CN106001566A - High-strength high-entropy alloy NbMoTaWV and preparation method thereof - Google Patents
High-strength high-entropy alloy NbMoTaWV and preparation method thereof Download PDFInfo
- Publication number
- CN106001566A CN106001566A CN201610508519.XA CN201610508519A CN106001566A CN 106001566 A CN106001566 A CN 106001566A CN 201610508519 A CN201610508519 A CN 201610508519A CN 106001566 A CN106001566 A CN 106001566A
- Authority
- CN
- China
- Prior art keywords
- nbmotawv
- alloy
- entropy alloy
- sintering
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 94
- 239000000956 alloy Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000005245 sintering Methods 0.000 claims abstract description 36
- 238000002490 spark plasma sintering Methods 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 19
- 239000011159 matrix material Substances 0.000 claims abstract description 17
- 238000005516 engineering process Methods 0.000 claims abstract description 10
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000006104 solid solution Substances 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 41
- 238000000498 ball milling Methods 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 229910052715 tantalum Inorganic materials 0.000 claims description 11
- 229910052721 tungsten Inorganic materials 0.000 claims description 11
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- 229910052758 niobium Inorganic materials 0.000 claims description 9
- 239000013590 bulk material Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000713 high-energy ball milling Methods 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 4
- 238000005266 casting Methods 0.000 abstract description 9
- 210000001787 dendrite Anatomy 0.000 abstract description 4
- 238000010891 electric arc Methods 0.000 abstract description 2
- 238000005204 segregation Methods 0.000 abstract description 2
- 239000011812 mixed powder Substances 0.000 description 13
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005275 alloying Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000004663 powder metallurgy Methods 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 3
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/045—Alloys based on refractory metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
Abstract
本发明属于高熵合金技术领域，公开了一种高强度高熵合金NbMoTaWV及其制备方法。该方法采用机械合金化和放电等离子烧结技术相结合的成形方法。本发明方法比传统真空电弧炉熔铸法操作更加简便，成形所需的温度大幅度降低，烧结时间短，一次烧结即可获得成分均匀且近全致密的块体材料，并且消除了合金的枝晶偏析，使晶粒明显细化，得到的合金密度为11.6～11.9g/cm3，其显微组织为等轴晶基体中弥散分布着颗粒状第二相，基体和第二相均为BCC结构固溶体，室温下最佳压缩力学性能：σ0.2为2770MPa，σbc为3661MPa，断裂时εp为12.5％，室温强度和塑性均显著提升，具有十分优异的综合力学性能。The invention belongs to the technical field of high-entropy alloys, and discloses a high-strength high-entropy alloy NbMoTaWV and a preparation method thereof. The method adopts a forming method combining mechanical alloying and spark plasma sintering technology. The method of the invention is easier to operate than the traditional vacuum electric arc furnace casting method, the temperature required for forming is greatly reduced, the sintering time is short, and a uniform and nearly fully dense block material can be obtained by one sintering, and the dendrite of the alloy is eliminated Segregation makes the grains significantly refined, and the obtained alloy has a density of 11.6-11.9g/cm 3 , and its microstructure is a granular second phase dispersed in an equiaxed crystal matrix, and both the matrix and the second phase are of BCC structure Solid solution, the best compressive mechanical properties at room temperature: σ 0.2 is 2770MPa, σ bc is 3661MPa, ε p is 12.5% at fracture, the strength and plasticity at room temperature are significantly improved, and it has very excellent comprehensive mechanical properties.
Description
技术领域technical field
本发明属于高熵合金技术领域，特别涉及一种高强度高熵合金NbMoTaWV及其制备方法。The invention belongs to the technical field of high-entropy alloys, in particular to a high-strength high-entropy alloy NbMoTaWV and a preparation method thereof.
背景技术Background technique
上世纪九十年代提出的高熵合金是一种突破传统合金设计理念的新型合金。这类合金的主要元素数目一般都大于五，每种元素的原子百分比大致相同，且没有一种组元的原子百分比会超过50％而成为唯一的主要元素。由于合金在凝固过程中存在高熵效应，故虽然主要元素较多，但这类合金不但不会生成各种复杂的金属间化合物，反而形成了简单的固溶体相(如：体心立方(BCC)，面心立方(FCC)或密排六方(HCP))。与传统合金相比，多主元的高熵合金具有高强度、高硬度、耐磨、耐腐蚀和抗高温软化等优异性能。The high-entropy alloy proposed in the 1990s is a new type of alloy that breaks through the traditional alloy design concept. The number of main elements in this type of alloy is generally greater than five, and the atomic percentage of each element is roughly the same, and no component has an atomic percentage of more than 50% and becomes the only main element. Due to the high entropy effect of the alloy during solidification, although there are many main elements, this type of alloy will not generate various complex intermetallic compounds, but will form a simple solid solution phase (such as: body centered cubic (BCC) , face centered cubic (FCC) or hexagonal close packed (HCP)). Compared with traditional alloys, multi-principal high-entropy alloys have excellent properties such as high strength, high hardness, wear resistance, corrosion resistance, and high temperature softening resistance.
