pressure 30Mpa, and Al 0.5 ( FeNiCoCr) 0.5 ceramic.
  • FIG. 10 is an XRD pattern of the Al 0.5 (FeNiCoCr) 0.5 high-entropy alloy boride block prepared in Example 4. As shown in FIG. 10, there is no boride.
  • FIG. 11 is an SEM photograph of the Al 0.5 (FeNiCoCr) 0.5 high-entropy alloy boride block prepared in Example 4.
  • Figure 12 is the hardness change curve of the Al y (FeNiCoCr) 1-xy B x high-entropy alloy boride block prepared in Examples 1-4 under different loads. Among them, the curves a, b, c, and d are the hardness of Examples 1-4, respectively.
  • Example 13 is an SEM photograph of the wear scar of the Al 0.5 (FeNiCoCr) 0.5 high-entropy alloy boride block prepared in Example 4 under a load of 5N and a friction and wear distance of 200 m.
  • Figure 13 shows that the wear scar width of the Al 0.5 (FeNiCoCr) 0.5 high-entropy alloy boride block is large, and the sample is not wear-resistant without B.
  • the Vickers hardness of the sintered block under a load of 20Kg is 557.6Hv.

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Abstract

一种高熵合金硼化物陶瓷及其制备方法。所述高熵合金硼化物陶瓷的分子式为Aly(FeNiCoCr)1-x-yBx，其中0≤x≤1，0≤y≤1，所述高熵合金硼化物是将Al、Fe、Ni、Co、Cr和B经球磨制得Aly(FeNiCoCr)1-x-yBx粉体；再通过放电等离子烧结，以加热速率50～200℃/min、在800～1500℃、恒定压力10～50Mpa下烧结，随炉冷却制得。该方法制备的Aly(FeNiCoCr)1-x-yBx高熵合金硼化物粉末为类球形且粒径小，该陶瓷主相为FCC固溶体中弥散分布着Fe、Cr金属硼化物，具有高致密度、较高的硬度和耐磨性能。

Description

一种高熵合金硼化物陶瓷及其制备方法和应用 技术领域
本发明属硼化物陶瓷材料技术领域，更具体地，涉及一种高熵合金硼化物陶瓷(Al y(FeNiCoCr) 1-x-yB x，0≤x≤1，0≤y≤1)及其制备方法和应用。
背景技术
上世纪末，提出高熵系列材料的概念，即由5种及以上元素组成，每种元素的原子百分比介于5％-35％之间，结构简单，多为BCC相、FCC相或BCC+FCC双相结构。合金组元高度无序，组织简单，多为BCC、FCC或BCC+FCC双相结构，高熵效应有效抑制了金属间化合物的产生。
近年来，高熵系材料因为其具有高强度、高硬度、耐磨、耐腐蚀和耐高温软化等特性而受到国内外学者的广泛研究。已报道的高熵材料文献主要是采用真空熔炼和铸造的方法制备，制备的块体尺寸较小，而且因为使用到材料如镍、钴、铬等比较昂贵，使得制备的材料成本高。自2004年Cantor等首先报道了具有单一结构FeCrNiCoMn合金以来，该合金已受到广泛关注。FeCrNiCoMn合金具有简单的fcc固溶体结构，且在1100℃下保温6h后仍能稳定存在。该合金同时还具有非常好的锻造特性以及低温屈服强度。尽管该合金具有这些优异的性能，但该合金以fcc结构固溶体为主，硬度较低，这大大限制了其作为表面材料使用的寿命和范围。
目前，高熵系列材料主要采用电弧熔炼法制备，为了使各元素分布均匀，合金锭需要重复多次熔炼，工序复杂，较难制备大尺寸复杂形状的样件。受电弧熔炼水冷铜坩埚冷却的影响，铸锭易产生枝晶偏析、成分偏析和形成粗大的枝晶与柱状晶组织。粉末冶金法和表面涂层技术为该类合金的研究提供了新的发展方向，粉末冶金法可有效避免成分偏析并能细化晶粒，制备的合金具有良好的组织和成分均匀性；
