WO2018006434A1 - 一种三维表面喷丸射流电沉积制造方法及装置 - Google Patents

一种三维表面喷丸射流电沉积制造方法及装置 Download PDF

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WO2018006434A1
WO2018006434A1 PCT/CN2016/089856 CN2016089856W WO2018006434A1 WO 2018006434 A1 WO2018006434 A1 WO 2018006434A1 CN 2016089856 W CN2016089856 W CN 2016089856W WO 2018006434 A1 WO2018006434 A1 WO 2018006434A1
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deposition
electrodeposition
liquid
conductive substrate
hard particles
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English (en)
French (fr)
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张朝阳
戴学仁
姜雨佳
焦健
曹增辉
蒋雯
顾秦铭
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Jiangsu University
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Jiangsu University
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/18—Electroplating using modulated, pulsed or reversing current
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/22—Electroplating combined with mechanical treatment during the deposition
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
    • C25D5/611—Smooth layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/67—Electroplating to repair workpiece

Definitions

  • the invention relates to the field of rapid prototyping processing in the manufacturing technology, in particular to a three-dimensional surface shot blasting electrode electrodeposition manufacturing method and device.
  • electrodeposition technology As a new type of processing and forming method, electrodeposition technology has been widely developed and applied in the fields of micro-fabrication technology and surface treatment technology with its good controllability of process parameters, such as micro-motors, micro-sensors, and micro-parts. Forming and repairing, surface coating and corrosion resistance of the parts have achieved good results. Therefore, electrodeposition technology is one of the most attractive research areas in the 21st century.
  • the publication number is: CN101994137A "High-speed jet injection electroforming processing method and device for a rotating body part", and proposes to use a high-speed jet to selectively scan the rotating body parts along a certain trajectory to build the required parts layer by layer.
  • the surface of the cast layer is rubbed by hard particles or friction members, thereby effectively removing defects such as surface burrs of the deposited layer surface.
  • the invention discloses a "laser-enhanced jet electrodeposition rapid prototyping processing apparatus and method" of CN103590080A, which proposes: synchronously shooting a high energy density laser beam and a high speed electrodeposition solution through a tubular passive anode center hole.
  • the combination of laser-enhanced electrodeposition technology and electrodeposition solution spraying can achieve high deposition speed and can realize regioselective deposition, and can quickly produce metal parts with dense structures and complex structures.
  • the method is simple, but the effect is not obvious, or the effect is good, but the device has low complexity and operability, which greatly limits the wide application of the electrodeposition technology. Moreover, the surface of the deposited layer will deteriorate the deposition quality with the deposition time, which will affect the compactness and uniformity of the material.
  • the present invention provides a three-dimensional surface shot blasting electrode electrodeposition manufacturing method and apparatus.
  • Mixing the deposition solution with the hard particles can not only achieve rapid fabrication of the electrodeposition technology, but also achieve spray
  • the purpose of surface strengthening of the pellets is to greatly increase the deposition rate of electrodeposition and improve the quality of the deposited layer.
  • the present invention achieves the above technical objects by the following technical means.
  • a three-dimensional surface shot blasting electrodeposition manufacturing method characterized in that the method comprises the following steps:
  • the deposition liquid is electrolytically deposited on the cathode conductive substrate; at the same time, the hard particles impact the instantaneous impact of the deposited surface, so that the grain arrangement of the deposited layer regularly forms sub-grains, flattening the tip portion of the surface of the deposited layer, and removing the cathode in time. Hydrogen bubbles and impurities, inhibiting the formation of nodules and pinhole pitting;
  • the deposition rate of the deposition liquid at the nozzle is 5 to 10 m/s.
