CN111618310A - Spherical vanadium alloy powder and preparation method and application thereof - Google Patents
Spherical vanadium alloy powder and preparation method and application thereof Download PDFInfo
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- B22F9/00—Making metallic powder or suspensions thereof
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- B22F9/14—Making metallic powder or suspensions thereof using physical processes using electric discharge
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/06—Metallic powder characterised by the shape of the particles
- B22F1/065—Spherical particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
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- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
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Abstract
本发明提供了一种球形钒合金粉末及其制备方法、应用。所述制备方法可包括：将钒合金棒置于真空环境中；向真空环境中通入惰性气体以置换空气，置换后真空环境中的氧含量在5ppm以下；利用电弧使钒合金棒端面熔化出液膜；旋转钒合金棒，在离心力作用下液膜破碎成微细液滴；冷却，得到球形钒合金粉。所述球形钒合金粉末可包括采用上述球形钒合金粉末的制备方法所制备出的粉末。所述应用可包括在激光或电子束增材制造领域中的应用，和/或，在激光或电子束熔覆领域中的应用，例如在电子束3D打印中的应用。本发明的有益效果可包括：制备效率高，成本低，安全性高；能够有效解决传统生产方法中粉末的球形度不好的难题。
The invention provides a spherical vanadium alloy powder and a preparation method and application thereof. The preparation method may include: placing the vanadium alloy rod in a vacuum environment; introducing an inert gas into the vacuum environment to replace air, and the oxygen content in the vacuum environment after the replacement is below 5 ppm; liquid film; rotating vanadium alloy rod, the liquid film is broken into fine droplets under the action of centrifugal force; cooled to obtain spherical vanadium alloy powder. The spherical vanadium alloy powder may include the powder prepared by the above-mentioned preparation method of spherical vanadium alloy powder. Such applications may include applications in the field of laser or e-beam additive manufacturing, and/or in the field of laser or e-beam cladding, such as in e-beam 3D printing. The beneficial effects of the present invention may include: high preparation efficiency, low cost and high safety; and can effectively solve the problem of poor sphericity of powder in traditional production methods.
Description
技术领域technical field
本发明涉及钒合金粉末的制备领域，特别地，涉及一种球形钒合金粉及其制备方法、应用。The invention relates to the field of preparation of vanadium alloy powder, in particular to a spherical vanadium alloy powder, a preparation method and application thereof.
背景技术Background technique
钒合金在国际上被公认为是聚变反应堆某关键结构部件的理想候选材料，最显著的优点是在中子辐照条件下的低激活特性和优良的高温强度性能。此外，钒及钒合金还具有良好的抗辐射诱变膨胀与损伤、良好的尺寸稳定性、热传导性能好、较低的热膨胀系数与弹性模量、低生物危害的安全性和环保特性、较好的抗蠕变性能、良好的加工性能以及对液体锂具有良好的耐腐蚀能力等优点。特别是钒合金：V-Cr-Ti系和V-W-Ti系更是核聚变反应堆的最重要的候选结构材料之一，因而该合金在聚变反应堆的第一壁、包层和偏滤器等结构设计中以及在航空航天、高温领域都具有广阔的应用前景。Vanadium alloys are internationally recognized as ideal candidates for a key structural component of fusion reactors. The most notable advantages are low activation properties under neutron irradiation and excellent high temperature strength properties. In addition, vanadium and vanadium alloys also have good resistance to radiation mutagenic expansion and damage, good dimensional stability, good thermal conductivity, low thermal expansion coefficient and elastic modulus, low biohazard safety and environmental protection characteristics, good It has the advantages of excellent creep resistance, good processability and good corrosion resistance to liquid lithium. Especially vanadium alloys: V-Cr-Ti series and V-W-Ti series are one of the most important candidate structural materials for nuclear fusion reactors. Therefore, the alloys are used in the structural design of the first wall, cladding and divertor of fusion reactors. It has broad application prospects in the fields of aerospace and high temperature.
在钒合金的应用中，通常需要制成各种结构件，如空间曲面壳体等。由于钒合金在高温下会产生V2O5，这是一种剧毒物质，因此，材料制备过程中如铸锭开坯、挤压等通常采用真空包套锻造的方法，如果壳体成形也采用这种方法，由于其变形量大，存在包套破裂释放有毒物质的风险，而且工艺较为复杂，具有余量大、成本高等问题。In the application of vanadium alloy, it is usually necessary to make various structural parts, such as space curved shell and so on. Since V 2 O 5 is produced at high temperature in vanadium alloys, which is a highly toxic substance, the method of vacuum encapsulation forging is usually adopted in the material preparation process, such as ingot blanking and extrusion. With this method, due to the large amount of deformation, there is a risk that the envelope is ruptured and toxic substances are released, and the process is relatively complicated, with large margins and high costs.
目前钒合金粉末，主要生产方法是：还原法、熔盐电解法、气雾化法、机械合金化的方法、以及破碎法和惰性气体雾化法等方法制取。惰性气体雾化法生产的粉末，其颗粒上卫星粉较多，同时还有一些空心粉，而且粉末颗粒的粒度分布的尺寸区间较宽，适合3D打印要求尺寸区间的粉末颗粒占比较低。At present, the main production methods of vanadium alloy powder are: reduction method, molten salt electrolysis method, gas atomization method, mechanical alloying method, crushing method and inert gas atomization method. The powder produced by the inert gas atomization method has more satellite powder on the particles and some hollow powder, and the size range of the particle size distribution of the powder particles is wide, and the proportion of powder particles suitable for the size range required by 3D printing is relatively low.
