CN110846547A - High-entropy alloy combined tungsten carbide hard alloy and preparation method thereof - Google Patents

Abstract

The invention provides a high-entropy alloy combined tungsten carbide hard alloy and a preparation method thereof, wherein the hard alloy comprises the following components in percentage by mass: the CoCrNiCuFe accounts for 5-30 wt.%, and the balance is WC. Firstly, preparing CoCrNiCuFe powder by adopting a ball milling method and refining WC powder; then mixing CoCrNiCuFe powder and WC powder in a ball mill according to different mass ratios; uniformly mixing, filling into a graphite mold and prepressing; and then, performing discharge plasma sintering on the pre-pressed sample to prepare the tungsten carbide hard alloy combined with the high-entropy alloy. The method of the invention effectively reduces the production cost and improves the hardness and the fracture toughness of the tungsten carbide hard alloy.

Description

Translated fromChinese

一种高熵合金结合的碳化钨硬质合金及其制备方法A kind of high-entropy alloy-bonded tungsten carbide cemented carbide and preparation method thereof

技术领域technical field

本发明涉及复合材料技术领域，具体而言，尤其涉及一种高熵合金结合的碳化钨硬质合金及其制备方法。The invention relates to the technical field of composite materials, in particular, to a high-entropy alloy-bonded tungsten carbide cemented carbide and a preparation method thereof.

背景技术Background technique

碳化钨硬质合金具有优异的耐热性、耐腐蚀性、高硬度和耐磨性，被广泛应用于刀具、模具、轧辊等材料。通常以WC为主要硬质相、以Co为粘结剂，采用粉末冶金方法合成。但金属钴的价格昂贵且具有毒性，因此，硬质合金行业需要寻找Co粘结剂的替代品，以降低生产成本，并促进行业的可持续发展。近年来，高熵合金(HEA)由于性能优异而被人们广泛研究。多种主元组成的HEA因具有高熵效应、晶格畸变效应、迟缓扩散效应和鸡尾酒效应等一系列特性，使其具有优异的物理、化学及力学性能，如高强度、高硬度、高耐磨性、高耐腐蚀性、高的低温韧性等，是一种潜在碳化钨硬质合金Co粘结剂的替代品。Tungsten carbide has excellent heat resistance, corrosion resistance, high hardness and wear resistance, and is widely used in tools, molds, rolls and other materials. Usually with WC as the main hard phase and Co as the binder, it is synthesized by powder metallurgy. But metal cobalt is expensive and toxic, so the cemented carbide industry needs to find alternatives to Co binders to reduce production costs and promote the sustainable development of the industry. In recent years, high-entropy alloys (HEAs) have been widely studied due to their excellent properties. HEA composed of various principal elements has a series of characteristics such as high entropy effect, lattice distortion effect, retarded diffusion effect and cocktail effect, which make it have excellent physical, chemical and mechanical properties, such as high strength, high hardness, high resistance Grinding, high corrosion resistance, high low temperature toughness, etc., is a potential substitute for tungsten carbide Co binder.

目前，关于不同高熵合金作为粘合剂的发展现状如下：At present, the development status of different high-entropy alloys as binders is as follows:

羊求民等研究了Mo含量对WC-CoCrCuFeNiMo硬质合金性能的影响，研究表明WC晶粒尺寸随Mo含量的增加呈变小的趋势。同时，Mo含量的增加会强化粘结相，使合金的硬度及抗弯强度提高。[羊求民，唐彦渊，赖星任，et al.Mo含量对烧结WC-CoCrCuFeNiMo硬质合金性能的影响[J].材料热处理学报，2018,11(39):46-51.]Yang Qiumin et al. studied the effect of Mo content on the properties of WC-CoCrCuFeNiMo cemented carbide. The study showed that the grain size of WC decreased with the increase of Mo content. At the same time, the increase of Mo content will strengthen the binder phase, which will increase the hardness and flexural strength of the alloy. [Yang Qiumin, Tang Yanyuan, Lai Xingren, et al. Effect of Mo content on the properties of sintered WC-CoCrCuFeNiMo cemented carbide[J]. Journal of Materials Heat Treatment, 2018,11(39):46-51.]

周盼龙等通过热压法制备超细晶WC-Al_xCrFeCoNi硬质合金，研究表明用Al_xCrFeCoNi高熵合金替代Co作为粘结相可抑制WC晶粒生长，起到细化晶粒的作用。与传统WC-10Co合金相比，超细晶WC-Al_xCrFeCoNi复合材料的硬度更高，同时具有良好的断裂韧性。其中的WC-10AlCrFeCoNi复合材料的硬度(HV)最高，达20.3GPa，WC-10Al_0.5CrFeCoNi具有最大断裂韧性，为12MPa·m^1/2。WC-10Al_xCrFeCoNi复合材料相较于WC-10Co传统硬质合金具有更好的耐腐蚀性能。[周盼龙,肖代红,周鹏飞,et al.热压法制备超细晶WC-Al_xCrFeCoNi复合材料及其组织与性能[J].粉末冶金材料科学与工程,2019,11(30):95-103.]Zhou Panlong et al. prepared ultra-fine-grained WC-Al_x CrFeCoNi cemented carbide by hot pressing. The study showed that replacing Co with Al_x CrFeCoNi high-entropy alloy as a binder phase can inhibit the growth of WC grains and play a role in refining grains. effect. Compared with the conventional WC-10Co alloy, the ultrafine-grained WC-Al_x CrFeCoNi composite has higher hardness and good fracture toughness. Among them, WC-10AlCrFeCoNi composite has the highest hardness (HV) of 20.3GPa, and WC-10Al_0.5 CrFeCoNi has the highest fracture toughness of 12MPa·m^1/2 . WC-10Al_x CrFeCoNi composite has better corrosion resistance than WC-10Co traditional cemented carbide. [Zhou Panlong, Xiao Daihong, Zhou Pengfei, et al. Preparation of ultrafine-grained WC-Al_x CrFeCoNi composites by hot pressing and their microstructure and properties [J]. Powder Metallurgy Materials Science and Engineering, 2019,11(30):95 -103.]

董定乾等以3～35％(质量分数，以下同)高熵合金为强化相，以0～30％Co、0～30％Ni、0～30％Fe、0～15％Cr为粘结相，以55～97％WC、0～10％TaC/NbC、0～5％VC/ZrC、0～5％Cr2C3的复合材料为硬质相，经过球磨、喷雾干燥、模压成坯料、梯度工艺烧结以及热处理制备了碳化钨硬质合金，具良好的耐磨性、韧性性能、抗氧化及优异的综合性能力学和机械性能。[董定乾；孙敬鸿；向新；杨伟.一种基于高熵合金的WC基硬质合金材料及其制备方法.108950343A.四川理工学院.2018-12-07.]Dong Dingqian et al. used 3-35% (mass fraction, the same below) high-entropy alloy as the strengthening phase, and 0-30% Co, 0-30% Ni, 0-30% Fe, 0-15% Cr as the binding phase, The composite materials of 55-97% WC, 0-10% TaC/NbC, 0-5% VC/ZrC, 0-5% Cr2C3 are used as the hard phase, and are ball-milled, spray-dried, molded into billets, sintered by gradient process and sintered. The tungsten carbide cemented carbide is prepared by heat treatment, which has good wear resistance, toughness, oxidation resistance and excellent comprehensive mechanical and mechanical properties. [Dong Dingqian; Sun Jinghong; Xiang Xin; Yang Wei. A high-entropy alloy-based WC-based cemented carbide material and its preparation method. 108950343A. Sichuan Institute of Technology. 2018-12-07.]