高熵合金元素体系的选择主要集中于后过渡金属，如Cr、Mn、Fe、Co、Ni、Cu等。2011年，Senkov O.N.等人通过熔铸法首先制备出以Nb、Mo、Ta、W、V高熔点金属为主要元素的新型高熵合金，其显微组织为单相BCC结构，室温下的压缩屈服强度为1246MPa，最大压缩强度为1270MPa，断裂时的塑性应变量为1.7％，并且在600～1600℃高温下仍能保持较高的强度，因此该合金极有可能成为新一代的高温合金、刀具、模具和耐磨材料，得到广泛应用。The selection of high-entropy alloy element systems mainly focuses on late transition metals, such as Cr, Mn, Fe, Co, Ni, Cu, etc. In 2011, Senkov O.N. et al. first prepared a new type of high-entropy alloy with Nb, Mo, Ta, W, and V high-melting point metals as main elements by melting and casting. Its microstructure is a single-phase BCC structure, and its compression yield at room temperature The strength is 1246MPa, the maximum compressive strength is 1270MPa, the plastic strain at fracture is 1.7%, and it can still maintain high strength at a high temperature of 600-1600°C, so this alloy is very likely to become a new generation of superalloys, cutting tools , molds and wear-resistant materials are widely used.
目前，高熵合金的制备以真空电弧炉熔铸法为主。然而，NbMoTaWV高熔点高熵合金的制备过程中却存在一系列难点：由于合金的熔点较高(约为2673℃)，传统的熔铸法必然要克服加热温度高的难题，工艺难度较大；为了使成分均匀，需要经过多次重熔；同时，熔铸法制备的NbMoTaWV合金晶粒易长大为粗大的树枝晶，平均晶粒尺寸约为80μm；熔液凝固过程中不可避免地会产生枝晶偏析等成分不均匀现象，这些都会对最终产品的性能产生较大的影响。At present, the preparation of high-entropy alloys is mainly based on vacuum electric arc furnace casting. However, there are a series of difficulties in the preparation process of NbMoTaWV high-melting-point high-entropy alloy: due to the high melting point of the alloy (about 2673 ° C), the traditional casting method must overcome the problem of high heating temperature, and the process is difficult; To make the composition uniform, it needs to undergo multiple remelting; at the same time, the NbMoTaWV alloy grains prepared by the melting casting method are easy to grow into thick dendrites, with an average grain size of about 80 μm; dendrites will inevitably occur during the solidification of the melt Inhomogeneous composition such as segregation will have a greater impact on the performance of the final product.
近年来，开始有学者采用粉末冶金法制备高熵合金。相比于传统的熔铸法，粉末冶金法工艺简单，且制备出的合金晶粒更加细小、组织更加均匀，综合力学性能甚至超过传统熔铸法制备出的合金。例如：采用机械合金化和放电等离子烧结法制备出的Al0.6CoNiFeTi0.4合金的压缩屈服强度和断裂强度分别达到2732MPa和3172MPa，塑性变形量达到了10.1％，表现出良好的综合力学性能(Materials Science&Engineering A,565(2013):439–444)。然而，采用粉末冶金法制备高熵合金的研究还处于起步阶段，该方法并未用于制备NbMoTaWV高熔点高熵合金。In recent years, some scholars have begun to use powder metallurgy to prepare high-entropy alloys. Compared with the traditional melting and casting method, the powder metallurgy method has a simpler process, and the prepared alloy has finer grains and a more uniform structure, and its comprehensive mechanical properties even exceed those prepared by the traditional melting and casting method. For example: the compressive yield strength and fracture strength of the Al 0.6 CoNiFeTi 0.4 alloy prepared by mechanical alloying and spark plasma sintering reached 2732MPa and 3172MPa respectively, and the plastic deformation reached 10.1%, showing good comprehensive mechanical properties (Materials Science & Engineering A, 565(2013):439–444). However, the research on the preparation of high-entropy alloys by powder metallurgy is still in its infancy, and this method has not been used to prepare NbMoTaWV high-melting-point high-entropy alloys.
目前关于高熔点高熵合金的文献十分有限，高熔点高熵合金NbMoTaWV的制备方法也仅限于电弧熔铸法。为了改善该类合金的组织和性能，同时降低加工所需温度，简化制备工艺，本发明采用粉末冶金的方法制备NbMoTaWV合金。本发明对于发展高熵合金的制备技术，提高高熵合金的力学性能，促进高熵合金的研究和应用都将具有十分重要的意义。At present, the literature on high melting point high entropy alloys is very limited, and the preparation method of high melting point high entropy alloy NbMoTaWV is limited to arc melting method. In order to improve the structure and performance of this type of alloy, reduce the temperature required for processing, and simplify the preparation process, the invention adopts a powder metallurgy method to prepare the NbMoTaWV alloy. The invention has very important significance for developing the preparation technology of the high-entropy alloy, improving the mechanical properties of the high-entropy alloy, and promoting the research and application of the high-entropy alloy.
发明内容Contents of the invention
为了克服上述现有技术的缺点与不足，本发明的首要目的在于提供一种高强度高熵合金NbMoTaWV的制备方法。本发明方法先采用机械合金化制备出单相体心立方(BCC)结构的合金粉末，再利用放电等离子烧结(SPS)进行烧结，得到块体材料，通过优化工艺，实现近净成形，获得组织均匀、晶粒细小、具有较高强度和塑性的块体材料。In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the primary purpose of the present invention is to provide a method for preparing a high-strength high-entropy alloy NbMoTaWV. The method of the invention first adopts mechanical alloying to prepare alloy powder with a single-phase body-centered cubic (BCC) structure, and then uses spark plasma sintering (SPS) to sinter to obtain a bulk material. Uniform, fine-grained bulk material with high strength and plasticity.