  • a three-dimensional surface shot blasting electrode electrodeposition manufacturing apparatus comprising: a five-axis linkage numerical control processing system, an electrodeposition system, a liquid circulation system, a hydraulic system and a hard particle circulation system;
  • the five-axis linkage numerical control machining system comprises a five-axis linkage numerical control machining robot and a numerical control device, wherein the numerical control device is used for controlling a spatial angle and a movement path of the manipulator;
  • the electrodeposition system includes a power source, a cathode conductive substrate and an anode, and a negative electrode and a positive electrode of the power source are respectively connected to a cathode conductive substrate and an anode, and the anode is fixed on the five-axis linkage robot and located above the cathode conductive substrate;
  • the liquid circulation system includes a liquid storage tank, a deposition tank, a filter, a circulation pump, the deposition tank is located below the cathode conductive substrate, and is connected to the liquid storage tank through a pipeline, and the circulation pump and the filter are disposed in the deposition tank and a pipe between the liquid storage tanks; the liquid storage tank is connected to the anode through a rubber hose;
  • the hydraulic system is disposed between the liquid storage tank and the rubber hose, and includes a filtering device, a hydraulic pump, a throttle valve, a pressure gauge, and an overflow valve disposed between the throttle valve and the liquid storage tank.
  • the hydraulic pump and the filtering device are connected by a stainless steel pipe, and the filtering device is placed in the liquid storage tank;
  • the hard particle circulation system includes a collection funnel, a recycler, a reservoir, the collection funnel is disposed under the cathode conductive substrate, the recovery device is connected between the collection funnel and the reservoir, and the storage device passes through the pipeline and the rubber Hose or anode connected.
  • a stirrer and a heater are further disposed in the liquid storage tank; the heater is provided with a temperature sensor.
  • the anode has an inner diameter of 3 to 5 mm.
  • the power source is an adjustable pulse power source, the frequency range is 0.5 to 2 MHz, the peak voltage is 2 to 15 V, and the pulse width is 30 to 500 ns; the hydraulic pump is a variable pump, the working pressure is 10 bar or more, and the rated flow rate is not less than 10 L/min.
  • the stainless steel tube and the rubber hose have an inner diameter of 15 to 25 mm, and both inner walls are smooth.
  • the hard particles have a diameter of 500 to 800 ⁇ m and are subjected to pickling to remove impurities and baking treatment.
  • the invention combines the shot peening technology and the electrodeposition technology reasonably, and can not only overcome the defects such as loose texture, pitting and pits of the deposited layer caused by hydrogen deposition and impurity adhesion of the conventional electrodeposited cathode, and significantly improves the density and uniformity of the material.
  • Sexuality can not only achieve rapid fabrication of electrodeposition technology, but also achieve the purpose of surface strengthening of shot peening, greatly improve the deposition rate of electrodeposition and improve the quality of deposited layer.
  • the CNC machining system it can realize three-dimensional space forming and forming, which is widely used in the production of modern complex shape parts, and can also be used for rapid coating and surface strengthening technology.
  • the surface of the deposited layer is impacted multiple times, so that the deposited layer is regularly arranged under the impact stress, and the smaller subgrains are formed, thereby achieving the effect of shot peening and improving The hardness and compactness of the deposited layer.
  • the instantaneous coverage and shielding of the hard particles on the surface of the cathode can also act as a resisting agent for the surface active additive, slowing the grain growth rate during the electrodeposition process and achieving the purpose of grain refinement.
  • the friction effect of hard particles on the surface of the cathode can homogenize the microstructure of the deposited layer and improve the microstructure of the deposited layer. At the same time, it can remove cathode hydrogen bubbles and impurities in time, and inhibit the formation of defects such as nodules and pinhole pitting. Achieve the purpose of leveling the surface of the deposited layer.
  • FIG. 1 is a schematic view showing the structure of a surface shot blasting electrodeposition deposition apparatus according to the present invention.
  • FIG. 2 is a schematic structural view of an embodiment of an anode.
  • Figure 3 is a schematic view of the structure of another embodiment of the anode.
  • the three-dimensional surface blasting jet electrodeposition manufacturing method of the invention performs grinding, degreasing, pickling and water washing on the surface of the cathode conductive substrate before processing.