杨梅等采用间歇式行星球磨制备出Fe:Co:Ni:Cu:Cr＝1:1:1:(0.4～0.6):(0.4～0.6)的非晶态的高熵合金粘结相粉末，然后将高熵合金粘结相粉末与硬质相粉末进行球磨混合，采用放电等离子烧结制备出了高熵合金粘结相硬质合金。[杨梅；罗霞；龙剑平.一种高熵合金粘结相硬质合金的制备方法.109161773A.成都理工大学.2019-01-08.]Yang Mei et al. used intermittent planetary ball milling to prepare amorphous high-entropy alloy binder phase powder with Fe:Co:Ni:Cu:Cr=1:1:1:(0.4~0.6):(0.4~0.6), and then The high-entropy alloy binder phase powder and the hard phase powder were ball-milled and mixed, and the high-entropy alloy binder phase cemented carbide was prepared by spark plasma sintering. [Yang Mei; Luo Xia; Long Jianping. A preparation method of high-entropy alloy binder phase cemented carbide. 109161773A. Chengdu University of Technology. 2019-01-08.]

刘允中等以组元为Al、Co、Cr、Cu、Fe和Ni中的至少五种的高熵合金为粘结相，且每种元素的原子百分比为5～35％，通过放电等离子体烧结获得高熵合金粘结相超细碳化钨硬质合金。[刘允中；罗文艳；沈君剑.一种高熵合金粘结相超细碳化钨硬质合金及其制备方法.109252081A.华南理工大学.2019-01-22.]Liu Yunzhong used high-entropy alloys whose components are at least five of Al, Co, Cr, Cu, Fe, and Ni as the binder phase, and the atomic percentage of each element was 5-35%, and sintered by discharge plasma. High-entropy alloy binder phase ultrafine tungsten carbide cemented carbide was obtained. [Liu Yunzhong; Luo Wenyan; Shen Junjian. A high-entropy alloy binder phase ultrafine tungsten carbide cemented carbide and its preparation method. 109252081A. South China University of Technology. 2019-01-22.]

戴品强以单质金属铁、钴、铬、镍、铝、钒、钛、铜、锆、锰等组成的高熵合金为粘结剂，采用三种不同的烧结方法制备WC基硬质合金。[戴品强；刘晓强；郭轲科；洪春福；常发；田君；王卫国.一种以高熵合金粉末为粘结剂的WC基硬质合金的制备方法.CN109371307A.福建工程学院.2019-02-22.]Dai Pinqiang used a high-entropy alloy composed of elemental metals such as iron, cobalt, chromium, nickel, aluminum, vanadium, titanium, copper, zirconium, and manganese as a binder, and used three different sintering methods to prepare WC-based cemented carbide. [Dai Pinqiang; Liu Xiaoqiang; Guo Keke; Hong Chunfu; Chang Fa; Tian Jun; ]

基于上述研究，不同的高熵合金对碳化钨合金制备起着不同的作用，出于降低硬质合金烧结温度、降低生产成本及提高碳化钨硬质合金硬度和断裂韧性的目的，有必要提供一种性能更好的高熵合金作为粘合剂以解决上述需求。Based on the above research, different high-entropy alloys play different roles in the preparation of tungsten carbide alloys. In order to reduce the sintering temperature of cemented carbide, reduce production costs and improve the hardness and fracture toughness of tungsten carbide, it is necessary to provide a A high-entropy alloy with better properties is proposed as a binder to solve the above-mentioned needs.

发明内容SUMMARY OF THE INVENTION

根据上述提出如何降低硬质合金烧结温度、降低生产成本，提高碳化钨硬质合金硬度和断裂韧性的技术问题，而提供一种高熵合金结合的碳化钨硬质合金及其制备方法。本发明主要采用CoCrNiCuFe高熵合金作为粘结剂，采用放电等离子烧结的方法制备碳化钨硬质合金，其中的金属单质均为常见的碳化钨硬质合金的粘结剂或重要添加元素，对WC的润湿性较好，制得的碳化钨硬质合金性能较好。According to the technical problem of how to reduce the sintering temperature of cemented carbide, reduce the production cost, and improve the hardness and fracture toughness of tungsten carbide cemented carbide, a high-entropy alloy-bonded tungsten carbide cemented carbide and its preparation method are provided. The present invention mainly adopts CoCrNiCuFe high-entropy alloy as the binder, and adopts the spark plasma sintering method to prepare the tungsten carbide hard alloy. The wettability of the tungsten carbide is better, and the obtained tungsten carbide cemented carbide has better performance.

本发明采用的技术手段如下：The technical means adopted in the present invention are as follows:

一种高熵合金结合的碳化钨硬质合金，其特征在于，所述硬质合金按照质量百分比计成分为：CoCrNiCuFe占5～30wt.％，余量为WC。A high-entropy alloy-bonded tungsten carbide cemented carbide is characterized in that the cemented carbide is composed of: CoCrNiCuFe accounts for 5-30 wt.%, and the balance is WC.

进一步地，所述CoCrNiCuFe的粒径为150nm以细；WC的纯度为＞99％，粒径为150nm以细。Further, the particle size of the CoCrNiCuFe is finer than 150 nm; the purity of WC is >99%, and the particle size is finer than 150 nm.

本发明还公开了上述高熵合金结合的碳化钨硬质合金的制备方法，其特征在于包括如下步骤，The present invention also discloses a method for preparing the above-mentioned high-entropy alloy-bonded tungsten carbide cemented carbide, which is characterized by comprising the following steps:

S1、CoCrNiCuFe粉末制备：在充满氩气的手套箱中将Co、Cr、Ni、Cu、Fe按1:1:1:1:1摩尔比混合装入WC硬质合金球磨罐中，球、料质量比为10:1～20:1，转速为300～600r/min，球磨时间为20～50h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末；S1. Preparation of CoCrNiCuFe powder: in a glove box filled with argon, mix Co, Cr, Ni, Cu, and Fe into a WC carbide ball mill in a molar ratio of 1:1:1:1:1. The mass ratio is 10:1～20:1, the rotating speed is 300～600r/min, the ball milling time is 20～50h, every 5h of revolution, the machine is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials sticking to the grinding ball and the inner wall of the tank are scraped off and mixed evenly. Then continue ball milling to obtain CoCrNiCuFe powder with a thickness of 150nm;

S2、WC粉末制备：将WC粉末进行球磨细化，球、料质量比为10:1～20:1，转速为250～400r/min，球磨时间为10～40h，每转5h停机30min进行散热，制得150nm以细的WC粉末；S2. Preparation of WC powder: The WC powder is ball-milled and refined, the mass ratio of ball to material is 10:1-20:1, the rotational speed is 250-400r/min, the ball-milling time is 10-40h, and the machine is stopped for 30min per revolution for 5h to dissipate heat. , to obtain 150nm fine WC powder;

S3、混料：在充满氩气的手套箱中，称取质量百分比为5～30wt.％由步骤S1制备的CoCrNiCuFe粉末，加入由步骤S2制备的WC粉末中后进行球磨混料，球、料质量比为5:1～10:1，转速为200～350r/min，球磨时间为2～5h，每转1h停机10min进行散热；S3. Mixing: In a glove box filled with argon, weigh the CoCrNiCuFe powder prepared in step S1 with a mass percentage of 5-30 wt. The mass ratio is 5:1~10:1, the speed is 200~350r/min, the ball milling time is 2~5h, and the machine is stopped for 10min after each revolution of 1h to dissipate heat;