中国工程物理研究院采用高纯钒粉、铬粉和钛粉为原材料，三种粉末的平均粒径约为35μm，通过混合粉末、研磨实现机械合金化的方法制取钒合金粉末，湿磨时采用丙酮作为过程控制剂，干磨时不加过程控制剂，采用惰性气氛保护的机械合金化方法，高效制备了微细钒合金粉末，但制取的粉末球形度欠佳，氧含量偏高。China Academy of Engineering Physics uses high-purity vanadium powder, chromium powder and titanium powder as raw materials. The average particle size of the three powders is about 35 μm. The vanadium alloy powder is prepared by mixing powders and grinding to achieve mechanical alloying. Acetone was used as the process control agent, no process control agent was added during dry grinding, and the micro-vanadium alloy powder was efficiently prepared by the mechanical alloying method protected by inert atmosphere, but the obtained powder had poor sphericity and high oxygen content.
CN201811156064.5公开了金属气基还原制备金属钒粉的方法，步骤包括：以氧化钒为原料，活泼金属为还原剂，活泼金属以气体形式与原料接触发生热还原反应，反应产物经酸洗过滤、干燥得到金属钒粉。CN201811156064.5 discloses a method for preparing metal vanadium powder by metal gas-based reduction. The steps include: using vanadium oxide as a raw material, an active metal as a reducing agent, the active metal in the form of a gas contacts the raw material to generate a thermal reduction reaction, and the reaction product is subjected to acid washing and filtering and drying to obtain metal vanadium powder.
CN201811222443.X公开了一种高纯钒粉的制备方法，先将含钒物料与碱金属或碱土金属氯化物盐混合，再与氢化钙混合，然后进行真空热还原，得到还原产物；再依次用氯化铵溶液、碱液和酸液进行洗涤，最后进行脱氢处理，即可得到高纯金属钒粉。CN201811222443.X discloses a preparation method of high-purity vanadium powder. First, the vanadium-containing material is mixed with alkali metal or alkaline earth metal chloride salt, and then mixed with calcium hydride, and then vacuum thermal reduction is performed to obtain a reduction product; Ammonium chloride solution, alkali solution and acid solution are washed, and finally dehydrogenation is carried out to obtain high-purity metal vanadium powder.
CN201410335895.4公开了一种钛铝钒合金粉末的制备方法，包括如下步骤：a、制备电极：将TiO2、Al2O3、V2O5粉末混匀，压制成型，高温烧结，制成钛铝钒电极；b、熔盐电解反应：以制备得到的钛铝钒电极为阴极，石墨棒为阳极，以NaCl-CaCl2为熔盐电解液，进行熔盐电解反应，阴极框中得到的粉末即为钛铝钒合金粉末。CN201410335895.4 discloses a preparation method of titanium-aluminum-vanadium alloy powder, comprising the following steps: a. Preparation of electrodes: mixing TiO 2 , Al 2 O 3 , V 2 O 5 powders uniformly, pressing and molding, sintering at high temperature to make Titanium-aluminum-vanadium electrode; b, molten salt electrolysis reaction: take the prepared titanium-aluminum-vanadium electrode as the cathode, the graphite rod as the anode, and use NaCl-CaCl2 as the molten salt electrolyte to carry out the molten salt electrolysis reaction, and the powder obtained in the cathode frame That is titanium aluminum vanadium alloy powder.
CN109628731A公开了一种短流程处理含钒原料提取制备钒及合金粉末的方法，首先将含钒原料与碱性化合物氧化焙烧，生成易溶于水的钒酸盐，经除杂、沉钒处理后形成高纯度的中间产物CaV2O6，将其与其他原料溶解在熔盐介质中形成均匀的反应体系，然后加入还原剂还原，经过分离、洗涤、烘干后得到了粒径在50～800nm之间，且纯度≥99.0wt.％的钒或钒合金粉末。CN109628731A discloses a method for extracting and preparing vanadium and alloy powder by treating vanadium-containing raw materials in a short process. First, the vanadium-containing raw materials and basic compounds are oxidized and roasted to generate vanadate which is easily soluble in water. Form a high-purity intermediate product CaV2O6, dissolve it and other raw materials in a molten salt medium to form a uniform reaction system, then add a reducing agent to reduce, and obtain a particle size between 50 and 800nm after separation, washing and drying. and vanadium or vanadium alloy powder with a purity of ≥99.0 wt.%.
上述方法制取的钒合金粉末的球形度和洁净度都比较低。The vanadium alloy powder prepared by the above method has relatively low sphericity and cleanliness.
发明内容SUMMARY OF THE INVENTION
针对现有技术中存在的不足，本发明的目的在于解决上述现有技术中存在的一个或多个问题。例如，本发明的目的之一在于制备出能够满足增材制造技术要求的钒合金粉末。Aiming at the deficiencies existing in the prior art, the purpose of the present invention is to solve one or more problems existing in the prior art mentioned above. For example, one of the objectives of the present invention is to prepare vanadium alloy powder that can meet the technical requirements of additive manufacturing.
为了实现上述目的，本发明一方面提供了一种球形钒合金粉末的制备方法。In order to achieve the above object, one aspect of the present invention provides a method for preparing spherical vanadium alloy powder.
