WO2023019882A1 - 一种盐膜法提高合金微区表面质量的方法及应用 - Google Patents

一种盐膜法提高合金微区表面质量的方法及应用 Download PDF

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WO2023019882A1
WO2023019882A1 PCT/CN2022/072777 CN2022072777W WO2023019882A1 WO 2023019882 A1 WO2023019882 A1 WO 2023019882A1 CN 2022072777 W CN2022072777 W CN 2022072777W WO 2023019882 A1 WO2023019882 A1 WO 2023019882A1
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alloy
micro
electrolytic machining
salt film
surface quality
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French (fr)
Inventor
郭鹏飞
吴�琳
王家昌
刘岩松
林鑫
兰红波
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Northwestern Polytechnical University
Qingdao University of Technology
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Northwestern Polytechnical University
Qingdao University of Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H3/00—Electrochemical machining, i.e. removing metal by passing current between an electrode and a workpiece in the presence of an electrolyte
    • B23H3/10—Supply or regeneration of working media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
    • B33Y40/20—Post-treatment, e.g. curing, coating or polishing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H11/00—Auxiliary apparatus or details, not otherwise provided for
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H3/00—Electrochemical machining, i.e. removing metal by passing current between an electrode and a workpiece in the presence of an electrolyte
    • B23H3/08—Working media
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23H—WORKING OF METAL BY THE ACTION OF A HIGH CONCENTRATION OF ELECTRIC CURRENT ON A WORKPIECE USING AN ELECTRODE WHICH TAKES THE PLACE OF A TOOL; SUCH WORKING COMBINED WITH OTHER FORMS OF WORKING OF METAL
    • B23H2200/00—Specific machining processes or workpieces
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention relates to the technical field of electrolytic processing for laser additive manufacturing, in particular to a method and application of a salt film method for improving the surface quality of alloy micro-regions.
  • laser stereoforming technology can realize high-performance, fully dense, and near-net shape of large, complex, and difficult-to-machine metal components. Therefore, it is widely used in aviation, aerospace, navigation, and nuclear power.
  • Nickel-based superalloys have attracted much attention due to their excellent mechanical properties, good structural stability and excellent oxidation resistance.
  • laser stereoforming technology has been proved to be one of the effective processing methods for complex components of large nickel-based superalloys.
  • the surface quality of laser three-dimensional formed nickel-base superalloy components is extremely poor, and surface treatment must be performed before the formed parts are applied.
  • nickel-based superalloys are prone to problems such as low processing efficiency, poor surface quality, and severe tool wear by traditional machining (turning, milling, planing, grinding, etc.).
  • the electrolytic processing technology characterized by electrochemical anodic dissolution and removal of materials can get rid of the limitations of the mechanical properties of the material itself, such as strength and hardness, and realize high-efficiency, low-cost, and tool-free processing. It has been widely used in laser three-dimensional forming Subsequent processing methods for large components.
  • the electrolyte commonly used in electrolytic machining technology is water-based neutral salt solution.
  • the metal undergoes anodic dissolution in the water-based electrolyte, it is very easy to form a surface super-passive film on its surface, which makes the processing efficiency of electrolytic machining low, the surface quality is poor, and the processing process is unstable.
  • the electrolyte Although a higher current density can effectively remove the super-passive film on the surface, due to the high solubility of metal ions in the water-based electrolyte, and the electrolyte generally has a high flow rate (generally greater than 10m/s), nickel The metal ions on the surface of the base superalloy will be quickly taken away by the electrolyte, and it is difficult to deposit on the surface of the sample to form a salt film, and it is difficult to obtain a good surface quality.
  • the microstructure of the deposited nickel-based superalloy contains a large number of irregularly shaped second-phase particles (Laves phase) with stable electrochemical properties.
  • the prior art discloses a technical solution for improving the surface quality of machining by using sodium chloride ethylene glycol electrolyte instead of water-based electrolyte.
  • the technical solution can effectively avoid water-based
  • the formation of an oxide film on the surface when the solution is used as the electrolyte can significantly improve the problems of low processing efficiency, poor surface quality, and unstable processing during electrolytic machining.
  • This technical solution can indeed improve the surface quality of the workpiece to a certain extent.
  • the inventors of the present application have found that even if sodium chloride ethylene glycol solution is used to replace the water-based salt solution as the electrolyte, the surface of the workpiece after electrolytic processing still has micro-region unevenness, which is because of different composition phases and segregation in the microstructure. There are still differences in the dissolution rate of the micro-regions. The problem of poor surface quality of the micro-regions will reduce the service life of the alloy and limit the further application of alloy materials including nickel-based superalloys.
  • electrolytic machining using sodium chloride ethylene glycol electrolyte can indeed improve the surface quality of nickel-based superalloys formed by laser stereoforming. Uneven, accompanied by faint defects, it is speculated that this defect may be related to the uneven microstructure. It can be seen that the surface of the workpiece alloy still has the problem of poor micro-area quality. The micro-area defects seriously affect the service life of the alloy device, especially in the place under dynamic load. These micro-area defects can easily induce crack initiation.