本发明另一目的在于提供上述方法制备的高强度高熵合金NbMoTaWV。Another object of the present invention is to provide the high-strength high-entropy alloy NbMoTaWV prepared by the above method.
本发明的目的通过下述方案实现：The object of the present invention is achieved through the following solutions:
一种高强度高熵合金NbMoTaWV的制备方法，该方法采用机械合金化和放电等离子烧结技术相结合的成形方法，具体为采用机械合金化制备单相BCC结构的NbMoTaWV高熵合金粉末，再利用放电等离子烧结技术对上述粉末进行烧结，得到高强度高熵合金NbMoTaWV块体材料。A preparation method of high-strength high-entropy alloy NbMoTaWV, which adopts a forming method combining mechanical alloying and spark plasma sintering technology, specifically preparing NbMoTaWV high-entropy alloy powder with a single-phase BCC structure by mechanical alloying, and then using electric discharge The plasma sintering technology sinters the above powder to obtain a high-strength high-entropy alloy NbMoTaWV bulk material.
更具体包括如下步骤和工艺条件：More specifically, the following steps and process conditions are included:
步骤一：采用机械合金化法制备NbMoTaWV高熵合金粉末Step 1: Preparation of NbMoTaWV high-entropy alloy powder by mechanical alloying method
将Nb、Mo、Ta、W、V单质粉末混合进行高能球磨，得到单相BCC结构的NbMoTaWV合金粉末；Mix Nb, Mo, Ta, W, V elemental powders for high-energy ball milling to obtain NbMoTaWV alloy powders with single-phase BCC structure;
步骤二：放电等离子烧结Step 2: Spark plasma sintering
采用放电等离子烧结炉烧结步骤一得到的合金粉末，其工艺条件如下：The alloy powder obtained in step 1 is sintered in a spark plasma sintering furnace, and the process conditions are as follows:
烧结设备：放电等离子烧结系统Sintering equipment: spark plasma sintering system
烧结电流类型：直流脉冲电流Sintering current type: DC pulse current
烧结温度：1300～1600℃Sintering temperature: 1300～1600℃
保温时间：5～20minHeat preservation time: 5～20min
烧结压力：30～50MPaSintering pressure: 30~50MPa
升温速率：50～200℃/minHeating rate: 50～200℃/min
经烧结获得NbMoTaWV高强度高熵合金块体材料。The NbMoTaWV high-strength high-entropy alloy bulk material is obtained by sintering.
步骤一中所述机械合金化过程中采用的球磨罐和磨球的材质优选为不锈钢或硬质合金，所述球磨的工艺条件为：球料比为5:1～14:1，转速为100～300r/min，球磨时间为10～80h。The material of the ball mill pot and balls used in the mechanical alloying process described in step 1 is preferably stainless steel or hard alloy, and the process conditions of the ball mill are: the ball-to-material ratio is 5:1 to 14:1, and the speed is 100 ~300r/min, ball milling time is 10~80h.
步骤一中所用Nb、Mo、Ta、W、V单质粉末的量优选为等原子比，也可选择非等原子比。The amount of Nb, Mo, Ta, W, and V elemental powders used in step 1 is preferably in an equiatomic ratio, or a non-equivalent atomic ratio can also be selected.
步骤一中的混合粉末在高能球磨过程中，逐渐实现合金化，最后形成单相BCC结构的合金粉末，此时，合金化过程完成，取出NbMoTaWV高熵合金粉末用于后续的烧结。The mixed powder in step 1 is gradually alloyed during the high-energy ball milling process, and finally forms an alloy powder with a single-phase BCC structure. At this time, the alloying process is completed, and the NbMoTaWV high-entropy alloy powder is taken out for subsequent sintering.
步骤一中的球磨过程优选在惰性气体保护下进行。The ball milling process in step 1 is preferably carried out under the protection of an inert gas.
本发明提供一种上述方法制备得到的NbMoTaWV高强度高熵合金块体材料，密度为11.6～11.9g/cm3，其显微组织为等轴晶基体中弥散分布着颗粒状第二相，其中基体和第二相均为BCC结构固溶体，且基体富集较多的W、Mo、Nb，其平均晶粒尺寸<6μm；而第二相富集较多的Ta、V，其平均晶粒尺寸<1μm。The present invention provides a NbMoTaWV high-strength high-entropy alloy bulk material prepared by the above method, with a density of 11.6 to 11.9 g/cm 3 , and a microstructure in which granular second phases are dispersed in an equiaxed crystal matrix, wherein Both the matrix and the second phase are solid solutions with a BCC structure, and the matrix is rich in W, Mo, and Nb, and its average grain size is <6 μm; while the second phase is rich in Ta, V, and its average grain size <1μm.