所述制备方法可包括以下步骤：将钒合金棒置于真空环境中；向真空环境中通入惰性气体以置换空气，置换后真空环境中氧含量在5ppm以下；利用电弧使钒合金棒端面熔化出液膜；旋转钒合金棒，在离心力作用下液膜破碎成微细液滴；冷却，得到球形钒合金粉。The preparation method may include the following steps: placing the vanadium alloy rod in a vacuum environment; introducing an inert gas into the vacuum environment to replace air, and the oxygen content in the vacuum environment after the replacement is below 5 ppm; using an electric arc to melt the end face of the vanadium alloy rod The liquid film is discharged; the vanadium alloy rod is rotated, and the liquid film is broken into fine droplets under the action of centrifugal force; the spherical vanadium alloy powder is obtained by cooling.
根据本发明的一个或多个示例性实施例，所述钒合金棒中钒的质量分数可以为89～92％。According to one or more exemplary embodiments of the present invention, the mass fraction of vanadium in the vanadium alloy rod may be 89-92%.
根据本发明的一个或多个示例性实施例，在所述利用电弧使钒合金棒端面熔化出液膜的起始阶段，所述真空环境的真空度控制在7×10-3Pa以下。According to one or more exemplary embodiments of the present invention, in the initial stage of using the arc to melt the end face of the vanadium alloy rod out of the liquid film, the vacuum degree of the vacuum environment is controlled below 7×10 -3 Pa.
根据本发明的一个或多个示例性实施例，所述钒合金棒旋转的转速可以为2000～26000rpm。According to one or more exemplary embodiments of the present invention, the rotating speed of the vanadium alloy rod may be 2000-26000 rpm.
根据本发明的一个或多个示例性实施例，所述电弧可以由电弧熔化系统输出，电弧熔化系统的工作电流输出可以为1500～4000A。According to one or more exemplary embodiments of the present invention, the arc may be output by an arc melting system, and the working current output of the arc melting system may be 1500-4000A.
根据本发明的一个或多个示例性实施例，所述惰性气体可以包括由氩气和氦气组成的混合气体，混合气体中氦气的体积占比为10～90％；或者，所述惰性气体可以包括氩气。According to one or more exemplary embodiments of the present invention, the inert gas may include a mixed gas consisting of argon and helium, and the volume ratio of helium in the mixed gas is 10-90%; or, the inert gas The gas may include argon.
根据本发明的一个或多个示例性实施例，所述将钒合金棒置于真空环境中的步骤可包括：将所述钒合金棒放入电弧熔化旋转雾化装置中，抽取真空并控制所述装置内真空度在7×10-3Pa以下。According to one or more exemplary embodiments of the present invention, the step of placing the vanadium alloy rod in a vacuum environment may include: placing the vanadium alloy rod in an arc melting rotary atomization device, extracting a vacuum and controlling the The degree of vacuum in the device is below 7×10 -3 Pa.
根据本发明的一个或多个示例性实施例，所述方法还可包括步骤：在保护气氛下，利用超声波振动筛或标准筛对所述冷却后的钒合金粉末进行筛分，按照粒度分级，获得不同级别的钒合金粉末。According to one or more exemplary embodiments of the present invention, the method may further include the steps of: sieving the cooled vanadium alloy powder with an ultrasonic vibration sieve or a standard sieve under a protective atmosphere, and classifying according to particle size, Obtain different grades of vanadium alloy powder.
本发明另一方面提供了一种球形钒合金粉末。所述球形钒合金粉末可包括采用上述球形钒合金粉末的制备方法所制备出的粉末。Another aspect of the present invention provides a spherical vanadium alloy powder. The spherical vanadium alloy powder may include the powder prepared by the above-mentioned preparation method of spherical vanadium alloy powder.
本发明再一方面提供了一种球形钒合金粉末的应用，应用可包括：在激光或电子束增材制造领域中的应用，在激光或电子束熔覆领域中的应用，例如在电子束3D打印中的应用。Another aspect of the present invention provides an application of spherical vanadium alloy powder, the application may include: application in the field of laser or electron beam additive manufacturing, application in the field of laser or electron beam cladding, for example, in the field of electron beam 3D application in printing.
与现有技术相比，本发明的有益效果可包括：制备效率高，成本低，安全性高；能够有效解决传统生产方法中粉末的球形度不好的难题；生产的钒合金粉基本没有空心粉和卫星粉，同时具有粒径分布区间窄、球形度高、流动性好、夹杂物少等优点。Compared with the prior art, the beneficial effects of the present invention may include: high preparation efficiency, low cost and high safety; can effectively solve the problem of poor sphericity of powder in traditional production methods; produced vanadium alloy powder basically has no hollow It also has the advantages of narrow particle size distribution, high sphericity, good fluidity, and few inclusions.
附图说明Description of drawings
通过下面结合附图进行的描述，本发明的上述和其他目的和特点将会变得更加清楚，其中：The above and other objects and features of the present invention will become more apparent from the following description in conjunction with the accompanying drawings, wherein:
图1示出了示例1中制备得到钒合金粉末的一个形貌图；Fig. 1 shows a topography of the vanadium alloy powder prepared in Example 1;
图2示出了示例2中制备得到钒合金粉末的一个形貌图；Figure 2 shows a topography of the vanadium alloy powder prepared in Example 2;
图3示出了示例2中制备得到钒合金粉末的一个粒度分布示意图。FIG. 3 shows a schematic diagram of the particle size distribution of the vanadium alloy powder prepared in Example 2. FIG.