  • the present disclosure provides a method and application of a salt film method for improving the surface quality of alloy micro-domains.
  • a salt film method for improving the surface quality of alloy micro-domains.
  • a method for improving the surface quality of an alloy micro-domain by a salt film method includes: adding nickel chloride to a sodium chloride ethylene glycol electrolyte until saturated and performing electrolytic machining.
  • the alloy member obtained by the above method is used, and the surface roughness Ra of the alloy member is 0.005-0.04 ⁇ m.
  • the above method is applied in the electrolytic processing of laser three-dimensional forming alloy.
  • the above-mentioned alloy components are used in the preparation of engines, gas turbines, and nuclear reactors.
  • the present disclosure finds that even if sodium chloride ethylene glycol is used for electrolytic machining, there are still problems of micro-area defects, poor micro-area quality, and complicated processing technology on the surface of alloy workpieces, but the prior art does not address electrolytic machining After further research on the surface of the alloy, the above-mentioned problems were not realized. It can be seen that the discovery of the above-mentioned problems in this disclosure is very important and innovative, and has far-reaching significance for promoting the further application of alloy components.
  • the present disclosure also finds that in the process of treating the surface of the alloy with saturated nickel chloride and sodium chloride ethylene glycol electrolyte, not only can the formation of product films and impurities that cause micro-region defects be suppressed, but also the electrolytic machining
  • the metal nickel ions produced in the process have no time to diffuse, and a supersaturated salt film (mainly nickel chloride) can be formed on the surface of the alloy workpiece.
  • the salt film can effectively reduce the dissolution of the surface concave area and accelerate the dissolution of the convex area, making the micro-area The surface becomes smooth, thereby effectively solving the problem of poor micro-area quality on the surface of alloy electrolytic machining.
  • the obtained alloy surface roughness Ra is 0.005-0.04 ⁇ m, which is far lower than that using The surface roughness of the alloy treated with sodium chloride ethylene glycol greatly improves the quality of the alloy components.
  • the alloy component obtained by using the above scheme is smooth and bright, and there is no microscopic unevenness, let alone weak defects, and the device prepared by using the alloy component has a long service life.
  • reagents or raw materials used in the present invention can be purchased through conventional channels. Unless otherwise specified, the reagents or raw materials used in the present invention are used in accordance with conventional methods in the art or according to product instructions. In addition, any methods and materials similar or equivalent to those described can be applied to the method of the present invention. The preferred implementation methods and materials described herein are for demonstration purposes only.
  • the existing technology has not found that using sodium chloride ethylene glycol as the electrolyte to electrolytically process the laser three-dimensionally formed nickel-based superalloy still has micro-area defects and poor surface quality of the micro-area, which affects the service life of alloy parts.
  • the present disclosure provides a method and application of a salt film method for improving the surface quality of alloy micro-domains.
  • a method for improving the surface quality of an alloy micro-domain by a salt film method includes: adding nickel chloride to a sodium chloride ethylene glycol electrolyte until saturated, and performing electrolytic machining.
  • chromium trichloride and/or ferrous chloride can be further added to the sodium chloride ethylene glycol electrolyte. Chromium trichloride or ferrous chloride and nickel chloride form a synergistic effect, which is beneficial to further promote the salt film formation.
  • Sodium chloride can improve the conductivity of the ethylene glycol solution.
  • the ethylene glycol solution can avoid the formation of oxides, hydroxides or other impurities on the surface of the workpiece during electrolytic machining, thus laying the foundation for obtaining a smooth surface.
  • Chlorine Nickel can effectively inhibit the diffusion of metal ions (mainly nickel ions) on the surface of the workpiece during electrolytic machining without being taken away by the electrolyte, so that it is easier to induce the formation of a saturated salt film on the surface. The appearance of a saturated salt film significantly improves the alloy Surface domain quality.
  • the conventional inventive concept of using sodium chloride ethylene glycol as the electrolyte for electrolytic machining to improve surface quality is to avoid the generation of surface oxide film during processing, thereby avoiding the selective dissolution of the anode workpiece due to the destruction of the oxide film.
  • the present disclosure promotes the formation of a saturated salt film during the electrolytic machining process, so as to precisely control the dissolution rate of each micro-area of the ⁇ -matrix/second phase/niobium segregation zone ternary system, which is a good solution The problem of poor micro-area quality was solved.
  • the present disclosure not only discovers the new problem of poor micro-domain quality on the alloy surface, but also proposes a new method to solve the poor micro-domain quality by using the salt film method.
  • the DC electrolytic machining process parameters are: DC electrolytic machining process parameters can be voltage 20-30V, machining gap 0.3-0.7mm, electrolyte flow rate 5-10ml/s, feed speed: 1-10mm/s, and the electrolyte is saturated chlorine Nickel, sodium chloride ethylene glycol electrolyte.