本发明相对于现有技术，具有如下的优点及有益效果：Compared with the prior art, the present invention has the following advantages and beneficial effects:
(1)本发明采用机械合金化和放电等离子烧结相结合的方法制备NbMoTaWV高熵合金，成形工艺比传统的真空电弧炉熔铸法操作更加简便，成形所需的温度大幅度降低(从≥2673℃降低至≤1600℃)，烧结时间短，一次烧结即可获得成分均匀且近全致密的块体材料，并且可实现近净成形。采用本发明工艺简化，实用性好，且有效地降低了能耗，因此具有良好的发展前景。(1) The present invention adopts the combined method of mechanical alloying and spark plasma sintering to prepare NbMoTaWV high-entropy alloy. The forming process is easier to operate than the traditional vacuum arc furnace casting method, and the temperature required for forming is greatly reduced (from ≥ 2673 °C reduced to ≤1600°C), the sintering time is short, a homogeneous and nearly fully dense bulk material can be obtained in one sintering, and a near-net shape can be achieved. The process of the invention is simplified, the practicability is good, and the energy consumption is effectively reduced, so it has a good development prospect.
(2)本发明消除了铸造高熵合金NbMoTaWV中的粗大枝晶组织，基体组织转变为细小的等轴晶，从而使平均晶粒尺寸减小、成分更加均匀，进而提高材料的强度和塑性，促进高强度高熵合金的研究和应用。(2) The present invention eliminates the coarse dendrite structure in the cast high-entropy alloy NbMoTaWV, and the matrix structure is transformed into fine equiaxed crystals, thereby reducing the average grain size and making the composition more uniform, thereby improving the strength and plasticity of the material, Promote the research and application of high-strength high-entropy alloys.
(3)本发明制备的高强度高熵合金NbMoTaWV室温下的最佳力学性能为：压缩屈服强度σ0.2＝2770MPa，最大抗压强度σbc＝3661MPa，断裂时的塑性应变量εp＝12.5％，与熔铸法获得的同类合金相比，在大幅度提高了室温强度的基础上，室温塑性也显著提升，从而改善了合金的综合力学性能。(3) The best mechanical properties of the high-strength high-entropy alloy NbMoTaWV prepared by the present invention at room temperature are: compressive yield strength σ 0.2 = 2770MPa, maximum compressive strength σ bc = 3661MPa, plastic strain ε p = 12.5% at fracture , compared with similar alloys obtained by melting and casting, on the basis of greatly improving the strength at room temperature, the plasticity at room temperature is also significantly improved, thereby improving the comprehensive mechanical properties of the alloy.
具体实施方式detailed description
下面结合实施例对本发明作进一步详细的描述，但本发明的实施方式不限于此。The present invention will be further described in detail below in conjunction with examples, but the embodiments of the present invention are not limited thereto.
实施例1Example 1
一种高强度高熵合金NbMoTaWV材料的制备方法采用机械合金化和放电等离子烧结技术相结合的成形方法，它包括如下步骤及其工艺条件：A preparation method of a high-strength high-entropy alloy NbMoTaWV material adopts a forming method combining mechanical alloying and spark plasma sintering technology, which includes the following steps and process conditions:
步骤一：采用机械合金化法制备NbMoTaWV高熵合金粉末Step 1: Preparation of NbMoTaWV high-entropy alloy powder by mechanical alloying method
(1)按等原子比称取Nb、Mo、Ta、W、V单质粉末各20at.％，并混合均匀。(1) Weigh 20 at.% each of Nb, Mo, Ta, W, and V elemental powders according to the equiatomic ratio, and mix them evenly.
(2)将混合粉末和磨球加入行星式高能球磨机的球磨罐中进行球磨，罐体材料及磨球的材质均为硬质合金，球磨罐内抽真空并充高纯氩气(99.99％)作为保护气氛。随着球磨时间的延长，混合粉末逐步实现合金化，由多种单质粉末的混合粉末转变为具有单相BCC结构的合金粉末，同时，粉末内部的晶粒不断细化。高能球磨过程中采用的球料比为10:1，转速为300r/min，球磨时间为10h。(2) Put the mixed powder and balls into the ball mill tank of the planetary high-energy ball mill for ball milling. The material of the tank body and the balls are all hard alloy. The ball mill tank is evacuated and filled with high-purity argon (99.99%) as a protective atmosphere. With the prolongation of ball milling time, the mixed powder gradually realizes alloying, and the mixed powder of various elemental powders is transformed into an alloy powder with a single-phase BCC structure. At the same time, the grains inside the powder are continuously refined. The ball-to-material ratio used in the high-energy ball milling process was 10:1, the rotational speed was 300r/min, and the ball-milling time was 10h.