具体实施方式Detailed ways
在下文中，将结合附图和示例性实施例详细地描述本发明的球形钒合金粉末(也可称为钒合金粉)及其制备方法、应用。Hereinafter, the spherical vanadium alloy powder (also referred to as vanadium alloy powder) of the present invention and its preparation method and application will be described in detail with reference to the accompanying drawings and exemplary embodiments.
选区激光熔融成型的增材制造技术为钒合金材料制备与零件精确成型一体化提供了一种全新的思路与方法，有望在保证零件质量与性能的前提下，极大地提高材料利用率，并大幅降低整体制造成本。然而增材制造技术用的金属粉末除需具备准确的化学成分、低的氧含量外，还必须满足增材制造技术对金属粉末要求的物理特性：粉末粒径细小、粒经分布区间窄、粉末颗粒球形度高、流动性好、松装密度大和振实密度高、夹杂物少等特殊要求指标。The additive manufacturing technology of selective laser melting and forming provides a new idea and method for the integration of vanadium alloy material preparation and precise forming of parts. Reduce overall manufacturing costs. However, in addition to accurate chemical composition and low oxygen content, metal powders used in additive manufacturing technology must also meet the physical properties required by additive manufacturing technology for metal powders: fine powder particle size, narrow particle distribution interval, powder Special requirements such as high particle sphericity, good fluidity, high bulk density, high tap density, and few inclusions.
对此，发明人提出了一种适用于增材制造领域的球形钒合金粉及其制备方法。In this regard, the inventor proposes a spherical vanadium alloy powder suitable for the field of additive manufacturing and a preparation method thereof.
本发明一方面提供了一种球形钒合金粉末的制备方法。One aspect of the present invention provides a method for preparing spherical vanadium alloy powder.
在本发明的一个示例性实施例中，所述球形钒合金粉末的制备方法可包括以下步骤：In an exemplary embodiment of the present invention, the preparation method of the spherical vanadium alloy powder may include the following steps:
将经真空熔化的钒合金棒或粉末冶金方法制取的钒合金棒料(也可称为钒合金棒材)，加工成原料棒(也可称为钒合金棒、钒合金原料棒等)。The vanadium alloy rods (also known as vanadium alloy rods) obtained by vacuum melting or powder metallurgy are processed into raw material rods (also known as vanadium alloy rods, vanadium alloy raw material rods, etc.).
原料棒放入电弧熔化离心雾化装置(也可称为电弧熔化旋转雾化装置)中，抽取真空，然后向装置通入惰性气体或混合惰性气体。The raw material rod is put into the arc melting centrifugal atomizing device (also called arc melting rotary atomizing device), vacuum is drawn, and then inert gas or mixed inert gas is introduced into the device.
在惰性气体保护下开启设备电弧，使钒合金原料棒前端熔化为液膜，控制旋转钒合金原料棒转速，原料棒前端熔化的液膜在离心力的作用下破碎成微细液滴，通过调整混合惰性气体的比例和流速，控制钒合金液破碎成微细液滴的冷却速度，在表面张力的作用下实现钒合金粉末的球形化，获得能满足增材制造技术要求用的球形钒合金粉末。The arc of the equipment is turned on under the protection of inert gas, so that the front end of the vanadium alloy raw material rod is melted into a liquid film, and the rotation speed of the rotating vanadium alloy raw material rod is controlled, and the molten liquid film at the front end of the raw material rod is broken into fine droplets under the action of centrifugal force. The proportion and flow rate of the gas, control the cooling rate of the vanadium alloy liquid broken into fine droplets, realize the spheroidization of the vanadium alloy powder under the action of surface tension, and obtain spherical vanadium alloy powder that can meet the technical requirements of additive manufacturing.
在本发明的另一个示例性实施例中，所述球形钒合金粉末的制备方法可包括以下步骤：In another exemplary embodiment of the present invention, the preparation method of the spherical vanadium alloy powder may include the following steps:
将钒合金原料棒放入电弧熔化旋转雾化装置中，抽取真空并控制装置内的真空度在7×10-3Pa以下，进一步地，可为3×10-3Pa～6×10-3Pa。抽取的装置内真空度过高将延长设备生产准备时间，降低工作效率，抽取的装置内真空度过低，需充入更多的惰性气体以置换排除氧气，不经济。Put the vanadium alloy raw material rod into the arc melting rotary atomization device, extract the vacuum and control the vacuum degree in the device to be below 7 × 10 -3 Pa, further, it can be 3 × 10 -3 Pa ~ 6 × 10 -3 Pa Pa. If the vacuum in the extracted device is too high, it will prolong the production preparation time of the equipment and reduce the work efficiency. If the vacuum in the extracted device is too low, more inert gas needs to be filled to replace and eliminate oxygen, which is uneconomical.
然后向装置通入的惰性气体，以确保装置离心雾化室内的氧含量≤5ppm，并在惰性气体保护下开启电弧熔化离心雾化装置。其中，惰性气体可以为氩气或者为由氩气与氦气组成的混合气体。其中，氩气纯度可在99.995％以上，氦气纯度也可在99.995％以上。进一步地，氩气与氦气的纯度可为99.999％。Then the inert gas is introduced into the device to ensure that the oxygen content in the centrifugal atomization chamber of the device is ≤5ppm, and the arc melting centrifugal atomization device is turned on under the protection of the inert gas. Wherein, the inert gas may be argon gas or a mixed gas composed of argon gas and helium gas. Among them, the purity of argon gas can be above 99.995%, and the purity of helium gas can also be above 99.995%. Further, the purity of argon and helium may be 99.999%.