  • the second is to directly use nanosecond pulse power to process the surface of alloy components.
  • the nanosecond pulse electrolytic machining process parameters are: the initial machining gap between the two poles is 1-3 ⁇ m, the electrolyte flow rate is 5-15ml/s, the pulse voltage is 10-24V, the pulse width is 1-100ns, and the duty cycle is 30- 60%, the feed speed is 1-10mm/s, and the electrolyte is ethylene glycol solution of saturated nickel chloride and sodium chloride.
  • the optimal parameters are that the initial machining gap between the two poles is 2 ⁇ m, the electrolyte flow rate is 5ml/s, the pulse width is 3ns, the duty cycle is 50%, and the feed rate is 2mm/s.
  • the electrolyte is saturated nickel chloride and sodium chloride in ethylene glycol solution.
  • the alloy described in the present invention is preferably nickel-base superalloy and has very important application value.
  • the alloy member obtained by the above processing method has a smooth and bright surface, a roughness Ra of 0.005-0.04 ⁇ m, and no microscopic unevenness, let alone weak defects.
  • the alloy component processed in the present disclosure has a more excellent surface quality, improves the mechanical properties of the alloy component, and prolongs the service life.
  • the above method is applied in electrolytic processing of laser three-dimensional forming alloy.
  • the application of the above-mentioned alloy components in the preparation of engines, gas turbines, and nuclear reactors the surface quality of the alloy components prepared in the above scheme is further improved, so that the assembly of the alloy components can be further improved.
  • the tool electrode is a stainless steel tube electrode (outer diameter 1.2mm, inner diameter 0.8mm)
  • the applied voltage is 24V
  • the machining gap is 0.5mm
  • the feed rate is 2mm/s
  • the electrolyte flow rate is 5ml/ s
  • the electrolyte is sodium chloride ethylene glycol electrolyte added with saturated nickel chloride.
  • Test results The surface morphology of the sample was observed with a laser confocal microscope, and the surface roughness Ra of the component was directly obtained to be 0.04 ⁇ m, and there was no micro-region unevenness and micro-defects.
  • a salt film method for improving the surface quality of alloy micro-regions, using nanosecond pulse electrolytic machining directly on the surface of alloy components specifically:
  • the laser three-dimensional forming Inconel 718 alloy component is completed, it is directly subjected to nanosecond pulse electrolytic machining. Due to the uneven surface of the component, when using a stainless steel tube electrode (1.2mm in outer diameter and 0.8mm in inner diameter) for processing, the highest point of the sample should be used as the reference for processing.
  • the distance between the end face of the tube electrode and the highest point of the sample is 2 ⁇ m
  • the feed rate in the horizontal plane is 2 mm/s
  • the flow rate of the electrolyte is 5 ml/s
  • the electrolyte is sodium chloride ethylene glycol electrolyte with saturated nickel chloride.
  • the applied potential is 10V
  • the pulse frequency is 10ns
  • the duty cycle is 50%.
  • the tube electrode is lowered for a certain distance to ensure that the distance from the tube electrode to the surface of the sample is 2 ⁇ m. After processing one layer, use the above process parameters in turn to process the remaining margin.
  • Test results The surface morphology of the sample was observed with a laser confocal microscope, and the surface roughness Ra of the component was directly obtained to be 0.1 ⁇ m, with micro-region unevenness and micro-defects.
  • Example 2 Comparing Example 1 and Example 2, it can be seen that the nanosecond pulse electrolytic machining process has no obvious advantages in improving the surface roughness Ra and improving the surface quality of the alloy, but due to the extremely low material removal rate of this process, the processing efficiency is reduced and the production cost is high. , and the treated metal surface still has micro-region unevenness and micro-defects.
  • a method for improving the surface quality of alloy micro-regions by using a salt film method, using direct current electrolytic machining on the surface of alloy components specifically:
  • the tool electrode is a stainless steel tube electrode (outer diameter 1.2mm, inner diameter 0.8mm)
  • the applied voltage is 24V
  • the machining gap is 0.5mm
  • the feed rate is 2mm/s
  • the electrolyte flow rate is 5ml/ s
  • the electrolyte is sodium chloride ethylene glycol electrolyte added with saturated nickel chloride and chromium trichloride.
  • Test results The surface morphology of the sample was observed with a laser confocal microscope, and the surface roughness Ra of the component was directly obtained to be 0.02 ⁇ m, and there was no micro-region unevenness and micro-defects.
  • a method for improving the surface quality of alloy micro-regions by using a salt film method, using direct current electrolytic machining on the surface of alloy components specifically:
  • the tool electrode is a stainless steel tube electrode (outer diameter 1.2mm, inner diameter 0.8mm), the applied voltage is 24V, the machining gap is 0.5mm, the feed rate is 2mm/s, and the electrolyte flow rate is 5ml/ s, the electrolyte is sodium chloride ethylene glycol electrolyte added with saturated nickel chloride, chromium trichloride and ferrous chloride.