S4、烧结制备：将由步骤S3混合后的混合料装入石墨模具中预压，预压压力为10～30MPa，预压60S；然后进行放电等离子烧结，真空度为40Pa，烧结压力为40～50MPa，烧结温度为1100～1400℃，升温速率为30～100℃/min，保温时间为3～30min；然后降温卸压，制得高熵合金结合的碳化钨硬质合金。S4, sintering preparation: put the mixture mixed in step S3 into a graphite mold for pre-pressing, the pre-pressing pressure is 10-30 MPa, and the pre-pressing is 60 s; then spark plasma sintering is performed, the vacuum degree is 40 Pa, and the sintering pressure is 40-50 MPa , the sintering temperature is 1100-1400°C, the heating rate is 30-100°C/min, and the holding time is 3-30min; then the temperature is lowered and the pressure is relieved to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

进一步地，所述Co、Cr、Ni、Cu、Fe粉末纯度为＞99％，其中，Co粉末粒径为1～3μm，Cr粉末粒径为＜75μm，其余金属单质粉末粒径为＜45μm。Further, the purity of the Co, Cr, Ni, Cu, and Fe powders is >99%, wherein, the particle size of the Co powder is 1-3 μm, the particle size of the Cr powder is <75 μm, and the particle size of the remaining metal powders is <45 μm.

进一步地，所述WC粉末的粒径为1～3μm，纯度为＞99％。Further, the particle size of the WC powder is 1-3 μm, and the purity is >99%.

进一步地，步骤S1、S2和S3的球磨过程均采用直径分别为8mm、5mm和2mm三种大、中、小规格的WC硬质合金球，其中，大、中、小规格的WC硬质合金球的质量比为3:1:1。Further, in the ball milling process of steps S1, S2 and S3, three kinds of large, medium and small WC cemented carbide balls with diameters of 8 mm, 5 mm and 2 mm are used, wherein the large, medium and small WC cemented carbide balls are used. The mass ratio of the balls is 3:1:1.

进一步地，步骤S4中具体烧结工艺为：首先，对样品缓慢施加压力至40～50MPa；然后，抽真空度至40Pa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以30～100℃/min的升温速率从600℃升到1100～1400℃，保温3～30min；随炉冷却，得到毛坯；将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。Further, the specific sintering process in step S4 is as follows: first, slowly apply pressure to the sample to 40-50MPa; then, pump the vacuum to 40Pa; then, heat from room temperature to 600°C in 5min, and keep the temperature at 600°C for 10min; Rising from 600°C to 1100°C to 1400°C at a heating rate of 30-100°C/min, holding for 3-30 minutes; cooling with the furnace to obtain a blank; subjecting the prepared blank to surface grinding and deburring to obtain a high-entropy alloy bond of tungsten carbide.

较现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:

1、本发明选取的CoCrNiCuFe高熵合金具有优异的综合性能，主要体现在，CoCrNiCuFe高熵合金中各金属单质均为常见的碳化钨硬质合金的粘结剂或重要添加元素，因此，CoCrNiCuFe高熵合金对WC的润湿性较好。并且，CoCrNiCuFe高熵合金烧结体的硬度和抗弯强度分别为420HV和1800MPa，超过了传统的Co、Ni、Fe等金属粘结剂，能提高碳化钨硬质合金的硬度和韧性。其次，在本发明实施例中，大部分CoCrNiCuFe高熵合金均能稳定地存在于硬质合金体系中。1. The CoCrNiCuFe high-entropy alloy selected in the present invention has excellent comprehensive performance, which is mainly reflected in the fact that each metal element in the CoCrNiCuFe high-entropy alloy is a common tungsten carbide cemented carbide binder or an important additive element. Therefore, CoCrNiCuFe has high The entropy alloy has better wettability to WC. In addition, the hardness and flexural strength of the CoCrNiCuFe high-entropy alloy sintered body are 420HV and 1800MPa, respectively, which exceed the traditional metal binders such as Co, Ni, and Fe, and can improve the hardness and toughness of tungsten carbide. Secondly, in the embodiments of the present invention, most of the CoCrNiCuFe high-entropy alloys can stably exist in the cemented carbide system.

2、本发明提供的制备方法能减少金属Co资源的使用，降低生产成本，减小对环境的污染。2. The preparation method provided by the present invention can reduce the use of metal Co resources, reduce the production cost, and reduce the pollution to the environment.

附图说明Description of drawings

为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图做以简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to illustrate the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.

图1为本发明提供的高熵合金的碳化钨硬质合金的XRD图，其中，(a)实施例6中的碳化钨硬质合金的XRD图；(b)实施例7中的碳化钨硬质合金的XRD图；(c)实施例8中的碳化钨硬质合金的XRD图。Fig. 1 is the XRD pattern of the tungsten carbide hard alloy of the high-entropy alloy provided by the present invention, wherein, (a) the XRD pattern of the tungsten carbide hard alloy in the embodiment 6; (b) the tungsten carbide hard alloy in the embodiment 7 XRD pattern of the alloy; (c) XRD pattern of the tungsten carbide cemented carbide in Example 8.

图2为本发明提供的高熵合金的碳化钨硬质合金表面的FESEM图，其中，(a)实施例6中的碳化钨硬质合金表面的FESEM图；(b)实施例7中的碳化钨硬质合金表面的FESEM图；(c)实施例8中的碳化钨硬质合金表面的FESEM图。Fig. 2 is the FESEM image of the surface of the tungsten carbide cemented carbide of the high-entropy alloy provided by the present invention, wherein, (a) the FESEM image of the surface of the tungsten carbide cemented carbide in Example 6; (b) the carbonization in Example 7 FESEM image of the surface of tungsten carbide; (c) FESEM image of the surface of tungsten carbide in Example 8.

具体实施方式Detailed ways

需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。下面将参考附图并结合实施例来详细说明本发明。It should be noted that the embodiments of the present invention and the features of the embodiments may be combined with each other under the condition of no conflict. The present invention will be described in detail below with reference to the accompanying drawings and in conjunction with the embodiments.

为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。以下对至少一个示例性实施例的描述实际上仅仅是说明性的，决不作为对本发明及其应用或使用的任何限制。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purposes, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments It is only a part of the embodiments of the present invention, but not all of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

需要注意的是，这里所使用的术语仅是为了描述具体实施方式，而非意图限制根据本发明的示例性实施方式。如在这里所使用的，除非上下文另外明确指出，否则单数形式也意图包括复数形式，此外，还应当理解的是，当在本说明书中使用术语“包含”和/或“包括”时，其指明存在特征、步骤、操作、器件、组件和/或它们的组合。It should be noted that the terminology used herein is for the purpose of describing specific embodiments only, and is not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly dictates otherwise, the singular is intended to include the plural as well, furthermore, it is to be understood that when the terms "comprising" and/or "including" are used in this specification, it indicates that There are features, steps, operations, devices, components and/or combinations thereof.