步骤二：放电等离子烧结Step 2: Spark plasma sintering
采用放电等离子烧结炉烧结步骤一中的合金粉末，其工艺条件如下：The alloy powder in step 1 is sintered in a spark plasma sintering furnace, and the process conditions are as follows:
烧结设备：放电等离子烧结系统Sintering equipment: spark plasma sintering system
烧结电流类型：直流脉冲电流Sintering current type: DC pulse current
烧结温度：1500℃Sintering temperature: 1500°C
保温时间：10minHeat preservation time: 10min
烧结压力：30MPaSintering pressure: 30MPa
升温速率：100℃/minHeating rate: 100°C/min
经本实施例烧结后，NbMoTaWV高熵合金的显微组织由BCC单相组织转变为两种BCC相的混合组织，析出的颗粒状第二相均匀分布于等轴晶基体中，基体的平均晶粒尺寸为2.7μm；第二相的平均晶粒尺寸为0.5μm，所占体积百分比约为13.8％。高熵合金烧结材料的密度为11.6g/cm3，室温下压缩屈服强度σ0.2达到2770MPa，最大抗压强度σbc达到3661MPa，断裂时的塑性应变量εp达到12.5％，显微硬度为774Hv。After sintering in this example, the microstructure of the NbMoTaWV high-entropy alloy changed from a BCC single-phase structure to a mixed structure of two BCC phases, and the precipitated granular second phase was uniformly distributed in the equiaxed crystal matrix, and the average grain size of the matrix The grain size is 2.7 μm; the average grain size of the second phase is 0.5 μm, accounting for about 13.8% by volume. The density of the high-entropy alloy sintered material is 11.6g/cm 3 , the compressive yield strength σ 0.2 at room temperature reaches 2770MPa, the maximum compressive strength σbc reaches 3661MPa , the plastic strain εp at fracture reaches 12.5%, and the microhardness is 774Hv .
实施例2Example 2
一种高强度高熵合金NbMoTaWV材料的制备方法采用机械合金化和放电等离子烧结技术相结合的成形方法，它包括如下步骤及其工艺条件：A preparation method of a high-strength high-entropy alloy NbMoTaWV material adopts a forming method combining mechanical alloying and spark plasma sintering technology, which includes the following steps and process conditions:
步骤一：采用机械合金化法制备NbMoTaWV高熵合金粉末Step 1: Preparation of NbMoTaWV high-entropy alloy powder by mechanical alloying method
(1)按等原子比称取Nb、Mo、Ta、W、V单质粉末各20at.％，并混合均匀。(1) Weigh 20 at.% each of Nb, Mo, Ta, W, and V elemental powders according to the equiatomic ratio, and mix them uniformly.
(2)将混合粉末和磨球加入行星式高能球磨机的球磨罐中进行球磨，罐体材料及磨球的材质均为不锈钢，球磨罐内抽真空并充高纯氩气(99.99％)作为保护气氛。随着球磨时间的延长，混合粉末逐步实现合金化，由多种单质粉末的混合粉末转变为具有单相BCC结构的合金粉末，同时粉末内部的晶粒不断细化。高能球磨过程中采用的球料比为5:1，转速为250r/min，球磨时间为80h。(2) Put the mixed powder and balls into the ball mill tank of the planetary high-energy ball mill for ball milling. The material of the tank body and the balls are all stainless steel. The ball mill tank is evacuated and filled with high-purity argon (99.99%) as a protection atmosphere. With the prolongation of ball milling time, the mixed powder gradually realizes alloying, and the mixed powder of various single powders is transformed into an alloy powder with a single-phase BCC structure, and the grains inside the powder are continuously refined. The ball-to-material ratio used in the high-energy ball milling process was 5:1, the rotational speed was 250r/min, and the ball-milling time was 80h.
步骤二：放电等离子烧结Step 2: Spark plasma sintering
采用放电等离子烧结炉烧结步骤一中的合金粉末，其工艺条件如下：The alloy powder in step 1 is sintered in a spark plasma sintering furnace, and the process conditions are as follows:
烧结设备：放电等离子烧结系统Sintering equipment: spark plasma sintering system
烧结电流类型：直流脉冲电流Sintering current type: DC pulse current
烧结温度：1600℃Sintering temperature: 1600°C
保温时间：5minHolding time: 5min
烧结压力：30MPaSintering pressure: 30MPa
升温速率：200℃/minHeating rate: 200°C/min
经本实施例烧结后，NbMoTaWV高熵合金的显微组织由BCC单相组织转变为两种BCC相的混合组织，析出的颗粒状第二相均匀分布于等轴晶基体中，基体的平均晶粒尺寸为5.2μm，第二相的平均晶粒尺寸为0.7μm，所占体积百分比约为19.9％。合金的密度为11.6g/cm3，室温下的最大抗压强度σbc为2059MPa，显微硬度为744Hv。After sintering in this example, the microstructure of the NbMoTaWV high-entropy alloy changed from a BCC single-phase structure to a mixed structure of two BCC phases, and the precipitated granular second phase was uniformly distributed in the equiaxed crystal matrix, and the average grain size of the matrix The grain size is 5.2 μm, the average grain size of the second phase is 0.7 μm, and the volume percentage is about 19.9%. The density of the alloy is 11.6g/cm 3 , the maximum compressive strength σ bc at room temperature is 2059MPa, and the microhardness is 744Hv.
实施例3Example 3
一种高强度高熵合金NbMoTaWV材料的制备方法采用机械合金化和放电等离子烧结技术相结合的成形方法，它包括如下步骤及其工艺条件：A preparation method of a high-strength high-entropy alloy NbMoTaWV material adopts a forming method combining mechanical alloying and spark plasma sintering technology, which includes the following steps and process conditions:
步骤一：采用机械合金化法制备NbMoTaWV高熵合金粉末Step 1: Preparation of NbMoTaWV high-entropy alloy powder by mechanical alloying method
(1)按等原子比称取Nb、Mo、Ta、W、V单质粉末各20at.％，并混合均匀。(1) Weigh 20 at.% each of Nb, Mo, Ta, W, and V elemental powders according to the equiatomic ratio, and mix them evenly.