  • the cathode conductive substrate is fixed, and the positive and negative poles of the power source are respectively connected with the anode and cathode conductive substrates, and the power source is turned on.
  • the hydraulic pump with adjustable flow rate continuously supplies liquid flow power to the acidic deposition liquid, and the flow of the deposition liquid in the rubber hose
  • the negative pressure is formed at the interface between the storage of the hard particles and the rubber hose, the hard particles are strongly sucked in, and are thoroughly mixed with the deposition liquid, so that the discharged hard particles have a sufficient impact velocity and form a jet with the deposition liquid.
  • the jet is ejected from the nozzle to form a jet impinging on the cathode conductive substrate.
  • the impact velocity of the hard particles should be such that the force of the hard particles impacting the deposited surface is greater than that of the shot peening in the pneumatic shot peening process. force.
  • the deposition liquid When the deposition liquid is ejected from the anode, a high-speed high-pressure liquid flow is obtained due to a reduction in the diameter of the anode outlet. Specifically, the deposition rate of the deposition liquid at the nozzle is 5 to 10 m/s. Due to the conduction of the anode, the deposition liquid is electrolyzed, and the metal cations in the deposition liquid are electronically reduced to metal atoms on the cathode conductive substrate, and the desired part shape is deposited. At the same time, the hard particles have a large momentum due to their relatively large mass, and a large impulse is generated when impacting the cathode conductive substrate. The force of the hard particles impacting the deposition surface can exceed the spray in the shot peening process. The force of the pill on the workpiece, so as to achieve the purpose of impact strengthening the surface, realize the composite deposition processing of shot peening and electrochemistry.
  • the high-speed moving hard particles continue to impact the deposited layer to remove the internal stress during the deposition process, and compressing the deposited layer increases the deposition strength.
  • the hard particles flow along with the liquid flow and continue to rub the surface, which not only helps to remove the buildup and bulge, but also improve the surface.
  • the unevenness of the height is also conducive to the discharge and precipitation of gases, increasing the density and smoothness of the material, and the periodic pulse power supply also contributes to the realization of the shot peening effect, and finally achieves rapid and efficient deposition.
  • the present invention is a high-speed jet spray deposition by mixing a deposition liquid stream with hard particles, wherein the hard particles are micron-sized particles having a uniform particle size, and the deposition liquid is used for electrodeposition.
  • Process deposition solution The jetting of the deposition liquid to the cathode substrate by jetting realizes the rapid manufacturing purpose of jet electrodeposition, and constitutes the jet electrodeposition manufacturing system; the high-speed liquid stream accelerates the hard particles, so that the hard particles can be more impact than the pneumatic shot peening. Force to achieve the purpose of surface strengthening of shot peening.
  • the invention combines the two to realize rapid deposition while strengthening the deposition layer, realizes rapid manufacturing of shot peening and electrochemical composite deposition, simplifies the processing process, improves deposition efficiency, and realizes high quality and high efficiency electrochemical composite deposition processing. Quickly repair part surface defects and enhance surface properties.
  • the five-axis linkage CNC machining system includes a five-axis linkage CNC machining robot and a numerical control device; the numerical control device is used to control the space angle and the movement path of the manipulator.
  • the electrodeposition system includes a power source, a cathode conductive substrate, and an anode, the anode being a titanium alloy insoluble anode.
  • the positive electrode of the power source is connected to the titanium alloy insoluble anode
  • the negative electrode is connected to the cathode conductive substrate
  • an ammeter is connected in series between the three for detecting the current.
  • the anode is fixed on the five-axis linkage robot and above the cathode conductive substrate.
  • the cathode conductive substrate is fixed to the support frame.
  • the liquid circulation system includes a liquid storage tank, a deposition tank, a filter, a circulation pump, the deposition tank is located below the cathode conductive substrate, and is connected to the liquid storage tank through a pipeline, and the circulation pump and the filter are disposed in the deposition tank and On the pipeline between the liquid storage tanks, the circulation pump delivers the filtered solution to the liquid storage tank; the liquid storage tank communicates with the anode through a rubber hose.