除非另外具体说明，否则在这些实施例中阐述的部件和步骤的相对布置、数字表达式和数值不限制本发明的范围。同时，应当清楚，为了便于描述，附图中所示出的各个部分的尺寸并不是按照实际的比例关系绘制的。对于相关领域普通技术人员己知的技术、方法和设备可能不作详细讨论，但在适当情况下，所述技术、方法和设备应当被视为授权说明书的一部分。在这里示出和讨论的所有示例中，任向具体值应被解释为仅仅是示例性的，而不是作为限制。因此，示例性实施例的其它示例可以具有不同的值。应注意到：相似的标号和字母在下面的附图中表示类似项，因此，一旦某一项在一个附图中被定义，则在随后的附图中不需要对其进行进一步讨论。The relative arrangement of the components and steps, the numerical expressions and numerical values set forth in these embodiments do not limit the scope of the invention unless specifically stated otherwise. Meanwhile, it should be understood that, for convenience of description, the dimensions of various parts shown in the accompanying drawings are not drawn in an actual proportional relationship. Techniques, methods, and devices known to those of ordinary skill in the relevant art may not be discussed in detail, but where appropriate, such techniques, methods, and devices should be considered part of the authorized specification. In all examples shown and discussed herein, any specific values should be construed as illustrative only and not limiting. Accordingly, other examples of exemplary embodiments may have different values. It should be noted that like numerals and letters refer to like items in the following figures, so once an item is defined in one figure, it does not require further discussion in subsequent figures.

本发明提供了一种高熵合金结合的碳化钨硬质合金，所述硬质合金中CoCrNiCuFe的质量百分比为5～30wt.％，余量为WC。其中，所述CoCrNiCuFe的粒径为150nm以细；WC的纯度为＞99％，粒径为150nm以细。The invention provides a tungsten carbide hard alloy combined with a high-entropy alloy. The mass percentage of CoCrNiCuFe in the hard alloy is 5-30 wt.%, and the balance is WC. Wherein, the particle size of the CoCrNiCuFe is finer than 150nm; the purity of WC is >99%, and the particle size is finer than 150nm.

本发明还提供了一种上述高熵合金结合的碳化钨硬质合金的制备方法，包括如下步骤，The present invention also provides a preparation method of the above-mentioned high-entropy alloy-bonded tungsten carbide cemented carbide, comprising the following steps:

S1、CoCrNiCuFe粉末制备：在充满氩气的手套箱中将Co、Cr、Ni、Cu、Fe按1:1:1:1:1摩尔比混合装入WC硬质合金球磨罐中，球、料质量比为10:1～20:1，转速为300～600r/min，球磨时间为20～50h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末；其中，所述Co、Cr、Ni、Cu、Fe粉末纯度为＞99％，其中，Co粉末粒径为1～3μm，Cr粉末粒径为＜75μm，其余金属单质粉末粒径为＜45μm。S1. Preparation of CoCrNiCuFe powder: in a glove box filled with argon, mix Co, Cr, Ni, Cu, and Fe into a WC carbide ball mill in a molar ratio of 1:1:1:1:1. The mass ratio is 10:1～20:1, the rotating speed is 300～600r/min, the ball milling time is 20～50h, every 5h of revolution, the machine is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials sticking to the grinding ball and the inner wall of the tank are scraped off and mixed evenly. Then continue ball milling to obtain CoCrNiCuFe powder with a thickness of 150 nm; wherein, the purity of the Co, Cr, Ni, Cu, Fe powders is >99%, and the particle size of the Co powder is 1-3 μm, and the particle size of the Cr powder is < 75μm, and the particle size of the remaining metal elemental powders is <45μm.

S2、WC粉末制备：将WC粉末进行球磨细化，球、料质量比为10:1～20:1，转速为250～400r/min，球磨时间为10～40h，每转5h停机30min进行散热，制得150nm以细的WC粉末；其中，所述WC粉末的粒径为1～3μm，纯度为＞99％。S2. Preparation of WC powder: The WC powder is ball-milled and refined, the mass ratio of ball to material is 10:1-20:1, the rotational speed is 250-400r/min, the ball-milling time is 10-40h, and the machine is stopped for 30min per revolution for 5h to dissipate heat. , to obtain a fine WC powder with a thickness of 150 nm; wherein, the particle size of the WC powder is 1-3 μm, and the purity is >99%.

S3、混料：在充满氩气的手套箱中，称取质量百分比为5～30wt.％由步骤S1制备的CoCrNiCuFe粉末，加入由步骤S2制备的WC粉末中后进行球磨混料，球、料质量比为5:1～10:1，转速为200～350r/min，球磨时间为2～5h，每转1h停机10min进行散热；S3. Mixing: In a glove box filled with argon, weigh the CoCrNiCuFe powder prepared in step S1 with a mass percentage of 5-30 wt. The mass ratio is 5:1~10:1, the speed is 200~350r/min, the ball milling time is 2~5h, and the machine is stopped for 10min after each revolution of 1h to dissipate heat;

上述步骤S1、S2和S3的球磨过程均采用直径分别为8mm、5mm和2mm三种大、中、小规格的WC硬质合金球，其中，大、中、小规格的WC硬质合金球的质量比为3:1:1。The ball milling process of the above-mentioned steps S1, S2 and S3 adopts three kinds of large, medium and small WC carbide balls with diameters of 8 mm, 5 mm and 2 mm respectively. The mass ratio is 3:1:1.

S4、烧结制备：将由步骤S3混合后的混合料装入石墨模具中预压，预压压力为10～30MPa，预压60S；然后进行放电等离子烧结，首先，对样品缓慢施加压力至40～50MPa；然后，抽真空度至40Pa；接着，根据SPS烧结特点确定升温方式为：用5min时间从室温加热到600℃，在600℃保温10min；再以30～100℃/min的升温速率从600℃升到1100～1400℃，保温3～30min；随炉冷却，得到毛坯；将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。具体地，在烧结过程中，温度在600℃以下阶段，合金粉体颗粒表面吸附的气体会逐渐解吸，此时合金基体的性能并未发生根本性的变化，这一阶段快速升温，一方面可以缩短烧结时间，另一方面还可以节约能源；600℃保温阶段作用有两点，一是平稳因上阶段快速升温引起的较大功率调整，二是让合金颗粒表面进行扩散，消除基体内的热应力，为后期烧结做好准备；在600℃上升到设定的烧结温度阶段，合金颗粒开始黏结，烧结颈扩大，气孔逐渐相互连通，晶界开始移动，晶粒开始正常生长，这一阶段以晶界和晶格扩散为主；在最后保温阶段，烧结反应充分进行，各组分变化、固相颗粒表面蒸发-凝聚传质和塑性流变过程均在此阶段达到最佳状态，烧结也渐渐进入后期。在降温阶段，降温速度的快慢可直接影响制品的硬度和强度，降温速度快，合金颗粒来不及继续长大，结晶较细小，起到细晶强化的作用。S4, sintering preparation: put the mixture mixed in step S3 into a graphite mold for pre-pressing, the pre-pressing pressure is 10-30 MPa, and the pre-pressing is 60 s; then spark plasma sintering is performed, first, slowly apply pressure to the sample to 40-50 MPa ; Then, vacuumize to 40Pa; then, according to the characteristics of SPS sintering, the heating method is determined as: heating from room temperature to 600 ℃ in 5 minutes, holding at 600 ℃ for 10 minutes; The temperature is raised to 1100-1400°C, and the temperature is kept for 3-30 minutes; cooled with the furnace to obtain a blank; the prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide. Specifically, during the sintering process, when the temperature is below 600°C, the gas adsorbed on the surface of the alloy powder particles will be gradually desorbed. At this time, the properties of the alloy matrix do not fundamentally change. The temperature rises rapidly at this stage. Shortening the sintering time, on the other hand, can also save energy; the 600 ℃ heat preservation stage has two functions, one is to stabilize the larger power adjustment caused by the rapid temperature rise in the previous stage, and the other is to diffuse the surface of the alloy particles to eliminate the heat in the matrix. stress to prepare for later sintering; at the stage of rising to the set sintering temperature at 600 °C, the alloy particles begin to bond, the sintering neck expands, the pores gradually connect with each other, the grain boundaries begin to move, and the grains begin to grow normally. Grain boundary and lattice diffusion are the main factors; in the final holding stage, the sintering reaction is fully carried out, the changes of components, the evaporation-coagulation mass transfer on the surface of the solid phase particles and the plastic rheological process all reach the best state at this stage, and the sintering also gradually into the later stage. In the cooling stage, the speed of cooling can directly affect the hardness and strength of the product. If the cooling speed is fast, the alloy particles have no time to continue to grow, and the crystals are small, which plays the role of fine-grain strengthening.