(2)将混合粉末和磨球加入行星式高能球磨机的球磨罐中进行球磨，罐体材料及磨球的材质均为不锈钢，球磨罐内抽真空并充高纯氩气(99.99％)作为保护气氛。随着球磨时间的延长，混合粉末逐步实现合金化，由多种单质粉末的混合粉末转变为具有单相BCC结构的合金粉末，同时粉末内部的晶粒不断细化。高能球磨过程中采用的球料比为14:1，转速为100r/min，球磨时间为60h。(2) Put the mixed powder and balls into the ball mill tank of the planetary high-energy ball mill for ball milling. The material of the tank body and the balls are all stainless steel. The ball mill tank is evacuated and filled with high-purity argon (99.99%) as a protection atmosphere. With the prolongation of ball milling time, the mixed powder gradually realizes alloying, and the mixed powder of various single powders is transformed into an alloy powder with a single-phase BCC structure, and the grains inside the powder are continuously refined. The ball-to-material ratio used in the high-energy ball milling process is 14:1, the rotating speed is 100r/min, and the ball-milling time is 60h.
步骤二：放电等离子烧结Step 2: Spark plasma sintering
采用放电等离子烧结炉烧结步骤一中的合金粉末，其工艺条件如下：The alloy powder in step 1 is sintered in a spark plasma sintering furnace, and the process conditions are as follows:
烧结设备：放电等离子烧结系统Sintering equipment: spark plasma sintering system
烧结电流类型：直流脉冲电流Sintering current type: DC pulse current
烧结温度：1300℃Sintering temperature: 1300°C
保温时间：15minHolding time: 15min
烧结压力：50MPaSintering pressure: 50MPa
升温速率：50℃/minHeating rate: 50°C/min
经本实施例烧结后，NbMoTaWV高熵合金的显微组织由BCC单相组织转变为两种BCC相的混合组织，析出的颗粒状第二相均匀分布于等轴晶基体中，基体平均晶粒尺寸为0.7μm；第二相的平均晶粒尺寸为0.2μm，所占体积百分比约为5.1％。合金的密度为11.8g/cm3，室温下的最大抗压强度σbc为2248MPa，显微硬度为851Hv。After sintering in this example, the microstructure of the NbMoTaWV high-entropy alloy changed from a BCC single-phase structure to a mixed structure of two BCC phases, and the precipitated granular second phase was evenly distributed in the equiaxed crystal matrix, and the average grain size of the matrix The size is 0.7 μm; the average grain size of the second phase is 0.2 μm, accounting for about 5.1% by volume. The density of the alloy is 11.8g/cm 3 , the maximum compressive strength σ bc at room temperature is 2248MPa, and the microhardness is 851Hv.
实施例4Example 4
一种高强度高熵合金NbMoTaWV材料的制备方法采用机械合金化和放电等离子烧结技术相结合的成形方法，它包括如下步骤及其工艺条件：A preparation method of a high-strength high-entropy alloy NbMoTaWV material adopts a forming method combining mechanical alloying and spark plasma sintering technology, which includes the following steps and process conditions:
步骤一：采用机械合金化法制备NbMoTaWV高熵合金粉末Step 1: Preparation of NbMoTaWV high-entropy alloy powder by mechanical alloying method
(1)按等原子比称取Nb、Mo、Ta、W、V单质粉末各20at.％，并混合均匀。(1) Weigh 20 at.% each of Nb, Mo, Ta, W, and V elemental powders according to the equiatomic ratio, and mix them uniformly.
(2)将混合粉末和磨球加入行星式高能球磨机的球磨罐中进行球磨，罐体材料及磨球的材质均为不锈钢，球磨罐内抽真空并充高纯氩气(99.99％)作为保护气氛。随着球磨时间的延长，混合粉末逐步实现合金化，由多种单质粉末的混合粉末转变为具有单相BCC结构的合金粉末，同时，粉末内部的晶粒不断细化。高能球磨过程中采用的球料比为8:1，转速为200r/min，球磨时间为40h。(2) Put the mixed powder and balls into the ball mill tank of the planetary high-energy ball mill for ball milling. The material of the tank body and the balls are all stainless steel. The ball mill tank is evacuated and filled with high-purity argon (99.99%) as a protection atmosphere. With the prolongation of ball milling time, the mixed powder gradually realizes alloying, and the mixed powder of various elemental powders is transformed into an alloy powder with a single-phase BCC structure. At the same time, the grains inside the powder are continuously refined. The ball-to-material ratio used in the high-energy ball milling process was 8:1, the rotational speed was 200r/min, and the ball-milling time was 40h.