  • the hydraulic system is disposed between the liquid storage tank and the rubber hose, and includes a filtering device, a hydraulic pump, a throttle valve, a pressure gauge, and an overflow valve disposed between the throttle valve and the liquid storage tank.
  • the hydraulic pump and the filtering device are connected by a stainless steel pipe, and the remaining devices of the hydraulic system are connected by a stainless steel pipe or a rubber hose, and the filtering device is placed in the liquid storage tank, and the hydraulic pump extracts the solution in the filtering device
  • the throttle valve, the relief valve and the pressure gauge are connected to the outlet of the hydraulic pump to adjust the output flow rate.
  • the hard particle circulation system includes a collection funnel, a recycler, a reservoir for storing hard particles, and is connected to a rubber hose or an anode through a pipe, and the collection funnel is placed under the cathode conductive substrate to collect the deposited
  • the hard particles are connected between the collection funnel and the reservoir for transporting the hard particles in the collection funnel to the reservoir.
  • the three-dimensional surface shot blasting electrodeposition deposition device of the invention is a three-dimensional surface shot blasting electrodeposition deposition device of the invention.
  • the positive electrode of the power source in the electrodeposition system is connected to the titanium alloy insoluble anode as the anode of the electrodeposition current loop; the negative electrode of the power source is connected to the cathode conductive substrate, and serves as the cathode of the electrodeposition circuit, and then the ammeter is connected in series in the circuit to detect the current.
  • the titanium alloy insoluble anode is fixed on the five-axis linkage CNC machining robot, and the input port of the titanium alloy insoluble anode is connected to the liquid storage tank through the rubber hose.
  • the cathode conductive substrate is placed on the support frame and positioned and clamped; the numerical control robot is connected with the numerical control device, and the spatial angle and the motion path of the numerical control robot are controlled by the program setting in the numerical control device to realize the three-dimensional space of the shot blasting electrodeposition. Processing and forming.
  • the liquid circulation system and the hard particle circulation system are provided, and the hydraulic circulation system provides power for the liquid circulation system and the hard particle circulation system, realizes mixing of the hard particles and the deposition liquid, and obtains the jet force.
  • the hydraulic pump 12 extracts the deposition liquid in the liquid storage tank 22 through the stainless steel tube through the filtering device 11, and is throttled by the throttle valve 7 and overflowed by the relief valve 8. After that, after the pressure measurement of the pressure gauge 6, the rubber hose 21 is entered. Due to the high-speed flow of the deposition liquid, a negative pressure is generated at the nozzle of the reservoir 5, and the hard particles are sucked into the rubber hose pipe by the high pressure, and the switch of the valve 4 is passed through the switch.
  • the flow and the stop of the mixed deposition liquid in the pipeline can be realized; when the deposition liquid flows through the titanium alloy insoluble anode 23, it is ejected from the nozzle through the electrolysis of the power source 1, and the metal crystal is reduced on the cathode conductive base 2 body.
  • the deposition layer 26 is obtained; the deposition liquid not involved in the deposition is collected into the deposition tank 15, filtered by the filter 14, and returned to the liquid storage tank 22 by the circulation pump 13 to be recycled again.
  • the hard particles after impacting the deposited layer are collected and collected by the collecting funnel 16 through the support frame 17, and returned to the accumulator 5 through the recovery device 19 to be reused, and the whole process can be continuously processed to realize high-speed and high-efficiency processing.
  • the three-dimensional surface blasting jet electrodeposition manufacturing device is further provided with a stirrer and a heater in the liquid storage tank; the heater is provided with a temperature sensor, and the mixing liquid and the temperature are adjusted.
  • the power supply adopts an adjustable pulse power source with a frequency range of 0.5 to 2 MHz, a peak voltage of 2 to 15 V, and a pulse width of 30 to 500 ns.