本发明所述的球磨机型号为QM-3SP4型(中国)。The model of the ball mill described in the present invention is QM-3SP4 (China).

本发明所述的放电等离子烧结仪型号为LABOXTM-110型(日本)。The model of the spark plasma sintering apparatus described in the present invention is LABOXTM-110 (Japan).

石墨模具为目前市场上销售的产品。Graphite molds are products currently on the market.

本发明所述的检测设备均为高校实验室常规检测手段所用仪器，如X射线衍射仪、硬度计、扫描电镜等。The detection equipments described in the present invention are all instruments used for routine detection methods in university laboratories, such as X-ray diffractometers, hardness testers, scanning electron microscopes, and the like.

实施例1Example 1

如表1所示，为制备CoCrNiCuFe的原料及其质量配比；如表2所示，为制备原料配方的称量按照下述百分比进行：As shown in Table 1, for preparing the raw material of CoCrNiCuFe and its mass ratio; as shown in Table 2, for preparing the weighing of the raw material formula, it is carried out according to the following percentages:

表1制备CoCrNiCuFe的原料及其质量配比Table 1 Raw materials for preparing CoCrNiCuFe and their mass ratios

表2制备40g碳化钨硬质合金的原料及其配比Table 2 prepares the raw material of 40g tungsten carbide cemented carbide and its ratio

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为10:1，转速为600r/min，球磨时间为30h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Mix 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in an argon-filled glove box, with a ball-to-material mass ratio of 10:1 , the rotation speed is 600r/min, the ball milling time is 30h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials adhering to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain 150nm fine CoCrNiCuFe powder.

S2、将WC粉末进行球磨细化，球、料质量比为10:1，转速为250r/min，球磨40h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 10:1, the rotational speed is 250r/min, the ball-milling is 40h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain fine WC powder with a thickness of 150nm.

S3、在充满氩气的手套箱中，称取2g CoCrNiCuFe和38g WC装入WC硬质合金球磨罐中。球、料质量比为5:1，转速为350r/min，球磨时间为5h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 2g of CoCrNiCuFe and 38g of WC into a WC carbide ball mill jar. The mass ratio of ball and material is 5:1, the rotation speed is 350r/min, the ball milling time is 5h, and the machine is stopped for 10min for each rotation 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为10MPa，预压60S；然后，抽真空度至40Pa，加压至40MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以30℃/min的升温速率从600℃升到1200℃，保温30min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4. First, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 10MPa, and the pre-pressing is 60S; then, the vacuum degree is evacuated to 40Pa, and the pressure is to 40MPa; Incubate at 600 °C for 10 min; then increase from 600 °C to 1200 °C at a heating rate of 30 °C/min for 30 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表3所示：After grinding and polishing the sintered tungsten carbide sample, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 3:

表3实施例1中碳化钨硬质合金的性能参数和具体数值Table 3 Performance parameters and specific values of tungsten carbide cemented carbide in Example 1

实施例2Example 2

采用表1和表2的成分制备，球磨转速、时间等进行调整：Use the ingredients in Table 1 and Table 2 to prepare, adjust the ball milling speed, time, etc.:

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为15:1，转速为300r/min，球磨时间为50h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Mix 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in an argon-filled glove box, with a ball-to-material mass ratio of 15:1 , the speed is 300r/min, the ball milling time is 50h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials sticking to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain CoCrNiCuFe powder with a thickness of 150nm.

S2、将WC粉末进行球磨细化，球、料质量比为10:1，转速为300r/min，球磨30h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 10:1, the rotation speed is 300r/min, the ball-milling is 30h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取2g CoCrNiCuFe和38g WC装入WC硬质合金球磨罐中。球、料质量比为5:1，转速为300r/min，球磨时间为4h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 2g of CoCrNiCuFe and 38g of WC into a WC carbide ball mill jar. The mass ratio of ball and material is 5:1, the rotation speed is 300r/min, the ball milling time is 4h, and the machine is stopped for 10min for each rotation 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为10MPa，预压60S；然后，抽真空度至40Pa，加压至50MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以50℃/min的升温速率从600℃升到1300℃，保温5min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4. First, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 10MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 50MPa; Incubate at 600 °C for 10 min; then increase from 600 °C to 1300 °C at a heating rate of 50 °C/min for 5 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表4所示：After grinding and polishing the sintered tungsten carbide sample, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 4:

表4实施例2中碳化钨硬质合金的性能参数和具体数值Performance parameters and specific values of tungsten carbide cemented carbide in Example 2 of Table 4

实施例3Example 3

原料配方的称量按照下述表5中的百分比进行：The weighing of the raw material formula is carried out according to the following percentages in Table 5:

表5制备40g碳化钨硬质合金的原料及其配比Table 5 prepares the raw material of 40g tungsten carbide cemented carbide and its ratio

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为20:1，转速为300r/min，球磨时间为45h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Put 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in a glove box filled with argon gas. The mass ratio of ball to material is 20:1 , the rotation speed is 300r/min, the ball milling time is 45h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials adhering to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain 150nm fine CoCrNiCuFe powder.

S2、将WC粉末进行球磨细化，球、料质量比为10:1，转速为350r/min，球磨20h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 10:1, the rotating speed is 350r/min, the ball-milling is 20h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取4g CoCrNiCuFe和36g WC装入WC硬质合金球磨罐中。球、料质量比为8:1，转速为200r/min，球磨时间为4.5h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 4g of CoCrNiCuFe and 36g of WC into a WC carbide ball mill jar. The mass ratio of balls and materials is 8:1, the rotation speed is 200r/min, the ball milling time is 4.5h, and the machine is stopped for 10min per revolution for 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为30MPa，预压60S；然后，抽真空度至40Pa，加压至50MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以30℃/min的升温速率从600℃升到1300℃，保温10min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4, first, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 30MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 50MPa; then, it is heated from room temperature to 600 ℃ in 5min time, Incubate at 600 °C for 10 min; then increase from 600 °C to 1300 °C at a heating rate of 30 °C/min for 10 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表6所示：After grinding and polishing the sintered tungsten carbide samples, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 6:

表6实施例3中碳化钨硬质合金的性能参数和具体数值Table 6 Performance parameters and specific values of tungsten carbide cemented carbide in Example 3

实施例4Example 4

采用表1和表5的成分制备，球磨转速、时间等进行调整：Use the ingredients in Table 1 and Table 5 to prepare, adjust the ball milling speed, time, etc.:

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为10:1，转速为500r/min，球磨时间为40h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Mix 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in an argon-filled glove box, with a ball-to-material mass ratio of 10:1 , the speed is 500r/min, the ball milling time is 40h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials sticking to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain 150nm fine CoCrNiCuFe powder.