  • the electrolyte is sodium chloride ethylene glycol electrolyte added with saturated nickel chloride, chromium trichloride and ferrous chloride.
  • Test results The surface morphology of the sample was observed with a laser confocal microscope, and the surface roughness Ra of the component was directly obtained to be 0.005 ⁇ m, and there was no micro-region unevenness and micro-defects.
  • Example 1 The difference from Example 1 is that the electrolyte is replaced by an ethylene glycol electrolyte saturated with sodium chloride, and other conditions remain unchanged.
  • Test results The surface morphology of the sample was observed with a laser confocal microscope, and the surface roughness Ra of the component was directly obtained to be 0.25 ⁇ m, with microscopic unevenness and weak defects.
  • Comparing Example 1 with Comparative Example 1 it can be seen that by using saturated nickel chloride and sodium chloride ethylene glycol electrolyte, it is very easy to form a supersaturated salt film on the surface of the alloy workpiece, thereby effectively solving the micro-area quality of the alloy electrolytic machining surface Poor puzzle.
  • Comparative Example 1 the means of reciprocating processing on the processing area is complicated, the number of reciprocating times is more, the processing efficiency is low, and the surface quality of the micro-area is still not up to the level of Example 1.
  • the addition of nickel chloride effectively solves the problem of micro-area surface unevenness and micro-defects on the surface of the alloy component after processing, greatly improves the quality of the alloy component and prolongs the service life.

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Abstract

本发明涉及激光增材制造的电解加工技术领域，具体为一种盐膜法提高合金微区表面质量的方法及应用，所述方法包括：采用饱和氯化镍、氯化钠乙二醇混合电解液进行电解加工。通过在工件表面形成过饱和的盐膜，从而进一步提高了工件表面微区质量，提高了合金器件的使用寿命。

Description

一种盐膜法提高合金微区表面质量的方法及应用 技术领域
本发明涉及激光增材制造的电解加工技术领域，具体为一种盐膜法提高合金微区表面质量的方法及应用。
背景技术
公开该背景技术部分的信息仅仅旨在增加对本发明的总体背景的理解，而不必然被视为承认或以任何形式暗示该信息构成已经成为本领域一般技术人员所公知的现有技术。
激光立体成形技术作为一种先进的增材制造技术，可实现大型、复杂、难加工金属构件的高性能、全致密、近净成形，因此被广泛应用在航空、航天、航海以及核电等领域。镍基高温合金以其力学性能优异、组织稳定性好以及抗氧化性能优良的特点而备受关注。目前，激光立体成形技术已经被证明是大型镍基高温合金复杂构件的有效加工方法之一。然而，激光立体成形镍基高温合金构件的表面质量极差，在成形件应用之前必须经过表面处理。而镍基高温合金作为一种典型的难加工材料，采用传统的机械加工(车、铣、刨、磨等)容易引起加工效率低、表面质量差、刀具磨损严重等问题。以电化学阳极溶解去除材料为技术特征的电解加工技术，可以摆脱材料本身强度、硬度等力学性能的限制，实现高效率、低成本、无工具电极磨损的加工，已被广泛应用于激光立体成形大型构件的后续加工 方法。