  • the hydraulic pump is a variable pump, the working pressure is more than 10 bar, and the rated flow is not less than 10 L/min.
  • the anode has a diameter of 3 to 5 mm.
  • the output voltage, pulse width, waveform and pulse frequency of the pulse power supply adjust the throttle valve to control the output flow of the hydraulic pump; adjust the opening size of the reservoir valve to control the content of hard particles in the sediment solution
  • the distance between the manipulator and the cathode conductive substrate is controlled by the numerical control device to achieve an optimal deposition effect.
  • the deposition liquid is ejected at a high speed through a nozzle on the insoluble anode of the titanium alloy, and an electron reduction reaction is obtained on the cathode conductive substrate to obtain a metal nano layer. Since the current density in the central region of the jet is large, a highly localized deposition effect can be obtained, and the desired three-dimensional shape can be obtained by cumulatively depositing the deposited layer in the deposition zone.
  • the metal conductive layer can be removed by rust removal under the impact of high-speed hard particles, and deposition is continued on the surface of the metal to strengthen the bonding strength with the substrate, and at the same time due to the hard particles.
  • the impact of the impact strengthens the mechanical properties of the substrate, and achieves shot peening at the same time as the impurity coating, simplifying the process and improving the working efficiency.
  • multiple nozzles can be installed at the same time to realize composite deposition and alternate deposition.
  • the composite deposition solution can also be configured to realize polycrystalline phase deposition and improve the performance of the substrate.
  • the anode can adopt a front mixed structure or a rear mixed structure; the two structures are basically the same in function, but the two structures have advantages in different occasions.
  • the anode of the front hybrid structure is directly connected to the titanium alloy insoluble anode 23 and the rubber hose 21 as shown in FIG. 2, and the titanium alloy insoluble anode is surrounded by a protective tempered glass cover 24, and the structure is relatively Simple, suitable for hard particles with a relatively large specific gravity. Since the hard particles are mixed with the deposition liquid earlier, the mixing of the two particles is relatively uniform, which is more conducive to the ejection of the fluid at the anode nozzle.
  • the equipment with the front hybrid structure is generally cumbersome and suitable for large equipment that does not frequently change the work site.
  • the anode of the post-mixing structure is shown in Fig. 3.
  • the titanium alloy insoluble anode 23 is provided with a branching pipe 25, which is made of the same material, is screwed and sealed, and has a protective tempered glass outside the titanium alloy insoluble anode 23.
  • the cover 24 is surrounded. Since the hard particles are mixed with the deposition liquid phase at the anode of the tool, the suction mode of the hard particles is generally suctioned by a negative pressure, and the tool anode is easily worn by the titanium alloy insoluble anode 23 due to the sudden inhalation of the hard particles. Therefore, when the anode of the post-mixing structure is used, it is suitable for the case where the specific gravity of the hard particles is relatively light, and the post-mixing device is also relatively light, and is suitable for frequently changing mobile devices in the workplace.
  • the hard particles may be 500-800 ⁇ m in diameter, but no matter which particle is selected It is necessary to ensure that the particles are similar in size and are acid washed to remove impurities and to be baked before use.
  • the circulation pump 13 is turned on to recycle the deposition liquid; the recovery device 19 is turned on to reuse the hard particles to achieve a solid-liquid circulation, and the processing is continued.
  • the stainless steel pipe of the front stage pressurized portion and the rubber hose of the rear conveying portion are 15 to 25 mm in diameter, and the inner walls of the two are ensured to be smooth.