机械合金化法能有效克服真空电弧熔炼法的问题，可制备良好化学均质性，细小晶粒甚至纳米晶高熵合金，还可制备陶瓷高熵合金复合材料。机械合金法不足之处在于球磨过程，球磨介质，球罐内气氛，过程控制剂可能会污染原料。因此，在制备高熵合金粉末以及烧结过程中，需严格控制和减少对粉末的污染，球磨引起加工硬化和非晶晶化，使得球磨后的合金粉末硬度显著增加。
硼是金属材料中重要的合金元素，硼作为固溶原子往往可极大的提高固溶体 的硬度和耐磨性能。研究表明在合金中引入硼元素会生成金属硼化物硬质第二相，从而可以显著提升合金的力学性能。已有有关含硼合金块体研究结果显示硼在高熵合金中主要以固溶体和硼化物析出相形式存在。现将AlFeNiCoCr高熵合金中添加硼元素，利用机械化学法将硼元素固溶于合金元素之间，通过高能球磨强化高熵合金的晶格畸化效应，重点增加B元素及其他元素的固溶度，再经放电等离子烧结、热压烧结、气压烧结制备高熵合金块体，减少金属间化合物的析出，并通过改变硼元素含量，以此强化AlFeNiCoCrB x高熵合金硼化物块体硬度并提高耐磨性。
发明内容
为了解决上述现有技术存在的不足和缺点，本发明提供一种Al y(FeNiCoCr) 1-x-yB x(0≤x≤1，0≤y≤1)高熵合金硼化物陶瓷。该陶瓷具有较高硬度和良好耐磨性能。
本发明的另一目的在于提供上述Al y(FeNiCoCr) 1-x-yB x高熵合金硼化物陶瓷的制备方法。通过机械化学法和放电等离子烧结得到微观组织为FCC固溶体基体中弥散分布着金属硼化物的高熵材料，并通过改变Al y(FeNiCoCr) 1-x-yB x高熵合金中B元素、Al元素的摩尔百分比，以调节FCC固溶体相和金属硼化物相的体积分数，得到具有较高硬度和良好耐磨性能的高熵硼化物陶瓷。
本发明再一目的在于提供上述高熵合金硼化物陶瓷的应用。
本发明的目的通过下述技术方案来实现：
一种高熵合金硼化物陶瓷，所述高熵合金硼化物陶瓷的分子式为Al y(FeNiCoCr) 1-x-yB x，其中0≤x≤1，0≤y≤1，所述高熵合金硼化物是采用机械化学法将Al、Fe、Ni、Co、Cr和B经球磨制得Al y(FeNiCoCr) 1-x-yB x粉体；再在恒定压力10～50Mpa下，以加热速率50～200℃/min，在800～1500℃下烧结(烧结方式可以采用放电等离子烧结、热压烧结或是气压烧结)，最后随炉冷却制得。
优选地，所述Al、Fe、Ni、Co、Cr和B粉末的纯度均为99.95～99.99wt.％。
所述的高熵合金硼化物陶瓷的制备方法，包括以下具体步骤：
S1.在充满氩气气氛下，将Al、Fe、Ni、Co、Cr、B粉末按照配比配料，混合均匀置于高能球磨机中进行球磨，经球磨后制得高熵合金硼化物粉末；
S2.取出球磨后的粉末，干燥、过筛，得到固溶完成的高熵合金硼化物粉末；
S3.将粉末放入放电等离子烧结模具中并进行预压，在Ar气气氛保护下进行烧结，烧结工艺参数为：加热速率50～200℃/min，烧结温度800～1500℃并保温，恒定压力10～50Mpa，最后随炉冷却，制得高熵合金硼化物陶瓷。
优选地，步骤S1中所述球磨的转速为300～1425rpm，所述球料比为(2～20)∶1，所述球磨的时间为5～200h。
优选地，步骤S1中所述高熵合金硼化物粉末的粒径为5～45μm。
优选地，步骤S3中所述烧结的时间为5～30min。
所述的高熵合金硼化物陶瓷在刀具领域中的应用。
与现有技术相比，本发明具有以下有益效果：
本发明利用机械化学法结合放电等离子烧结经(热压烧结或气压烧结)获得组织均匀、不易偏析、晶粒细小的高熵合金硼化物陶瓷，得到一种微观结构以FCC固溶体为基体，弥散分布着Fe、Cr的硼化物Al y(FeNiCoCr) 1-x-yB x高熵合金硼化物，以此强化Al y(FeNiCoCr) 1-x-yB x(0≤x≤1，0≤y≤1)高熵合金硼化物块体硬度并提高耐磨性。
附图说明
图1A和图1B为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物粉末在不同放大倍数下的SEM照片。
图2为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的XRD图。
图3为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的SEM照片。
图4为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的金相显微镜照片。
图5为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的在维氏硬度计10Kg载荷下压痕的SEM照片。
图6为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的在载荷5N、摩擦磨损距离为200m时磨痕的SEM照片。