当前，电解加工技术普遍采用的电解液为水基中性盐溶液。通常情况下，金属在水基电解液中发生阳极溶解时，极易在其表面形成一层表面超钝化膜，使得电解加工的加工效率低、表面质量差、加工过程不稳定。尽管较高的电流密度可以有效的去除表面超钝化膜，但是由于金属离子在水基电解液中的溶解度很大，且电解液一般具有较高的流速(一般大于10m/s)，因此镍基高温合金表面的金属离子会迅速被电解液带走，不易沉积在试样表面形成盐膜，很难获得较好的表面质量。需要指出的是，激光立体成形过程中，由于激光熔池的非平衡快速凝固，使得沉积态镍基高温合金微观组织包含了大量的形状不规则的电化学性能稳定的第二相颗粒(Laves相以及碳化物相)以及铌元素偏析区，采用水基电解液进行电解加工时，即便在高电流密度情况下，阳极材料加工表面亦较为粗糙，这主要是由于微观组织表面形成的超钝化膜的不均匀破裂使得各组成部分的阳极溶解速率存在差异(如铌偏析区溶解速率最快，γ基体相次之，第二相溶解速率最慢)，最终使得表面存在明显的微区不平整度。不难看出，采用水基电解液进行电解加工时，表面质量极易受到阳极材料内部微观组织的影响，尤其对于微观组织结构复杂的激光立体成形镍基高温合金构件。
为了提高工件表面质量，现有技术公开了利用氯化钠乙二醇电解液替换水基电解液来提高加工表面质量的技术方案，该技术方案通过采用乙二醇电解液，可有效避免水基溶液作为电解液时表面氧化膜的形成，显著改 善电解加工时的加工效率低、表面质量差、加工过程不稳定等问题。该技术方案确实能够在一定程度上提高工件表面质量。然而，工艺过程极为复杂，需要往复扫描加工；另外，现有技术工艺对于成形构件后续表面处理仅仅止步于此，并没有发现利用氯化钠乙二醇作为电解液进行电解加工后的工件表面仍然存在一系列的问题。
本申请发明人发现，即使采用氯化钠乙二醇溶液替换水基盐溶液作为电解液，经过电解加工之后的工件表面仍然存在微区不平整，这是因为微观组织中的不同组成相及偏析区的溶解速率仍然存在差异，这种微区表面质量差的问题将会降低合金的使用寿命，限制合金材料包括镍基高温合金的进一步应用。
发明内容
虽然，已经有大量的研究采用氯化钠乙二醇电解液来对合金进行电解加工，并通过采用特定的电解加工工艺获得了较好的表面质量，但是都只针对于单相合金(TiAl)或两相合金(钛合金)；另外，电解加工工艺较为复杂(如，较快的进给速率以及往复扫描等)。而对于微观组织极不均匀的激光立体成形镍基高温合金构件(γ基体/第二相/铌偏析区)，采用氯化钠乙二醇电解液电解加工之后，并没有获得理想的表面质量。
然而，本公开发明人发现，利用氯化钠乙二醇电解液进行电解加工确实能够提高激光立体成形镍基高温合金表面质量，但是，经过仔细研究发现，电解加工之后的合金表面仍然存在微区不平整，并伴随着微弱的缺陷，猜测这种缺陷可能与微观组织不均匀有关。可见，工件合金表面仍然存在 着微区质量差的问题，微区缺陷严重影响着合金器件的使用寿命，尤其是承受动载的场所，这些微区缺陷极易诱导裂纹萌生。
由此可见，本公开发明人对于采用氯化钠乙二醇溶液作为电解液进行电解加工之后仍然存在构件表面微区缺陷、表面质量差问题的发现具有深刻而显著的研究意义。
为了解决上述问题，本公开提供了一种盐膜法提高合金微区表面质量的方法及应用，通过在工件表面形成过饱和的盐膜，实现对微区溶解行为的精确控制，从而进一步提高了工件表面微区质量，提高了合金器件的使用寿命。
具体地，本公开的技术方案如下所述：
在本公开的第一方面，一种盐膜法提高合金微区表面质量的方法，所述方法包括：在氯化钠乙二醇电解液中添加氯化镍直至饱和并进行电解加工。
在本公开的第二方面，采用上述方法得到的合金构件，所述合金构件表面粗糙度Ra为0.005-0.04μm。
在本公开的第三方面，上述的方法在激光立体成形合金电解加工中的应用。
在本公开的第四方面，上述的合金构件在制备发动机、燃气轮机、核反应器中的应用。
本公开中的一个或多个技术方案具有如下有益效果：
(1)、首先，本公开发现了即使利用氯化钠乙二醇进行电解加工， 合金工件表面仍然存在微区缺陷、微区质量差、加工工艺复杂的问题，而现有技术没有对电解加工后的合金表面进行进一步研究，并没有意识到上述问题，可见，本公开关于上述问题的发现本身就具有非常重要的创新性，对于推动合金构件的进一步应用具有深远的意义。
(2)、本公开还发现，采用饱和氯化镍、氯化钠乙二醇电解液，处理合金表面的过程中，不仅可以抑制造成微区缺陷的产物膜、杂质的形成，而且，电解加工过程中产生的金属镍离子来不及扩散，可在合金工件表面形成过饱和的盐膜(主要为氯化镍)，盐膜可有效降低表面凹陷区域的溶解并加速凸起区域的溶解，使得微区表面变得平整，从而有效解决合金电解加工表面微区质量差的难题。
(3)、利用上述方法进一步解决合金微区质量差的问题，相对于现有技术进一步提高了合金工件表面微区质量，得到的合金表面粗糙度Ra为0.005-0.04μm，远远低于采用氯化钠乙二醇处理后的合金表面粗糙度，极大的提升了合金构件的质量。
(4)、利用上述方案得到的合金构件，合金表明光滑明亮，不存在微观不平整度，更不存在微弱的缺陷，利用该合金构件制备的器件具有较长的使用寿命。