步骤二：放电等离子烧结Step 2: Spark plasma sintering
采用放电等离子烧结炉烧结步骤一中的合金粉末，其工艺条件如下：The alloy powder in step 1 is sintered in a spark plasma sintering furnace, and the process conditions are as follows:
烧结设备：放电等离子烧结系统Sintering equipment: spark plasma sintering system
烧结电流类型：直流脉冲电流Sintering current type: DC pulse current
烧结温度：1400℃Sintering temperature: 1400°C
保温时间：20minHeat preservation time: 20min
烧结压力：40MPaSintering pressure: 40MPa
升温速率：100℃/minHeating rate: 100°C/min
经本实施例烧结后，NbMoTaWV高熵合金的显微组织由BCC单相组织转变为两种BCC相的混合组织，析出的颗粒状第二相均匀分布于等轴晶基体中，基体平均晶粒尺寸为1.0μm；第二相的平均晶粒尺寸为0.4μm，所占体积百分比约为12.4％。合金的密度为11.9g/cm3，室温下的最大抗压强度σbc为2639MPa，显微硬度为802Hv。After sintering in this example, the microstructure of the NbMoTaWV high-entropy alloy changed from a BCC single-phase structure to a mixed structure of two BCC phases, and the precipitated granular second phase was evenly distributed in the equiaxed crystal matrix, and the average grain size of the matrix The size is 1.0 μm; the average grain size of the second phase is 0.4 μm, accounting for about 12.4% by volume. The density of the alloy is 11.9g/cm 3 , the maximum compressive strength σ bc at room temperature is 2639MPa, and the microhardness is 802Hv.
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、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。The above-mentioned embodiment is a preferred embodiment of the present invention, but the embodiment of the present invention is not limited by the above-mentioned embodiment, and any other changes, modifications, substitutions, combinations, Simplifications should be equivalent replacement methods, and all are included in the protection scope of the present invention.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610508519.XA CN106001566A (en) | 2016-06-29 | 2016-06-29 | High-strength high-entropy alloy NbMoTaWV and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610508519.XA CN106001566A (en) | 2016-06-29 | 2016-06-29 | High-strength high-entropy alloy NbMoTaWV and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106001566A true CN106001566A (en) | 2016-10-12 |
Family
ID=57104876
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610508519.XA Pending CN106001566A (en) | 2016-06-29 | 2016-06-29 | High-strength high-entropy alloy NbMoTaWV and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106001566A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841672A (en) * | 2017-10-25 | 2018-03-27 | 武汉理工大学 | High density ReWTaMoNb containing RexHigh entropy alloy material and preparation method |
| CN109108273A (en) * | 2018-10-11 | 2019-01-01 | 中国人民解放军国防科技大学 | Preparation method of NbZrTiTa refractory high-entropy alloy powder and NbZrTiTa refractory high-entropy alloy powder |
| CN109182877A (en) * | 2018-11-07 | 2019-01-11 | 北京科技大学 | (NbMoTaW)100-xMxIt is infusibility high-entropy alloy and preparation method thereof |
| CN109778050A (en) * | 2019-04-04 | 2019-05-21 | 合肥工业大学 | A kind of WVTaTiZr refractory high entropy alloy and preparation method thereof |
| CN110106490A (en) * | 2019-06-12 | 2019-08-09 | 大连理工大学 | A kind of high temperature resistant high-entropy alloy NbMoTaWV film and preparation method thereof |
| CN110195208A (en) * | 2019-06-12 | 2019-09-03 | 大连理工大学 | A kind of NbMoTaWV high-entropy alloy sull of variable band gap and preparation method thereof |
| CN111168057A (en) * | 2020-02-28 | 2020-05-19 | 华南理工大学 | A nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing and its preparation method and application |
| CN111334697A (en) * | 2020-03-10 | 2020-06-26 | 中国人民解放军军事科学院国防科技创新研究院 | W-Ta-Mo-Nb-C high-temperature high-entropy alloy and preparation method thereof |
| CN112958770A (en) * | 2021-02-02 | 2021-06-15 | 合肥工业大学 | Preparation method of WRe/TZM composite material |
| US20230020010A1 (en) * | 2020-03-26 | 2023-01-19 | Hitachi Metals, Ltd. | Alloy and member |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001226734A (en) * | 2000-02-15 | 2001-08-21 | Chokoon Zairyo Kenkyusho:Kk | Niobium-based composite material and method for producing the same |
| CN102618807A (en) * | 2011-12-29 | 2012-08-01 | 北京理工大学 | Aluminum-based amorphous/nanocrystalline composite material and preparation method thereof |
| CN103710576A (en) * | 2013-11-25 | 2014-04-09 | 叶绿均 | Scandium-tantalum reinforced high-strength nickel-niobium alloy material |
| CN105543621A (en) * | 2016-01-18 | 2016-05-04 | 南京工程学院 | Endogenous nano ceramic reinforcement high-entropy alloy composite material and preparing method |
-
2016
- 2016-06-29 CN CN201610508519.XA patent/CN106001566A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001226734A (en) * | 2000-02-15 | 2001-08-21 | Chokoon Zairyo Kenkyusho:Kk | Niobium-based composite material and method for producing the same |
| CN102618807A (en) * | 2011-12-29 | 2012-08-01 | 北京理工大学 | Aluminum-based amorphous/nanocrystalline composite material and preparation method thereof |
| CN103710576A (en) * | 2013-11-25 | 2014-04-09 | 叶绿均 | Scandium-tantalum reinforced high-strength nickel-niobium alloy material |
| CN105543621A (en) * | 2016-01-18 | 2016-05-04 | 南京工程学院 | Endogenous nano ceramic reinforcement high-entropy alloy composite material and preparing method |