控制钒合金原料棒旋转的转速为2000～26000rpm，例如5000rpm、12000rpm、18000rpm等，通过电弧熔化系统将钒合金棒熔化并产生液膜，在离心力的作用下，液膜破碎成微细液滴，通过调整混合惰性气体的比例，控制钒合金微细液滴的冷却速度，在表面张力的作用下冷却凝固实现钒合金粉末球形化。同时对钒合金棒料连续进给，补充熔化飞离的液体膜，原料棒的进料速度为6～240mm/min之间并连续可调，以获得持续生产球形钒合金粉，例如进料速度可以为60mm/min、70mm/min、100mm/min、120mm/min、170mm/min、210mm/min、230mm/min等。The rotation speed of the vanadium alloy raw material rod is controlled to be 2000-26000rpm, such as 5000rpm, 12000rpm, 18000rpm, etc., and the vanadium alloy rod is melted by the arc melting system to produce a liquid film. Under the action of centrifugal force, the liquid film is broken into fine droplets, which pass through The proportion of mixed inert gas is adjusted, the cooling rate of vanadium alloy fine droplets is controlled, and the vanadium alloy powder is spheroidized by cooling and solidification under the action of surface tension. At the same time, the vanadium alloy bar is continuously fed to supplement the melted and flying liquid film. The feeding speed of the raw bar is between 6 and 240 mm/min and can be continuously adjusted to obtain continuous production of spherical vanadium alloy powder. For example, the feeding speed It can be 60mm/min, 70mm/min, 100mm/min, 120mm/min, 170mm/min, 210mm/min, 230mm/min, etc.
在本实施例中，电弧熔化旋转雾化装置主要包括：In this embodiment, the arc melting rotary atomization device mainly includes:
(1)电弧熔化系统：电弧熔化系统可以将原料棒熔化为液膜。(1) Arc melting system: The arc melting system can melt the raw material rod into a liquid film.
(2)旋转离心雾化系统(可简称旋转系统)：旋转离心雾化系统可具有一个离心雾化室，将原料棒放入旋转离心雾化室中，旋转系统能够控制原料棒的转速，旋转系统能够使原料棒产生离心力，在离心力的作用下原料棒前端熔化的液膜雾化为液滴冷却成粉。(2) Rotary centrifugal atomization system (referred to as rotary system): The rotary centrifugal atomization system can have a centrifugal atomization chamber, and the raw material rods are put into the rotary centrifugal atomization chamber. The system can make the raw material rod generate centrifugal force, under the action of centrifugal force, the molten liquid film at the front end of the raw material rod is atomized into droplets and cooled into powder.
(3)给进系统：给进系统可连接原料棒的一端。给进系统可通过对棒料(即原料棒)连续进给来补充熔化飞离的液体膜，进料速度可以在60～240mm/min连续可调。(3) Feeding system: The feeding system can be connected to one end of the raw material bar. The feeding system can supplement the molten and flying liquid film by continuously feeding the bar material (ie, the raw material bar), and the feeding speed can be continuously adjusted between 60 and 240 mm/min.
在本实施例中，电弧熔化旋转雾化装置中电弧熔化系统的工作电流输出可以为1500～4000A，例如2000±800A，电弧长可以35～80mm，例如55±10mm，弧柱直径可以为40～55mm，例如47±3mm。In this embodiment, the working current output of the arc melting system in the arc melting rotary atomizing device can be 1500-4000A, such as 2000±800A, the arc length can be 35-80mm, such as 55±10mm, and the arc column diameter can be 40- 55mm, eg 47±3mm.
在本实施例中，钒合金棒可包括经真空熔化或粉末冶金方法制取的钒合金棒。In this embodiment, the vanadium alloy rod may include a vanadium alloy rod prepared by vacuum melting or powder metallurgy.
在本实施例中，在制备开始时，原料棒可完全放入装置的真空腔内，原料棒旋转同时给进，当距离到达弧长35～80mm要求时，开启电弧。其中，原料棒的一端可连接给进系统，另一端可通过电弧连接等离子枪。In this embodiment, at the beginning of the preparation, the raw material rod can be completely put into the vacuum chamber of the device, and the raw material rod is rotated and fed at the same time. When the distance reaches the arc length requirement of 35-80 mm, the arc is turned on. Among them, one end of the raw material rod can be connected to the feeding system, and the other end can be connected to the plasma gun through the arc.
在本实施例中，钒合金棒可包括按照质量百分比计的以下成分：In this embodiment, the vanadium alloy rod may include the following components in mass percent:
89～92％钒，例如90％、91％等89~92% vanadium, such as 90%, 91%, etc.
7.7～10.7％为钛、铬、钨元素中的一种或多种，其它元素≤0.3％。7.7-10.7% is one or more of titanium, chromium and tungsten elements, and other elements are less than or equal to 0.3%.
钒合金棒的相对密度可以在98％以上，例如，98.5％、99％等。The relative density of the vanadium alloy rod may be above 98%, for example, 98.5%, 99%, and the like.
钒合金棒的直径可以为50～90mm，长度可以为250～550mm。The diameter of the vanadium alloy rod may be 50-90 mm, and the length may be 250-550 mm.
在本实施例中，在将钒合金棒放入电弧熔化旋转雾化装置之前，所述方法还可包括步骤：将钒合金棒按适合旋转雾化装置要求进行加工，加工为合适的尺寸。In this embodiment, before placing the vanadium alloy rod into the arc melting rotary atomization device, the method may further include the step of: processing the vanadium alloy rod into a suitable size according to the requirements of the rotary atomization device.