S2、将WC粉末进行球磨细化，球、料质量比为10:1，转速为400r/min，球磨15h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 10:1, the rotation speed is 400r/min, the ball-milling is 15h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取4g CoCrNiCuFe和36g WC装入WC硬质合金球磨罐中。球、料质量比为8:1，转速为250r/min，球磨时间为5h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 4g of CoCrNiCuFe and 36g of WC into a WC carbide ball mill jar. The mass ratio of balls and materials is 8:1, the rotation speed is 250r/min, the ball milling time is 5h, and the machine is stopped for 10min for each rotation of 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为30MPa，预压60S；然后，抽真空度至40Pa，加压至50MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以50℃/min的升温速率从600℃升到1200℃，保温5min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4, first, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 30MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 50MPa; then, it is heated from room temperature to 600 ℃ in 5min time, Incubate at 600 °C for 10 min; then increase from 600 °C to 1200 °C at a heating rate of 50 °C/min for 5 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表7所示：After grinding and polishing the sintered tungsten carbide sample, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 7:

表7实施例4中碳化钨硬质合金的性能参数和具体数值Table 7 Performance parameters and specific values of tungsten carbide cemented carbide in Example 4

实施例5Example 5

采用表1和表5的成分制备，球磨转速、时间等进行调整：Use the ingredients in Table 1 and Table 5 to prepare, adjust the ball milling speed, time, etc.:

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为10:1，转速为400r/min，球磨时间为50h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Mix 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in an argon-filled glove box, with a ball-to-material mass ratio of 10:1 , the speed is 400r/min, the ball milling time is 50h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials adhering to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain 150nm fine CoCrNiCuFe powder.

S2、将WC粉末进行球磨细化，球、料质量比为15:1，转速为250r/min，球磨35h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 15:1, the rotation speed is 250r/min, the ball-milling is 35h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取4g CoCrNiCuFe和36g WC装入WC硬质合金球磨罐中。球、料质量比为8:1，转速为300r/min，球磨时间为3h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 4g of CoCrNiCuFe and 36g of WC into a WC carbide ball mill jar. The mass ratio of balls and materials is 8:1, the rotation speed is 300r/min, the ball milling time is 3h, and the machine is stopped for 10min for each rotation of 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为30MPa，预压60S；然后，抽真空度至40Pa，加压至50MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以100℃/min的升温速率从600℃升到1400℃，保温3min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4, first, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 30MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 50MPa; then, it is heated from room temperature to 600 ℃ in 5min time, Incubate at 600 °C for 10 min; then increase the temperature from 600 °C to 1400 °C at a heating rate of 100 °C/min, and hold for 3 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表8所示：After grinding and polishing the sintered tungsten carbide samples, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 8:

表8实施例5中碳化钨硬质合金的性能参数和具体数值Table 8 Performance parameters and specific values of tungsten carbide cemented carbide in Example 5

实施例6Example 6

原料配方的称量按照下述表9中的百分比进行：The weighing of the raw material formulations is carried out according to the following percentages in Table 9:

表9制备40g碳化钨硬质合金的原料及其配比Table 9 prepares the raw material of 40g tungsten carbide cemented carbide and its ratio

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为15:1，转速为400r/min，球磨时间为45h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Mix 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in an argon-filled glove box, with a ball-to-material mass ratio of 15:1 , the speed is 400r/min, the ball milling time is 45h, every 5h of rotation is stopped for 30min to dissipate heat, every 10h of stoppage, the raw materials that stick to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain CoCrNiCuFe powder with a thickness of 150nm.

S2、将WC粉末进行球磨细化，球、料质量比为15:1，转速为300r/min，球磨25h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 15:1, the rotational speed is 300r/min, the ball-milling is 25h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取8g CoCrNiCuFe和32g WC装入WC硬质合金球磨罐中。球、料质量比为10:1，转速为350r/min，球磨时间为2.5h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 8g of CoCrNiCuFe and 32g of WC into a WC carbide ball mill jar. The mass ratio of balls and materials is 10:1, the rotation speed is 350r/min, the ball milling time is 2.5h, and the machine is stopped for 10min for each rotation 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为30MPa，预压60S；然后，抽真空度至40Pa，加压至40MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以50℃/min的升温速率从600℃升到1200℃，保温10min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4, first, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 30MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 40MPa; then, it is heated from room temperature to 600 ℃ in 5min time, Incubate at 600 °C for 10 min; then increase from 600 °C to 1200 °C at a heating rate of 50 °C/min for 10 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表10所示：After grinding and polishing the sintered tungsten carbide samples, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 10:

表10实施例6中碳化钨硬质合金的性能参数和具体数值Table 10 Performance parameters and specific values of tungsten carbide cemented carbide in Example 6

实施例7Example 7

采用表1和表9的成分制备，球磨转速、时间等进行调整：Use the ingredients in Table 1 and Table 9 to prepare, adjust the ball milling speed, time, etc.:

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为15:1，转速为500r/min，球磨时间为35h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Mix 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in an argon-filled glove box, with a ball-to-material mass ratio of 15:1 , the rotation speed is 500r/min, the ball milling time is 35h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials adhering to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain 150nm fine CoCrNiCuFe powder.

S2、将WC粉末进行球磨细化，球、料质量比为15:1，转速为400r/min，球磨10h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 15:1, the rotation speed is 400r/min, the ball-milling is 10h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取8g CoCrNiCuFe和32g WC装入WC硬质合金球磨罐中。球、料质量比为10:1，转速为300r/min，球磨时间为3h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 8g of CoCrNiCuFe and 32g of WC into a WC carbide ball mill jar. The mass ratio of balls and materials is 10:1, the rotation speed is 300r/min, the ball milling time is 3h, and the machine is stopped for 10min for each rotation 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为30MPa，预压60S；然后，抽真空度至40Pa，加压至40MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以50℃/min的升温速率从600℃升到1300℃，保温15min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4, first, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 30MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 40MPa; then, it is heated from room temperature to 600 ℃ in 5min time, Incubate at 600 °C for 10 min; then increase the temperature from 600 °C to 1300 °C at a heating rate of 50 °C/min, and maintain for 15 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表11所示：After grinding and polishing the sintered tungsten carbide samples, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 11:

表11实施例7中碳化钨硬质合金的性能参数和具体数值Table 11 Performance parameters and specific values of tungsten carbide cemented carbide in Example 7

实施例8Example 8

采用表1和表9的成分制备，球磨转速、时间等进行调整：Use the ingredients in Table 1 and Table 9 to prepare, adjust the ball milling speed, time, etc.:

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为20:1，转速为400r/min，球磨时间为40h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Put 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in a glove box filled with argon gas. The mass ratio of ball to material is 20:1 , the rotation speed is 400r/min, the ball milling time is 40h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials adhering to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain CoCrNiCuFe powder with a thickness of 150nm.