具体实施方式
下面结合具体实施例，进一步阐述本公开。应理解，这些实施例仅用于说明本公开而不用于限制本公开的范围。下列实施例中未注明具体条件的实验方法，通常按照常规条件或按照制造厂商所建议的条件。
除非另行定义，文中所使用的所有专业与科学用语与本领域熟练人员所熟悉的意义相同。本发明所使用的试剂或原料均可通过常规途径购买获得，如无特殊说明，本发明所使用的试剂或原料均按照本领域常规方式使用或者按照产品说明书使用。此外，任何与所记载内容相似或均等的方法及材料皆可应用于本发明方法中。文中所述的较佳实施方法与材料仅作示范之用。
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公开的示例性实施方式。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、操作和/或它们的组合。
目前，现有技术并没有发现采用氯化钠乙二醇为电解液对激光立体成形镍基高温合金进行电解加工处理后仍然存在微区缺陷、微区表面质量较差从而影响合金部件使用寿命的问题，因此，本公开提供了一种盐膜法提高合金微区表面质量的方法及应用。
在本公开的一种实施方式中，一种盐膜法提高合金微区表面质量的方法，所述方法包括：在氯化钠乙二醇电解液中添加氯化镍直至饱和并进行电解加工。此外，还可以在氯化钠乙二醇电解液中进一步添加三氯化铬和/或氯化亚铁，三氯化铬或氯化亚铁与氯化镍形成协同作用，有利于进一步促进盐膜的生成。
氯化钠可提高乙二醇溶液的导电性，乙二醇溶液可避免工件表面在电 解加工过程中形成氧化物、氢氧化物或其他杂质的产生，从而为获得一个光整表面奠定基础，氯化镍可有效的抑制电解加工过程中工件表面金属离子(主要是镍离子)的扩散而不被电解液带走，从而更容易诱导表面饱和盐膜的形成，饱和盐膜的出现显著提高了合金表面微区质量。
然而，常规的利用氯化钠乙二醇作为电解液进行电解加工提高表面质量的发明构思在于避免加工过程中表面氧化膜的产生，从而避免因氧化膜破坏引起阳极工件的选择性溶解。可是，不同于常规思路，本公开通过在电解加工过程中促进饱和盐膜的形成，从而对γ基体/第二相/铌偏析区三元体系各微区溶解速率进行精确调控，很好的解决了微区质量差的问题。
因此，本公开不仅发现了合金表面微区质量差的新的问题，而且，又提出了利用盐膜法解决微区质量差的新的方法。
采用盐膜法进行电解加工可以有两种方式：
一种是直接采用直流电源对激光立体成形镍基高温合金构件表面进行加工。直流电解加工工艺参数为：直流电解加工工艺参数可以为电压20-30V，加工间隙0.3-0.7mm，电解液流速5-10ml/s，进给速度：1-10mm/s，电解液选用饱和氯化镍、氯化钠的乙二醇电解液。最佳的，直流电解加工工艺参数：电压24V，加工间隙0.5mm，电解液流速5ml/s，电解液选用饱和氯化镍、氯化钠的乙二醇电解液。
第二种是直接采用纳秒脉冲电源对合金构件表面进行加工。其中，纳秒脉冲电解加工工艺参数为：两极初始加工间隙为1-3μm，电解液流速为5-15ml/s，脉冲电压为10-24V，脉冲宽度为1-100ns，占空比为30-60％， 进给速度为1-10mm/s，电解液选用饱和氯化镍、氯化钠的乙二醇溶液。为了优化合金构件表面，提高合金构件质量，最优参数，两极初始加工间隙为2μm，电解液流速为5ml/s，脉冲宽度为3ns，占空比为50％，进给速度为2mm/s，电解液为饱和氯化镍、氯化钠的乙二醇溶液。
激光立体成形Inconel 718镍基高温合金其电解加工表面微区存在严重的不平整问题，限制了镍基高温合金的进一步应用，因此，本发明所述合金优选为镍基高温合金具有非常重要的应用价值。
在本公开的一种实施方式中，采用上述加工方法得到的合金构件，表面光滑明亮，粗糙度Ra为0.005-0.04μm，不存在微观不平整度，更不存在微弱的缺陷。显然，本公开加工后的合金构件具有更优异的表面质量，提高了合金构件的力学性能，延长了使用寿命。
在本公开的一种实施方式中，上述的方法在激光立体成形合金电解加工中的应用。
在本公开的一种实施方式中，上述的合金构件在制备发动机、燃气轮机、核反应器中的应用，在上述方案制备的合金构件的表面质量被进一步提高，从而能够进一步提高利用该合金构件组装而成的发动机、燃气轮机、核反应器等装置的使用寿命。
为了使得本领域技术人员能够更加清楚地了解本公开的技术方案，以下将结合具体的实施例详细说明本公开的技术方案。
实施例1
一种盐膜法提高合金微区表面质量的方法，采用直接对合金构件表面 进行直流电解加工，具体为：
激光立体成形Inconel 718合金构件完成后，直接对其进行直流电解加工。直流电解加工工艺参数为：工具电极为不锈钢管电极(外径为1.2mm，内径为0.8mm)，外加电压为24V，加工间隙为0.5mm，进给速率为2mm/s，电解液流速5ml/s，电解液选用添加饱和氯化镍的氯化钠乙二醇电解液。加工完一层后，调节管电极高度使得加工间隙为0.5mm，并开始新一层的加工，直至加工完剩余余量。
测试结果：采用激光共聚焦显微镜观察试样表面形貌，并直接获取构件表面粗糙度Ra为0.04μm，不存在微区不平整度和微缺陷。
实施例2
一种盐膜法提高合金微区表面质量的方法，采用直接对合金构件表面进行纳秒脉冲电解加工，具体为：