图7为实施例2制备的Al 0.2(FeNiCoCr) 0.6B 0.2高熵合金硼化物块体的XRD图。
图8为实施例2制备的Al 0.2(FeNiCoCr) 0.6B 0.2高熵合金硼化物块体的在载荷5N、摩擦磨损距离为200m时磨痕的SEM照片。
图9为实施例3制备的Al 0.25(FeNiCoCr) 0.25B 0.25高熵合金硼化物块体的XRD图。
图10为实施例4制备的Al 0.5(FeNiCoCr) 0.5高熵合金硼化物块体的XRD图。
图11为实施例4制备的Al 0.5(FeNiCoCr) 0.5高熵合金硼化物块体的SEM照片。
图12为实施例1-4制备的Al y(FeNiCoCr) 1-x-yB x高熵合金硼化物块体在不同载荷下硬度变化曲线。
图13为实施例4制备的Al 0.5(FeNiCoCr) 0.5高熵合金硼化物块体的在载荷5N、摩擦磨损距离为200m时磨痕的SEM照片。
具体实施方式
下面结合具体实施例进一步说明本发明的内容，但不应理解为对本发明的限制。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。除非特别说明，本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。
本发明实施例中粉体制备过程全程氩气保护，采用美国SPEX公司型号为8000M的高能球磨机进行粉末合成。所用的碳化钨磨球一共六个，尺寸为11.20mm，球与混合粉末的质量之比为4∶1。
实施例1
一种Al y(FeNiCoCr) 1-x-yB x(x＝1/3，y＝1/3)高熵合金硼化物粉末，高熵合金硼化物粉末由Al、Fe、Ni、Co、Cr和B元素组成，各元素含量摩尔比为Al∶Fe∶Ni∶Co∶Cr∶B＝1∶1∶1∶1∶1∶1。放入球磨罐后按球磨设计工艺参数进行球磨200h，球磨后粉末。
其次将球磨后的高熵合金硼化物粉末放入放电等离子烧结模具中进行烧结，烧结工艺参数为：加热速率100℃/min，烧结温度1100℃，保温时间10min，恒定压力30Mpa，制得Al 1/3(FeNiCoCr) 1/3B 1/3陶瓷。
图1为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物粉末在不同放大倍数下的SEM照片。其中，1A为放大500倍，1B为放大4000倍。由图1可知，球磨后粉末的颗粒形貌为粒度均匀的球形或近似球形，粒度范围5～45μm。图2为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的XRD图。由图2可知，生成了有硼化物。图3为本实施例制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵 合金硼化物块体的SEM照片。其中，(a)为Al 1/3(FeNiCoCr) 1/3B 1/3断面SEM图，(b)为Al 1/3(FeNiCoCr) 1/3B 1/3腐蚀面SEM图，腐蚀液配置摩尔比为HCl∶FeCl 3∶H 2O＝1∶1∶10，由图3可知，网状结构区富集Fe、Cr、B形成硼化物。图5为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的在维氏硬度计10Kg载荷下压痕的SEM照片。图6为实施例1制备的Al 1/3(FeNiCoCr) 1/3B 1/3高熵合金硼化物块体的在载荷5N、摩擦磨损距离为200m时磨痕的SEM照片。20Kg载荷下维氏硬度为1195.2Hv；压痕法测得断裂韧性为4.42Mpa·m 1/2。
实施例2
一种Al y(FeNiCoCr) 1-x-yB x(x＝1/5，y＝2/5)高熵合金硼化物粉末，高熵合金粉末由Al、Fe、Ni、Co、Cr和B组成，各元素含量摩尔比为Al∶Fe∶Ni∶Co∶Cr∶B＝1∶1∶1∶1∶1∶0.5。放入球磨罐后按球磨设计工艺参数进行球磨60h，颗粒形貌为粒度均匀的球形或近似球形，粒径范围5～45μm。
其次将球磨后的高熵合金硼化物粉末放入放电等离子烧结模具中进行烧结，烧结工艺参数为：加热速率100℃/min，烧结温度1100℃，保温时间10min，恒定压力30Mpa，制得Al 0.2(FeNiCoCr) 0.6B 0.2陶瓷。
图7为实施例2制备的Al 0.2(FeNiCoCr) 0.6B 0.2高熵合金硼化物块体的XRD图。如图7可知，硼化物生成量少；图8为实施例2制备的Al 0.2(FeNiCoCr) 0.6B 0.2高熵合金硼化物块体的在载荷5N、摩擦磨损距离为200m时磨痕的SEM照片。烧结后块体在20Kg载荷下维氏硬度为804.1Hv；压痕法测得断裂韧性为5.13Mpa·m 1/2。
实施例3