S2、将WC粉末进行球磨细化，球、料质量比为20:1，转速为250r/min，球磨15h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 20:1, the rotation speed is 250r/min, the ball-milling is 15h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取8g CoCrNiCuFe和32g WC装入WC硬质合金球磨罐中。球、料质量比为10:1，转速为200r/min，球磨时间为4h，每转1h停机10min进行散热。S3. In an argon-filled glove box, weigh 8g of CoCrNiCuFe and 32g of WC into a WC carbide ball mill jar. The mass ratio of balls and materials is 10:1, the rotation speed is 200r/min, the ball milling time is 4h, and the machine is stopped for 10min for each rotation of 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为10MPa，预压60S；然后，抽真空度至40Pa，加压至40MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以50℃/min的升温速率从600℃升到1400℃，保温20min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4. First, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 10MPa, and the pre-pressing is 60S; then, the vacuum degree is evacuated to 40Pa, and the pressure is to 40MPa; Incubate at 600 °C for 10 min; then increase from 600 °C to 1400 °C at a heating rate of 50 °C/min for 20 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表12所示：After grinding and polishing the sintered tungsten carbide sample, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 12:

表12实施例8中碳化钨硬质合金的性能参数和具体数值Table 12 Performance parameters and specific values of tungsten carbide cemented carbide in Example 8

实施例9Example 9

原料配方的称量按照下述表13中的百分比进行：The raw material formulations were weighed according to the following percentages in Table 13:

表13制备40g碳化钨硬质合金的原料及其配比Table 13 The raw materials and their proportions for preparing 40g tungsten carbide cemented carbide

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为20:1，转速为500r/min，球磨时间为30h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Put 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in a glove box filled with argon gas. The mass ratio of ball to material is 20:1 , the rotation speed is 500r/min, the ball milling time is 30h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials adhering to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain 150nm fine CoCrNiCuFe powder.

S2、将WC粉末进行球磨细化，球、料质量比为20:1，转速为300r/min，球磨20h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 20:1, the rotation speed is 300r/min, the ball-milling is 20h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain fine WC powder with a thickness of 150nm.

S3、在充满氩气的手套箱中，称取12g CoCrNiCuFe和28g WC装入WC硬质合金球磨罐中。球、料质量比为7:1，转速为350r/min，球磨时间为4.5h，每转1h停机10min进行散热。S3. In a glove box filled with argon, weigh 12g of CoCrNiCuFe and 28g of WC into a WC carbide ball mill jar. The mass ratio of balls and materials is 7:1, the rotation speed is 350r/min, the ball milling time is 4.5h, and the machine is stopped for 10min for each rotation 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为20MPa，预压60S；然后，抽真空度至40Pa，加压至40MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以100℃/min的升温速率从600℃升到1100℃，保温5min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4, first, put the mixture into the graphite mold for pre-pressing, the pre-pressing pressure is 20MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 40MPa; then, it is heated from room temperature to 600 ℃ in 5min time, Incubate at 600 °C for 10 min; then increase the temperature from 600 °C to 1100 °C at a heating rate of 100 °C/min, and hold for 5 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表14所示：After grinding and polishing the sintered tungsten carbide sample, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 14:

表14实施例9中碳化钨硬质合金的性能参数和具体数值Table 14 Performance parameters and specific values of tungsten carbide cemented carbide in Example 9

实施例10Example 10

采用表1和表13的成分制备，球磨转速、时间等进行调整：Use the ingredients in Table 1 and Table 13 to prepare, adjust the ball milling speed, time, etc.:

S1、在充满氩气的手套箱中将2.039g Co、1.799g Cr、2.031g Ni、2.199g Cu和1.932g Fe混合装入WC硬质合金球磨罐中，球、料质量比为20:1，转速为300r/min，球磨时间为45h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末。S1. Put 2.039g Co, 1.799g Cr, 2.031g Ni, 2.199g Cu and 1.932g Fe into a WC carbide ball mill in a glove box filled with argon gas. The mass ratio of ball to material is 20:1 , the rotation speed is 300r/min, the ball milling time is 45h, every 5h of rotation is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials adhering to the grinding ball and the inner wall of the tank are scraped off and mixed, and then ball-milling is continued to obtain 150nm fine CoCrNiCuFe powder.

S2、将WC粉末进行球磨细化，球、料质量比为20:1，转速为350r/min，球磨10h，每转5h停机30min进行散热，制得150nm以细的WC粉末。S2. The WC powder is ball-milled and refined, the mass ratio of ball to material is 20:1, the rotational speed is 350r/min, the ball-milling is 10h, and the machine is stopped for 30min per revolution for 5h to dissipate heat to obtain 150nm fine WC powder.

S3、在充满氩气的手套箱中，称取12g CoCrNiCuFe和28g WC装入WC硬质合金球磨罐中。球、料质量比为7:1，转速为300r/min，球磨时间为3.5h，每转1h停机10min进行散热。S3. In a glove box filled with argon, weigh 12g of CoCrNiCuFe and 28g of WC into a WC carbide ball mill jar. The mass ratio of ball and material is 7:1, the rotation speed is 300r/min, the ball milling time is 3.5h, and the machine is stopped for 10min for each rotation 1h to dissipate heat.

S4、首先，将混合料装入石墨模具中预压，预压压力为20MPa，预压60S；然后，抽真空度至40Pa，加压至50MPa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以100℃/min的升温速率从600℃升到1200℃，保温5min。随炉冷却，得到毛坯。将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。S4. First, put the mixture into a graphite mold for pre-pressing, the pre-pressing pressure is 20MPa, and the pre-pressing is 60S; then, the vacuum degree is 40Pa, and the pressure is 50MPa; Incubate at 600 °C for 10 min; then increase the temperature from 600 °C to 1200 °C at a heating rate of 100 °C/min, and maintain for 5 min. After cooling in the furnace, a blank is obtained. The prepared blank is subjected to surface grinding and deburring treatment to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.

将烧结后碳化钨硬质合金试样打磨抛光后进行组织及性能检测，所得烧结体技术参数如表15所示：After grinding and polishing the sintered tungsten carbide sample, the microstructure and properties were tested. The technical parameters of the obtained sintered body are shown in Table 15:

表15实施例10中碳化钨硬质合金的性能参数和具体数值Table 15 Performance parameters and specific values of tungsten carbide cemented carbide in Example 10

以实施例6、实施例7、实施例8为例，如图1所示，高熵合金结合的碳化钨硬质合金中均含有WC相、FCC相的CoCrNiCuFe以及Cr₂O₃相；随着烧结温度升高和保温时间延长，WC衍射峰的相对强度逐渐增强。如图2所示，随着烧结温度升高和保温时间延长，部分WC晶粒逐渐长大成多边形，WC之间结合更紧密，致密度先升高后降低。Taking Example 6, Example 7, and Example 8 as examples, as shown in Figure 1, the high-entropy alloy-bonded tungsten carbide cemented carbides all contain WC phase, FCC phase CoCrNiCuFe and Cr₂ O₃ phase; The relative intensity of WC diffraction peaks increased gradually with the increase of sintering temperature and the prolongation of holding time. As shown in Fig. 2, with the increase of sintering temperature and the prolongation of holding time, part of the WC grains gradually grew into polygons, the bonding between WCs was tighter, and the density first increased and then decreased.

实验数据总结：通过实施例1-10可知，CoCrNiCuFe高熵合金含量、烧结温度以及保温时间对高熵合金结合的碳化钨硬质合金的性能影响较大。由实施例4和实施例10可知，CoCrNiCuFe高熵合金含量增加，硬质合金的硬度降低，韧性和致密度升高。由实施例5和实施例9可知，CoCrNiCuFe高熵合金含量继续增加时，韧性提高较小，而硬度下降较快，只有确保CoCrNiCuFe高熵合金含量在适当范围内，才能得到综合性能较好的硬质合金烧结体。由实施例6、实施例7和实施例8可知，随着烧结温度升高和保温时间延长，硬质合金的硬度、韧性和致密度先升高后降低。由实施例1和实施例2可知，球磨转速和球磨时间可相互平衡，提高转速可以缩短球磨时间，增加球磨时间可以降低转速。Summary of experimental data: It can be seen from Examples 1-10 that the content of CoCrNiCuFe high-entropy alloy, sintering temperature and holding time have great influence on the properties of tungsten carbide cemented with high-entropy alloy. It can be seen from Example 4 and Example 10 that the content of CoCrNiCuFe high-entropy alloy increases, the hardness of cemented carbide decreases, and the toughness and density increase. It can be seen from Example 5 and Example 9 that when the content of CoCrNiCuFe high-entropy alloy continues to increase, the increase in toughness is small, while the hardness decreases rapidly. Alloy sintered body. It can be seen from Example 6, Example 7 and Example 8 that with the increase of sintering temperature and the prolongation of holding time, the hardness, toughness and density of cemented carbide first increased and then decreased. It can be seen from Example 1 and Example 2 that the ball milling speed and the ball milling time can be balanced with each other, increasing the speed can shorten the ball milling time, and increasing the ball milling time can reduce the speed.