Non-Patent Citations (1)
| Title |
|---|
| SEOUNG WOO KUK: "Fabrication of W-Nb-Mo-Ta-V High Entropy Alloys by Mechanical Alloying and Spark Plasma Sintering", 《TRANSACTIONS OF THE KOREAN NUCLEAR SOCIETY SPRING MEETING》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841672A (en) * | 2017-10-25 | 2018-03-27 | 武汉理工大学 | High density ReWTaMoNb containing RexHigh entropy alloy material and preparation method |
| CN109108273A (en) * | 2018-10-11 | 2019-01-01 | 中国人民解放军国防科技大学 | Preparation method of NbZrTiTa refractory high-entropy alloy powder and NbZrTiTa refractory high-entropy alloy powder |
| CN109182877A (en) * | 2018-11-07 | 2019-01-11 | 北京科技大学 | (NbMoTaW)100-xMxIt is infusibility high-entropy alloy and preparation method thereof |
| CN109778050A (en) * | 2019-04-04 | 2019-05-21 | 合肥工业大学 | A kind of WVTaTiZr refractory high entropy alloy and preparation method thereof |
| CN110106490A (en) * | 2019-06-12 | 2019-08-09 | 大连理工大学 | A kind of high temperature resistant high-entropy alloy NbMoTaWV film and preparation method thereof |
| CN110195208A (en) * | 2019-06-12 | 2019-09-03 | 大连理工大学 | A kind of NbMoTaWV high-entropy alloy sull of variable band gap and preparation method thereof |
| CN110195208B (en) * | 2019-06-12 | 2021-03-19 | 大连理工大学 | A variable bandgap NbMoTaWV high-entropy alloy oxide film and its preparation method |
| CN111168057A (en) * | 2020-02-28 | 2020-05-19 | 华南理工大学 | A nano-ceramic reinforced high-entropy alloy composite powder for additive manufacturing and its preparation method and application |
| CN111334697A (en) * | 2020-03-10 | 2020-06-26 | 中国人民解放军军事科学院国防科技创新研究院 | W-Ta-Mo-Nb-C high-temperature high-entropy alloy and preparation method thereof |
| CN111334697B (en) * | 2020-03-10 | 2021-07-09 | 中国人民解放军军事科学院国防科技创新研究院 | A kind of W-Ta-Mo-Nb-C high-temperature high-entropy alloy and preparation method thereof |
| US20230020010A1 (en) * | 2020-03-26 | 2023-01-19 | Hitachi Metals, Ltd. | Alloy and member |
| CN112958770A (en) * | 2021-02-02 | 2021-06-15 | 合肥工业大学 | Preparation method of WRe/TZM composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108103381B (en) | A kind of high-strength FeCoNiCrMn high-entropy alloy and preparation method thereof | |
| CN106001566A (en) | High-strength high-entropy alloy NbMoTaWV and preparation method thereof | |
| CN105950945B (en) | A kind of high intensity high-entropy alloy NbMoTaWVCr and preparation method thereof | |
| CN104372230B (en) | High-strength high-toughness ultrafine-grained high-entropy alloy and preparation method thereof | |
| CN104862510B (en) | A kind of high-entropy alloy particle enhanced aluminum-based composite material and preparation method thereof | |
| CN104674038B (en) | A kind of high-strength and tough alloy material and its semi-solid sintering preparation method and application | |
| CN105950944B (en) | A kind of high-melting-point high-entropy alloy NbMoTaWVTi and preparation method thereof | |
| CN109108273B (en) | Preparation method of NbZrTiTa refractory high-entropy alloy powder and NbZrTiTa refractory high-entropy alloy powder | |
| CN103240412B (en) | Method for preparing powder super-alloy by near net shape | |
| CN106167870A (en) | A kind of NbMoTaW high-entropy alloy and preparation method thereof | |
| CN110093548B (en) | A kind of ultrafine grain high strength and toughness high entropy alloy containing rare earth Gd and preparation method thereof | |
| CN107557641A (en) | A kind of high-entropy alloy of resistance to strong acid corrosion and preparation method thereof | |
| CN103233182B (en) | Forming method for nanometer beta' phase element and nanometer oxide composite reinforced Fe-based ODS alloy | |
| CN107841672B (en) | Re-containing high-density ReWTaMoNbx high-entropy alloy material and preparation method | |
| CN104388788B (en) | Low-cost method for preparing niobium-base alloy | |
| CN104232995B (en) | A kind of high tough Ultra-fine Grained composite construction titanium alloy and preparation method thereof and application | |
| CN104711471B (en) | Method for preparing NiMnX alloy target | |
| CN102925780A (en) | Titanium-nickel-aluminum alloy material and its preparation process | |
| CN111206174A (en) | Magnetic ultrafine-grain high-strength high-entropy alloy and preparation method thereof | |
| CN105238954A (en) | Multi-scale and double-state structure titanium alloy based on eutectic transformation, preparation and application | |
| CN108546863A (en) | A kind of more pivot high temperature alloys and preparation method thereof | |
| CN108588534B (en) | A kind of in-situ self-generated carbide dispersion reinforced multi-principal alloy and preparation method thereof | |
| CN110079722A (en) | A kind of infusibility high-entropy alloy TiZrNbMoTa and its method for preparing powder metallurgy containing B | |
| CN103469119B (en) | Amorphous composite materials, and preparation method and applications thereof | |
| CN100595303C (en) | Preparation method of single-phase Sm2Co17 nanocrystalline bulk material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20161012 |