一种Al y(FeNiCoCr) 1-x-yB x(x＝1/2，y＝1/4)高熵合金硼化物粉末，高熵合金硼化物粉末由Al、Fe、Ni、Co、Cr和B组成，各元素含量摩尔比为Al∶Fe∶Ni∶Co∶Cr∶B＝1∶1∶1∶1∶1∶2。放入球磨罐后按球磨设计工艺参数进行球磨60h，颗粒形貌为粒度均匀的球形或近似球形，粒径范围5～45μm。
其次将球磨后的高熵合金硼化物粉末放入放电等离子烧结模具中进行烧结，烧结工艺参数为：加热速率100℃/min，烧结温度1100℃，保温时间10min，恒定压力30Mpa，制得Al 0.25(FeNiCoCr) 0.25B 0.25陶瓷。图9为实施例3制备的Al 0.25(FeNiCoCr) 0.25B 0.25高熵合金硼化物块体的XRD图。如图9可知，硼化物生 成量多；烧结后块体在20Kg载荷下维氏硬度为1044.0Hv；压痕法测得断裂韧性为5.13Mpa·m 1/2。
实施例4
一种Al y(FeNiCoCr) 1-x-yB x(x＝0，y＝1/2)高熵合金硼化物粉末，高熵合金粉末由Al、Fe、Ni、Co、Cr和B六种元素组成，各元素含量摩尔比为Al∶Fe∶Ni∶Co∶Cr∶B＝1∶1∶1∶1∶1∶0。放入球磨罐后按球磨设计工艺参数进行球磨60h，球磨后粉末的SEM图如图，颗粒形貌为粒度均匀的球形或近似球形，粒径范围5-45μm。
其次将球磨后的高熵硼化物粉末放入放电等离子烧结模具中进行烧结，烧结工艺参数为：加热速率100℃/min，烧结温度1100℃，保温时间10min，恒定压力30Mpa，制得Al 0.5(FeNiCoCr) 0.5陶瓷。
图10为实施例4制备的Al 0.5(FeNiCoCr) 0.5高熵合金硼化物块体的XRD图。如图10可知，没有硼化物图11为实施例4制备的Al 0.5(FeNiCoCr) 0.5高熵合金硼化物块体的SEM照片。图12为实施例1-4制备的Al y(FeNiCoCr) 1-x-yB x高熵合金硼化物块体在不同载荷下硬度变化曲线。其中，曲线a、b、c和d分别是实施例1-4硬度，实施例1的样品硬度比实施例4硬度提高近一倍，说明添加B能有效提高硬度；在实施例1的样品硬度最高。图13为实施例4制备的Al 0.5(FeNiCoCr) 0.5高熵合金硼化物块体的在载荷5N、摩擦磨损距离为200m时磨痕的SEM照片。图13可知，Al 0.5(FeNiCoCr) 0.5高熵合金硼化物块体的磨痕宽度大，不含B时样品不耐磨。烧结后块体在20Kg载荷下维氏硬度为557.6Hv。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合和简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (8)

  1. 一种高熵合金硼化物陶瓷，其特征在于，所述高熵合金硼化物陶瓷的分子式为Al y(FeNiCoCr) 1-x-yB x，其中0≤x≤1，0≤y≤1，所述高熵合金硼化物是采用机械化学法将Al、Fe、Ni、Co、Cr和B经球磨制得Al y(FeNiCoCr) 1-x-yB x粉体；将上述粉体在Ar气气氛保护下，恒定压力10～50Mpa，以加热速率50～200℃/min，在800～1500℃下烧结，最后随炉冷却制得。
  2. 根据权利要求1所述的高熵合金硼化物陶瓷，其特征在于，所述Al、Fe、Ni、Co、Cr和B粉末的纯度均为99.95～99.99wt.％。
  3. 根据权利要求1所述的高熵合金硼化物陶瓷，其特征在于，所述Al y(FeNiCoCr) 1-x-yB x粉体的粒径为5～45μm。
  4. 根据权利要求1-3任一项所述的高熵合金硼化物陶瓷的制备方法，其特征在于，包括以下具体步骤：
    S1.在充满氩气气氛下，将Al、Fe、Ni、Co、Cr、B粉末按照配比配料，混合均匀置于高能球磨机中进行球磨，经球磨后制得高熵合金硼化物粉末；
    S2.取出球磨后的粉末，干燥、过筛，得到固溶完成的高熵合金硼化物粉末；
    S3.将粉末放入放电等离子烧结模具中并进行预压，在Ar气气氛保护下，恒定压力10～50Mpa，以速率50～200℃/min升温至800～1500℃并保温，最后随炉冷却，制得高熵合金硼化物陶瓷。
  5. 根据权利要求4所述的高熵合金硼化物陶瓷的制备方法，其特征在于，步骤S1中所述球磨的转速为300～1425rpm，所述球料比为(2～20)∶1，所述球磨的时间为5～200h。
  6. 根据权利要求4所述的高熵合金硼化物陶瓷的制备方法，其特征在于，步骤S1中所述高熵合金硼化物粉末的粒径为5～45μm。
  7. 根据权利要求4所述的高熵合金硼化物陶瓷的制备方法，其特征在于，步骤S3中所述烧结的时间为5～30min。
  8. 权利要求1-3任一项所述的高熵合金硼化物陶瓷在刀具领域中的应用。
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