在本实施例中，氩气或者混合气体进入电弧熔化旋转雾化装置中惰性气体总流量可以为300～900L/min，例如600±200L/min，其压力可以为0.3～0.8MPa，例如0.6±0.1MPa。In this embodiment, the total flow of argon gas or mixed gas into the arc melting rotary atomizing device can be 300-900L/min, for example, 600±200L/min, and the pressure can be 0.3-0.8MPa, for example, 0.6±200L/min. 0.1MPa.
混合气体中氦气的体积占比可以为10～90％，例如50±20％，氦气的占比可根据钒合金粉产品的粒度要求而变。The volume proportion of helium in the mixed gas can be 10-90%, for example, 50±20%, and the proportion of helium can be changed according to the particle size requirements of the vanadium alloy powder product.
在本实施例中，在雾化腔内氧含量≤5ppm时，电弧熔化系统的工作电流输出1500～4000A，电弧长35～80mm，弧柱直径40～55mm。In this embodiment, when the oxygen content in the atomization chamber is less than or equal to 5ppm, the working current output of the arc melting system is 1500-4000A, the arc length is 35-80mm, and the diameter of the arc column is 40-55mm.
在金属粉末的过程中，由于金属性质不同及熔点不同，金属液粘度也不同，熔化电弧能量密度的高低决定了原料棒熔化端面液膜层的厚薄，进而影响粉末粒度和雾化过程的顺利进行。电弧能量密度过低，将延长原料棒熔化完成时间，导致大量热量传递到电机轴、轴承，使电机不能正常工作。电弧能量密度过高，原料棒熔化端面液膜层太厚不但使粉末变粗而且还易产生飞边并加大原料棒的振动，使雾化过程不能进行。工作电流决定了电弧能量密度的高低。原料棒的旋转速度、工作电流大小、弧距的长短及原料棒的给进速度是本发明的重要工艺参数，这些工艺参数的组合协同才能使得雾化过程顺利实现。In the process of metal powder, due to the different metal properties and melting points, the viscosity of the molten metal is also different. The energy density of the melting arc determines the thickness of the liquid film layer on the melting end face of the raw material rod, which in turn affects the powder particle size and the smooth progress of the atomization process. . If the arc energy density is too low, the melting completion time of the raw material bar will be prolonged, and a large amount of heat will be transferred to the motor shaft and bearing, so that the motor cannot work normally. The arc energy density is too high, and the liquid film layer on the melting end face of the raw material rod is too thick, which not only makes the powder thicker, but also tends to produce flash and increase the vibration of the raw material rod, so that the atomization process cannot be carried out. The working current determines the level of arc energy density. The rotation speed of the raw material rod, the size of the working current, the length of the arc distance and the feeding speed of the raw material rod are the important process parameters of the present invention, and the combination and coordination of these process parameters can make the atomization process smoothly realized.
采用本发明的钒合金粉制备方法可实现批量化化制备能满足增材制造技术要求的球形钒合金粉。制备出钒合金粉的化学成分基本与原料棒的相当。By adopting the vanadium alloy powder preparation method of the present invention, the spherical vanadium alloy powder that can meet the technical requirements of additive manufacturing can be prepared in batches. The chemical composition of the prepared vanadium alloy powder is basically the same as that of the raw material rod.
钒合金粉粒度在2000μm以下，例如15μm、20μm、50μm、100μm、500μm、1100μm、1900μm等。粉末颗粒形貌与标准圆之比的球形度可在90％以上，进一步地，可在92％以上，例如93％。The particle size of vanadium alloy powder is below 2000 μm, such as 15 μm, 20 μm, 50 μm, 100 μm, 500 μm, 1100 μm, 1900 μm and so on. The sphericity of the ratio of powder particle morphology to standard circle can be above 90%, further, can be above 92%, for example, 93%.
制粉生产过程氧增量：≤100ppm，氮增量：≤30ppm。Oxygen increment in milling production process: ≤100ppm, nitrogen increment: ≤30ppm.
为了更好地理解本发明的上述示例性实施例，下面结合具体示例对其进行进一步说明。In order to better understand the above-mentioned exemplary embodiments of the present invention, they are further described below with reference to specific examples.
示例1Example 1
采用V-6W-2.5Ti系钒合金棒材作为原料，钒合金棒材的主要化学元素含量如表1所示，其相对密度大于98％，将棒材加工成直径为Ф50×550mm钒合金原料棒，并除去表面氧化物及杂质。The V-6W-2.5Ti series vanadium alloy bar is used as the raw material. The main chemical element content of the vanadium alloy bar is shown in Table 1, and its relative density is greater than 98%. The bar is processed into a vanadium alloy raw material with a diameter of Ф50×550mm. rod, and remove surface oxides and impurities.
将除去表面氧化物及杂质的钒合金原料棒放入电弧离心雾化装置(即电弧熔化旋转雾化装置)中，抽真空度到6×10-3Pa，然后向装置通入混合惰性气体，确保雾化腔内氧含量≤5ppm。Put the vanadium alloy raw material rod with the surface oxide and impurities removed into the arc centrifugal atomization device (ie arc melting rotary atomization device), vacuumize to 6×10 -3 Pa, and then feed the mixed inert gas into the device, Make sure that the oxygen content in the atomizing chamber is less than or equal to 5ppm.