最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that: The technical solutions described in the foregoing embodiments can still be modified, or some or all of the technical features thereof can be equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the technical solutions of the embodiments of the present invention. scope.

Claims (7)

Translated fromChinese

1.一种高熵合金结合的碳化钨硬质合金，其特征在于，所述硬质合金按照质量百分比计成分为：CoCrNiCuFe占5～30wt.％，余量为WC。1. A high-entropy alloy combined tungsten carbide cemented carbide is characterized in that, the cemented carbide is composed of: CoCrNiCuFe accounts for 5～30wt.% according to mass percentage, and the remainder is WC.2.根据权利要求1所述的高熵合金结合的碳化钨硬质合金，其特征在于，所述CoCrNiCuFe的粒径为150nm以细；WC的纯度为＞99％，粒径为150nm以细。2 . The high-entropy alloy-bonded tungsten carbide cemented carbide according to claim 1 , wherein the particle size of the CoCrNiCuFe is finer than 150 nm; the purity of WC is >99%, and the particle size is finer than 150 nm. 3 .3.一种如权利要求1或2所述高熵合金结合的碳化钨硬质合金的制备方法，其特征在于包括如下步骤，3. a preparation method of the tungsten carbide cemented carbide combined by the high entropy alloy as claimed in claim 1 or 2, is characterized in that comprising the steps,S1、CoCrNiCuFe粉末制备：在充满氩气的手套箱中将Co、Cr、Ni、Cu、Fe按1:1:1:1:1摩尔比混合装入WC硬质合金球磨罐中，球、料质量比为10:1～20:1，转速为300～600r/min，球磨时间为20～50h，每转5h停机30min散热，每10h停机把粘到磨球及罐内壁的原料刮掉混匀后继续球磨，制得150nm以细的CoCrNiCuFe粉末；S1. Preparation of CoCrNiCuFe powder: in a glove box filled with argon, mix Co, Cr, Ni, Cu, and Fe into a WC carbide ball mill in a molar ratio of 1:1:1:1:1. The mass ratio is 10:1～20:1, the rotating speed is 300～600r/min, the ball milling time is 20～50h, every 5h of revolution, the machine is stopped for 30min to dissipate heat, and every 10h of stoppage, the raw materials sticking to the grinding ball and the inner wall of the tank are scraped off and mixed evenly. Then continue ball milling to obtain CoCrNiCuFe powder with a thickness of 150nm;S2、WC粉末制备：将WC粉末进行球磨细化，球、料质量比为10:1～20:1，转速为250～400r/min，球磨时间为10～40h，每转5h停机30min进行散热，制得150nm以细的WC粉末；S2. Preparation of WC powder: The WC powder is ball-milled and refined, the mass ratio of ball to material is 10:1-20:1, the rotational speed is 250-400r/min, the ball-milling time is 10-40h, and the machine is stopped for 30min per revolution for 5h to dissipate heat. , to obtain 150nm fine WC powder;S3、混料：在充满氩气的手套箱中，称取质量百分比为5～30wt.％由步骤S1制备的CoCrNiCuFe粉末，加入由步骤S2制备的WC粉末中后进行球磨混料，球、料质量比为5:1～10:1，转速为200～350r/min，球磨时间为2～5h，每转1h停机10min进行散热；S3. Mixing: In a glove box filled with argon, weigh the CoCrNiCuFe powder prepared in step S1 with a mass percentage of 5-30 wt. The mass ratio is 5:1~10:1, the speed is 200~350r/min, the ball milling time is 2~5h, and the machine is stopped for 10min after each revolution of 1h to dissipate heat;S4、烧结制备：将由步骤S3混合后的混合料装入石墨模具中预压，预压压力为10～30MPa，预压60S；然后进行放电等离子烧结，真空度为40Pa，烧结压力为40～50MPa，烧结温度为1100～1400℃，升温速率为30～100℃/min，保温时间为3～30min；然后降温卸压，制得高熵合金结合的碳化钨硬质合金。S4, sintering preparation: put the mixture mixed in step S3 into a graphite mold for pre-pressing, the pre-pressing pressure is 10-30 MPa, and the pre-pressing is 60 s; then spark plasma sintering is performed, the vacuum degree is 40 Pa, and the sintering pressure is 40-50 MPa , the sintering temperature is 1100-1400°C, the heating rate is 30-100°C/min, and the holding time is 3-30min; then the temperature is lowered and the pressure is relieved to obtain a high-entropy alloy-bonded tungsten carbide cemented carbide.4.根据权利要求3所述的制备方法，其特征在于，所述Co、Cr、Ni、Cu、Fe粉末纯度为＞99％，其中，Co粉末粒径为1～3μm，Cr粉末粒径为＜75μm，其余金属单质粉末粒径为＜45μm。4 . The preparation method according to claim 3 , wherein the purity of the Co, Cr, Ni, Cu, and Fe powders is >99%, wherein the particle size of the Co powder is 1-3 μm, and the particle size of the Cr powder is 1-3 μm. 5 . <75μm, and the particle size of other metal element powders is <45μm.5.根据权利要求3所述的制备方法，其特征在于，所述WC粉末的粒径为1～3μm，纯度为＞99％。5 . The preparation method according to claim 3 , wherein the particle size of the WC powder is 1-3 μm, and the purity is >99%. 6 .6.根据权利要求3所述的制备方法，其特征在于，步骤S1、S2和S3的球磨过程均采用直径分别为8mm、5mm和2mm三种大、中、小规格的WC硬质合金球，其中，大、中、小规格的WC硬质合金球的质量比为3:1:1。6. preparation method according to claim 3 is characterized in that, the ball milling process of step S1, S2 and S3 all adopts the WC carbide balls with diameters of three kinds of large, medium and small sizes of 8mm, 5mm and 2mm, respectively, Among them, the mass ratio of large, medium and small WC carbide balls is 3:1:1.7.根据权利要求3所述的制备方法，其特征在于，步骤S4中具体烧结工艺为：首先，对样品缓慢施加压力至40～50MPa；然后，抽真空度至40Pa；接着，用5min时间从室温加热到600℃，在600℃保温10min；再以30～100℃/min的升温速率从600℃升到1100～1400℃，保温3～30min；随炉冷却，得到毛坯；将制备的毛坯进行表面磨削、去毛刺处理，得到高熵合金结合的碳化钨硬质合金。7. The preparation method according to claim 3, wherein the specific sintering process in step S4 is: first, slowly apply pressure to the sample to 40-50MPa; then, vacuumize to 40Pa; Heating at room temperature to 600°C, holding at 600°C for 10min; then raising the temperature from 600°C to 1100-1400°C at a heating rate of 30-100°C/min, holding for 3-30min; cooling with the furnace to obtain a blank; Surface grinding and deburring treatment to obtain high-entropy alloy-bonded tungsten carbide cemented carbide.

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