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Abstract

提供一种三维表面的喷丸射流电沉积制造方法及装置，将沉积液与硬质颗粒相混合以喷射的方式沉积到导电基板（2）上，实现电沉积的快速制造技术，减缓电沉积过程的晶粒长大速率，达到晶粒细化目的，显著提高沉积层质量。将二者相结合能有效克服单一电沉积阴极析氢和杂质粘附产生的沉积层质地疏松、麻点和凹坑等缺陷，提高沉积层的硬度和致密性。同时，引入五轴联动数控加工系统，可实现三维空间加工成型，提高沉积层均匀性和形状精度。该技术可广泛应用于贵重金属器件和复杂形状零件的生产，也可用于表面快速涂镀和强化技术等。

Description

一种三维表面喷丸射流电沉积制造方法及装置 技术领域
本发明涉及制造技术中快速成型加工领域，尤其是一种三维表面喷丸射流电沉积制造方法及装置。
背景技术
电沉积技术作为一种新型的加工成型方法，以其良好的工艺参数可控性等特点，在微细制造技术和表面处理技术领域取得了广泛的发展和应用，如微型马达、微传感器、微型零件成型和修复，零件表面涂镀和耐腐蚀等方面的应用取得了良好的效果。因此，电沉积技术是21世纪最具吸引力的研究领域之一。
由于普通电沉积方法在沉积速度、沉积的区域选择性、沉积层与基体的结合强度以及沉积层本身的晶粒尺寸、物理特性和表面形貌等方面存在诸多不足，使得电沉积的优越性难以显现。将电沉积方法加以适当的改进并与其他的加工方法相融合，便能取得良好的效果。如中国专利“一种超声波电铸装置”，专利号：CN103276415A中提出：采用超声波高频振荡提高电沉积反应的物质传输速率，降低浓差极化，并清洁电极表面析出氢气泡，改善沉积效果。又如，公开号为：CN101994137A的“回转体零件的高速射流喷射电铸加工方法及装置”，提出：利用高速射流向回转体零件沿一定轨迹进行选择性扫描喷射逐层堆砌成所需的零件，同时通过硬质粒子或摩擦件对铸层表面进行摩擦，有效去除沉积层表面积瘤毛刺等缺陷。在复合电沉积方面，公开号为CN103590080A的“一种激光强化喷射电沉积快速成形加工装置及方法”，提出：将高能量密度激光束和高速电沉积溶液通过管状的钝性阳极中心孔同步射向阴极表面，实现激光强化电沉积技术与电沉积溶液喷射的结合，达到很高的沉积速度且能够实现区域选择性沉积，可快速制造出形状复杂结构致密的金属零件。
在现有的电沉积技术所实现的沉积方法中，或方法简易但效果不明显，或效果良好但装置复杂可操作性低等原因极大的限制了电沉积技术的广泛应用。且沉积层的表面会随着沉积时间的延长使沉积质量变差，进而影响材料的致密性和均匀性。
发明内容
针对现有技术中存在不足，本发明提供了一种三维表面喷丸射流电沉积制造方法及装置。将沉积液与硬质颗粒相混合，既能实现电沉积技术的快速制造成形，又能实现喷 丸的表面强化目的，极大提高电沉积的沉积速率，改善沉积层的质量。
本发明是通过以下技术手段实现上述技术目的的。
一种三维表面喷丸射流电沉积制造方法，其特征在于，包含以下步骤：
(1)先对阴极导电基板表面进行研磨、除油、酸洗和水洗，然后固定阴极导电基板，将电源的正负极分别与阳极和阴极导电基板相连接，开启电源；
(2)采用可调节流量的液压泵为酸性沉积液加速，并将沉积液与粒度大小均匀的微米级硬质颗粒充分混合，再以流动的沉积液产生的负压为硬质颗粒提供动力，使硬质颗粒混入沉积液，使喷出的硬质颗粒具有足够的冲击速度，并与沉积液形成射流从喷嘴中喷出形成射流，冲击到阴极导电基板上，所述硬质颗粒的冲击速度的大小应满足：硬质颗粒冲击沉积表面的作用力大于气动喷丸强化工艺中喷丸对工件的作用力；