在惰性气体保护下开启电弧熔化离心雾化装置，通过控制电弧熔化的工作电流大小控制功率，进而控制对钒合金棒的熔化速度，工作电流输出2400A，电弧长60mm，原料钒棒的转速为2600rpm；钒合金原料棒前端被电弧熔化成液膜，经旋转离心将液膜破碎为细小的钒合金液滴，在混合惰性气体环境中冷却凝固，钒合金原料棒进料速度为180mm/min。Open the arc melting centrifugal atomization device under the protection of inert gas, control the power by controlling the working current of arc melting, and then control the melting speed of the vanadium alloy rod. The working current output is 2400A, the arc length is 60mm, and the speed of the raw vanadium rod is 2600rpm. ; The front end of the vanadium alloy raw material rod is melted into a liquid film by the arc, and the liquid film is broken into small vanadium alloy droplets by rotary centrifugation, and cooled and solidified in a mixed inert gas environment. The feeding speed of the vanadium alloy raw material rod is 180mm/min.
制取的钒合金粉待冷却至室温后取出，在氩气的保护下用超声波振动筛进行筛分，按照粒度分级，获得不同级别的球形钒合金粉，用塑料膜真空包装成为产品。The prepared vanadium alloy powder is taken out after cooling to room temperature, sieved with an ultrasonic vibrating sieve under the protection of argon gas, and classified according to particle size to obtain spherical vanadium alloy powder of different grades, which is vacuum-packed with plastic film to become a product.
其中，混合惰性气体中纯度为99.995％氩气体积占比为10％，纯度为99.995％的氦气体积占比为90％。混合惰性气体的流量为890L/min，其压力为0.6±0.05MPa。Among them, argon gas with a purity of 99.995% in the mixed inert gas accounts for 10% by volume, and helium gas with a purity of 99.995% accounts for 90% by volume. The flow rate of the mixed inert gas is 890L/min, and its pressure is 0.6±0.05MPa.
所制取的球形钒合金粉产品的颗粒形貌呈球形或类球形如图1所示，钒合金粉产品的主要化学元素含量如表2所示，钒合金粉的粒度在1200～1500微米，粉末颗粒的氧含量为471ppm，其制取过程氧增量为59ppm，氮含量为113ppm，氮增量为18ppm，球形度为92％。The particle morphology of the prepared spherical vanadium alloy powder product is spherical or spherical as shown in Figure 1. The main chemical element content of the vanadium alloy powder product is shown in Table 2. The particle size of the vanadium alloy powder is 1200-1500 microns. The oxygen content of the powder particles was 471 ppm, the oxygen increment during the preparation process was 59 ppm, the nitrogen content was 113 ppm, the nitrogen increment was 18 ppm, and the sphericity was 92%.
表1 V-6W-2.5Ti系钒合金棒材的主要化学成分(质量分数，wt％)Table 1 Main chemical components of V-6W-2.5Ti series vanadium alloy bars (mass fraction, wt%)
表2示例1制取得到的钒合金粉末的主要化学成分(质量分数，wt％)Table 2 Main chemical components (mass fraction, wt%) of vanadium alloy powder prepared in Example 1
示例2Example 2
采用V-5Cr-5Ti系钒合金棒材作为原料，其主要化学元素含量如表3所示，其相对密度大于99％。将棒材加工成直径为Ф80×350mm钒合金原料棒，并除去表面氧化物及杂质。The V-5Cr-5Ti series vanadium alloy bar is used as the raw material, and the content of its main chemical elements is shown in Table 3, and its relative density is greater than 99%. The bar is processed into a vanadium alloy raw material bar with a diameter of Ф80×350mm, and the surface oxides and impurities are removed.
将除去表面氧化物及杂质的钒合金原料棒放入电弧离心雾化装置中，抽真空度到6×10-3Pa，然后向装置通入混合惰性气体，确保雾化腔内氧含量为3ppm时。Put the vanadium alloy raw material rod with the surface oxides and impurities removed into the arc centrifugal atomization device, vacuumize to 6×10 -3 Pa, and then pass the mixed inert gas into the device to ensure that the oxygen content in the atomization chamber is 3ppm Time.
在惰性气体保护下开启电弧熔化离心雾化装置，通过控制电弧熔化的工作电流大小来控制对钒合金棒的熔化速度，工作电流输出2800A，电弧长45mm，原料钒合金棒的转速为23000rpm；钒合金原料棒前端被电弧熔化成液膜，经旋转离心将液膜破碎为细小的钒合金液滴，在混合惰性气体环境中冷却凝固，钒合金原料棒进料速度为96mm/min。Open the arc melting centrifugal atomization device under the protection of inert gas, and control the melting speed of the vanadium alloy rod by controlling the working current of the arc melting. The working current output is 2800A, the arc length is 45mm, and the speed of the raw vanadium alloy rod is 23000rpm; The front end of the alloy raw material rod is melted into a liquid film by the electric arc, and the liquid film is broken into small vanadium alloy droplets by rotating and centrifugation, which is cooled and solidified in a mixed inert gas environment. The feeding speed of the vanadium alloy raw material rod is 96mm/min.
制取的钒合金粉待冷却至室温后取出，再氩气的保护下用超声波振动筛进行筛分，按照粒度分级，获得不同级别的球形钒合金粉，用塑料膜真空包装成为产品。The prepared vanadium alloy powder is taken out after cooling to room temperature, and then sieved with an ultrasonic vibrating screen under the protection of argon gas, and classified according to particle size to obtain spherical vanadium alloy powder of different grades, which is vacuum-packed with plastic film to become a product.