激光立体成形Inconel 718合金构件完成后，直接对其进行纳秒脉冲电解加工。由于构件表面凹凸不平，采用不锈钢管电极(外径为1.2mm，内径为0.8mm)进行加工时，要以试样的最高点为基准，进行加工。管电极的端面距离试样的最高点为2μm，水平面内的进给速率为2mm/s，电解液流速为5ml/s，电解液选用添加饱和氯化镍的氯化钠乙二醇电解液。外加电位为10V，脉冲频率为10ns，占空比为50％。加工完本层后，管电极再下降一定距离，确保管电极到试样表面的距离为2μm。加工完一层后，依次采用以上工艺参数进行剩余余量的加工。
测试结果：采用激光共聚焦显微镜观察试样表面形貌，并直接获取构 件表面粗糙度Ra为0.1μm，存在微区不平整度和微缺陷。
数据分析：
实施例1和实施例2比较可知，纳秒脉冲电解加工工艺在提高表面粗糙度Ra、提高合金表面质量方面没有明显优势，但由于该工艺材料去除速率极低，降低了加工效率，生产成本高，而且处理得到的金属表面仍然存在微区不平整度和微缺陷。
实施例3：
一种盐膜法提高合金微区表面质量的方法，采用直接对合金构件表面进行直流电解加工，具体为：
激光立体成形Inconel 718合金构件完成后，直接对其进行直流电解加工。直流电解加工工艺参数为：工具电极为不锈钢管电极(外径为1.2mm，内径为0.8mm)，外加电压为24V，加工间隙为0.5mm，进给速率为2mm/s，电解液流速5ml/s，电解液选用添加了饱和氯化镍、三氯化铬的氯化钠乙二醇电解液。加工完一层后，调节管电极高度使得加工间隙为0.5mm，并开始新一层的加工，直至加工完剩余余量。
测试结果：采用激光共聚焦显微镜观察试样表面形貌，并直接获取构件表面粗糙度Ra为0.02μm，不存在微区不平整度和微缺陷。
实施例4：
一种盐膜法提高合金微区表面质量的方法，采用直接对合金构件表面进行直流电解加工，具体为：
激光立体成形Inconel 718合金构件完成后，直接对其进行直流电解加 工。直流电解加工工艺参数为：工具电极为不锈钢管电极(外径为1.2mm，内径为0.8mm)，外加电压为24V，加工间隙为0.5mm，进给速率为2mm/s，电解液流速5ml/s，电解液选用添加了饱和氯化镍、三氯化铬和氯化亚铁的氯化钠乙二醇电解液。加工完一层后，调节管电极高度使得加工间隙为0.5mm，并开始新一层的加工，直至加工完剩余余量。
测试结果：采用激光共聚焦显微镜观察试样表面形貌，并直接获取构件表面粗糙度Ra为0.005μm，不存在微区不平整度和微缺陷。
对比例1
与实施例1的区别在于：将电解液替换为饱和氯化钠的乙二醇电解液，其他条件不变。
测试结果：采用激光共聚焦显微镜观察试样表面形貌，并直接获取构件表面粗糙度Ra为0.25μm，存在微观不平整度和微弱缺陷。
数据分析：
实施例1和对比例1比较，可见，通过采用饱和氯化镍、氯化钠乙二醇电解液，极易在合金工件表面形成过饱和的盐膜，从而有效解决合金电解加工表面微区质量差的难题。另外，对比例1中，对加工区域进行往复加工的手段，工艺复杂，往复次数更多，加工效率低下，而且微区表面质量仍然达不到实施例1的水平。实施例1中，氯化镍的加入，有效解决了加工后合金构件表面存在微区表面不平整以及微缺陷的问题，极大的提升了合金构件的质量延长了使用寿命。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，尽管 参照前述实施例对本发明进行了详细的说明，对于本领域的技术人员来说，其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种盐膜法提高合金微区表面质量的方法，其特征是，所述方法包括：在氯化钠乙二醇电解液中添加氯化镍直至饱和并进行电解加工。
  2. 如权利要求1所述的一种盐膜法提高合金微区表面质量的方法，其特征是，所述氯化钠乙二醇电解液中进一步添加三氯化铬和/或氯化亚铁。
  3. 如权利要求1所述的一种盐膜法提高合金微区表面质量的方法，其特征是：所述电解加工采用直流电解加工或脉冲电解加工；优选的为所述电解加工为直流电解加工。
  4. 如权利要求1所述的一种盐膜法提高合金微区表面质量的方法，其特征是，所述合金包括固溶强化型合金、沉淀强化型合金或颗粒增强型金属基复合材料，优选的，所述合金为沉淀强化型合金。
  5. 如权利要求4所述的一种盐膜法提高合金微区表面质量的方法，其特征是，所述沉淀强化型合金为镍基高温合金。
  6. 如权利要求3所述的一种盐膜法提高合金微区表面质量的方法，其特征是，所述直流电解加工工艺参数：电压20-30V，加工间隙0.3-0.7mm，电解液流速5-15ml/s；优选的，直流电解加工工艺参数：电压24V，加工间隙0.5mm，电解液流速5ml/s。
  7. 采用权利要求1-6任一所述的方法得到的合金构件，其特征是，所述合金构件表面粗糙度Ra为0.005-0.04μm。
  8. 权利要求1-6任一所述的方法在激光立体成形合金电解加工中的应用。
  9. 权利要求7所述的合金构件在制备发动机、燃气轮机、核反应器中 的应用。
  10. 如权利要求9所述的应用，其特征是，所述的合金构件为热端部件。
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040050715A1 (en) * 2002-09-13 2004-03-18 Zhu Joseph Shoulian Electropolishing solution and methods for its use and recovery