其中，混合惰性气体中纯度为99.995％的氩气占体积占比为90％，纯度为99.995％的氦气体积占比为10％；混合惰性气体的流量为690L/min，其压力为0.4MPa。Among them, argon with a purity of 99.995% in the mixed inert gas accounts for 90% of the volume, and helium with a purity of 99.995% accounts for 10% of the volume; the flow rate of the mixed inert gas is 690L/min, and its pressure is 0.4MPa .
所制取的球形钒合金粉产品的颗粒形貌呈球形或类球形如图2所示，球形度达到90％。钒合金粉产品的主要化学元素含量如表4所示；粉末颗粒的氧含量为583ppm，其制取过程氧增量为62ppm，氮含量为132ppm，其氮增量为21ppm。球形钒合金粉的粒度分布如图3所示，获得的钒合金粉末颗粒的粒度分布主要在53～150微米区间，粉末流动性为23s/50g。The particle morphology of the prepared spherical vanadium alloy powder product is spherical or quasi-spherical, as shown in Figure 2, and the sphericity reaches 90%. The main chemical element content of the vanadium alloy powder product is shown in Table 4; the oxygen content of the powder particles is 583ppm, the oxygen increment in the preparation process is 62ppm, the nitrogen content is 132ppm, and the nitrogen increment is 21ppm. The particle size distribution of the spherical vanadium alloy powder is shown in Figure 3. The particle size distribution of the obtained vanadium alloy powder particles is mainly in the range of 53-150 microns, and the powder fluidity is 23s/50g.
表3 V-5Cr-5Ti系钒合金棒材的主要化学成分(质量分数，wt％)Table 3 Main chemical compositions of V-5Cr-5Ti series vanadium alloy bars (mass fraction, wt%)
表4示例2制取得到的钒合金粉末的主要化学成分(质量分数，wt％)Table 4 Main chemical components (mass fraction, wt%) of the vanadium alloy powder obtained in Example 2
本发明另一方面提供了一种球形钒合金粉。球形钒合金粉可包括采用上述的制备方法所制备出的钒合金粉。Another aspect of the present invention provides a spherical vanadium alloy powder. The spherical vanadium alloy powder may include the vanadium alloy powder prepared by the above-mentioned preparation method.
钒合金粉末的球形度高，粒度尺寸区间分布窄，具有准确均匀的化学成分和低的氧含量。此外，钒合金粉末的物理特性还具有：粉末粒径细小、粒经分布区间窄、粉末颗粒球形度高、流动性好、松装密度大和振实密度高、夹杂物少等优点。钒合金粉末的粒度可在15～2000μm。Vanadium alloy powder has high sphericity, narrow particle size distribution, accurate and uniform chemical composition and low oxygen content. In addition, the physical properties of vanadium alloy powder also have the advantages of fine powder particle size, narrow particle distribution interval, high powder particle sphericity, good fluidity, high bulk density and high tap density, and few inclusions. The particle size of vanadium alloy powder can be 15-2000μm.
本发明再一方面提供了一种球形钒合金粉末的应用。应用可包括在激光或电子束3D打印领域中的应用，例如在高速激光熔覆沉积领域、电子束选区熔化领域等。Another aspect of the present invention provides an application of spherical vanadium alloy powder. Applications can include applications in the field of laser or electron beam 3D printing, such as high-speed laser cladding deposition, electron beam selective melting, etc.
综上所述，本发明的球形钒合金粉末及其制备方法、应用的优点可包括：To sum up, the advantages of the spherical vanadium alloy powder of the present invention and its preparation method and application may include:
(1)本发明制备方法的生产效率高、成本低。(1) The preparation method of the present invention has high production efficiency and low cost.
(2)本发明将电弧熔化系统和旋转离心雾化系统结合，生产的钒合金粉具有：粉末粒径细小、粒经分布区间窄、粉末颗粒球形度高、流动性好、松装密度大、振实密度高和夹杂物少的特点。(2) The present invention combines the arc melting system and the rotary centrifugal atomization system, and the vanadium alloy powder produced has the following characteristics: fine powder particle size, narrow particle distribution interval, high powder particle sphericity, good fluidity, large bulk density, Features high tap density and less inclusions.
(3)在钒有毒性的情况下，本发明装置密封效果好，采用了真空加惰性气体保护的方式，减小了钒污染物泄露的风险。(3) Under the condition that vanadium is toxic, the device of the present invention has a good sealing effect, and adopts the method of vacuum and inert gas protection, which reduces the risk of leakage of vanadium pollutants.
(4)本发明制备出的球形钒合金粉可以通过增材制造技术开发出大量的复杂钒合金粉零件，以满足航天航空及国防军工的需要。(4) The spherical vanadium alloy powder prepared by the present invention can develop a large number of complex vanadium alloy powder parts through the additive manufacturing technology, so as to meet the needs of aerospace, national defense and military industries.
尽管上面已经通过结合示例性实施例和附图描述了本发明，但是本领域技术人员应该清楚，在不脱离权利要求所限定的精神和范围的情况下，可对本发明的示例性实施例进行各种修改和改变。Although the present invention has been described above in conjunction with the exemplary embodiments and the accompanying drawings, it should be apparent to those skilled in the art that various exemplary embodiments of the present invention can be made without departing from the spirit and scope defined by the claims. modifications and changes.
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