CN103360695A (zh) * 2012-03-30 2013-10-23 中国石油化工股份有限公司 耐久型聚氯乙烯盐膜组合物及其制备方法
CN105624770A (zh) * 2014-11-26 2016-06-01 乐普（北京）医疗器械股份有限公司 一种用于钴基合金的电化学抛光液
CN107335450A (zh) * 2017-05-26 2017-11-10 昆明理工大学 一种低共熔型离子液体中电沉积制备高催化析氧性能纳米多孔镍铁硫合金的方法
CN108914167A (zh) * 2018-07-13 2018-11-30 安徽迈德福新材料有限责任公司 一种电沉积法制备因瓦合金箔的工艺
CN110607541A (zh) * 2019-08-17 2019-12-24 山东理工大学 一种电火花加工金刚石用铜镍复合电极及其制备方法
CN112008166A (zh) * 2019-05-29 2020-12-01 天津大学 一种用于镍钛记忆合金微细电解加工的电解液
CN113618177A (zh) * 2021-08-17 2021-11-09 青岛理工大学 一种盐膜法提高合金微区表面质量的方法及应用

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005042810A2 (en) * 2003-10-31 2005-05-12 E.I Du Pont De Nemours And Company Membrane -mediated electropolishing
JP4334579B2 (ja) * 2007-03-28 2009-09-30 株式会社東芝 非水電解質電池用負極活物質、非水電解質電池、電池パック及び自動車
CN103703603B (zh) * 2012-04-16 2017-02-08 松下电器产业株式会社 电化学装置用非水电解质、其制造方法及使用其的电化学装置
CN103422116B (zh) * 2013-08-15 2016-08-17 重庆大学 一种多孔镍基钌氧化物复合析氢电极的制备方法
JP5601435B1 (ja) * 2013-11-05 2014-10-08 三菱電機株式会社 電解加工方法、電解加工装置および電解加工液
CN106191943A (zh) * 2016-07-19 2016-12-07 佛山市零碳节能光电科技有限公司 一种钴‑镍合金光亮防护镀层的超临界电镀制备方法及其制备系统
CN109267123A (zh) * 2018-12-04 2019-01-25 沈阳理工大学 用于镍钴合金镀层的氯化胆碱类离子液体型电解液及制法
CN109972193A (zh) * 2019-04-21 2019-07-05 山东理工大学 一种镍钛合金管电解抛光的抛光液及方法
US11193216B2 (en) * 2019-06-06 2021-12-07 Honeywell International Inc. Methods and systems for electrochemical machining of articles formed by additive manufacturing
GB2591763B (en) * 2020-02-05 2022-05-04 Texture Jet Ltd An electrolyte solution

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040050715A1 (en) * 2002-09-13 2004-03-18 Zhu Joseph Shoulian Electropolishing solution and methods for its use and recovery
CN103360695A (zh) * 2012-03-30 2013-10-23 中国石油化工股份有限公司 耐久型聚氯乙烯盐膜组合物及其制备方法
CN105624770A (zh) * 2014-11-26 2016-06-01 乐普（北京）医疗器械股份有限公司 一种用于钴基合金的电化学抛光液
CN107335450A (zh) * 2017-05-26 2017-11-10 昆明理工大学 一种低共熔型离子液体中电沉积制备高催化析氧性能纳米多孔镍铁硫合金的方法
CN108914167A (zh) * 2018-07-13 2018-11-30 安徽迈德福新材料有限责任公司 一种电沉积法制备因瓦合金箔的工艺
CN112008166A (zh) * 2019-05-29 2020-12-01 天津大学 一种用于镍钛记忆合金微细电解加工的电解液
CN110607541A (zh) * 2019-08-17 2019-12-24 山东理工大学 一种电火花加工金刚石用铜镍复合电极及其制备方法
CN113618177A (zh) * 2021-08-17 2021-11-09 青岛理工大学 一种盐膜法提高合金微区表面质量的方法及应用

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