(3)沉积液在阴极导电基板上电解沉积；同时硬质颗粒冲击沉积表面的瞬间冲量，使沉积层的晶粒排列规则形成亚晶粒，平整沉积层表面凸起的尖端部分，及时去除阴极氢气泡和杂质，抑制结瘤和针孔麻点的产生；
(4)通过五轴联动数控加工系统调整喷嘴的空间喷射角度，持续沉积形成所需要的三维空间形状；
(5)收集未沉积的沉积液和硬质颗粒，并循环使用。
进一步地，所述步骤(2)中，所述喷嘴处沉积液喷射速度5～10m/s。
一种三维表面喷丸射流电沉积制造装置，其特征在于，包括：五轴联动数控加工系统、电沉积系统、液体循环系统、液压系统和硬质颗粒循环系统；
所述五轴联动数控加工系统包括五轴联动数控加工机械手和数控装置，所述数控装置用于控制机械手的空间角度和运动路径；
所述电沉积系统包括电源、阴极导电基体和阳极，所述电源的负极与正极分别与阴极导电基体和阳极相互连接，所述阳极固定于五轴联动机械手上、并位于阴极导电基体上方；
所述液体循环系统包括储液槽、沉积槽、过滤器、循环泵，所述沉积槽位于阴极导电基体下方、并通过管道与储液槽连接，所述循环泵、过滤器设置在沉积槽与储液槽之间的管道上；储液槽通过橡胶软管与阳极连通；
所述液压系统设置在储液槽和橡胶软管之间，包括依次连接的过滤装置、液压泵、节流阀、压力表，以及设在节流阀与储液槽之间的溢流阀，所述液压泵与过滤装置之间通过不锈钢管连接，所述过滤装置置于储液槽中；
所述硬质颗粒循环系统包括收集漏斗、回收器、储存器，所述收集漏斗置于阴极导电基体下方，所述回收器连接在收集漏斗与储存器之间，所述储存器通过管道与橡胶软管或阳极连通。
进一步地，所述储液槽中还设有搅拌器和加热器；所述加热器带有温度传感器。
进一步地，所述阳极内径3～5mm。
进一步地，所述电源为可调脉冲电源，频率范围0.5～2MHz、峰值电压2～15V、脉冲宽度30～500ns；所述液压泵为变量泵，工作压力10bar以上，额定流量不小于10L/min；所述不锈钢管和橡胶软管内径15～25mm，且二者内壁光滑。
进一步地，所述硬质颗粒直径500～800μm，且要经过酸洗去杂质和烘焙处理。
本发明将喷丸强化技术与电沉积技术合理的结合，不仅可以克服传统电沉积阴极析氢和杂质粘附产生的沉积层质地疏松、麻点和凹坑等缺陷而显著提高材料的致密度和均匀性，既能实现电沉积技术的快速制造成形，又能实现喷丸的表面强化目的，极大提高电沉积的沉积速率，改善沉积层的质量。而且与数控加工系统相结合，可实现三维空间加工成形，从而广泛应用于现代复杂形状零件的生产，也可用于快速涂镀和表面强化技术等。
本发明的技术优势及有益效果：
1)沉积中利用硬质颗粒的瞬间冲量，多次冲击沉积层表面，使沉积层在冲击应力作用下，晶粒排列规则，形成更小的亚晶粒，从而实现喷丸强化的效果，提高沉积层的硬度和致密性。
2)硬质颗粒对沉积层表面的均匀冲压，使表面凸起的尖端部分受到更多几率的冲击和更大的压力，从而使沉积层表面更加平整光亮。
3)硬质颗粒对阴极表面的瞬时覆盖和屏蔽，也可起到表面活性添加剂的阻化作用，减缓电沉积过程的晶粒长大速率，达到晶粒细化目的。
4)硬质颗粒对阴极表面的摩擦作用，能够均匀化沉积层组织结构和提高沉积层组织性能，同时又能及时去除阴极氢气泡和杂质，抑制结瘤和针孔麻点等缺陷的产生，达到平整沉积层表面的目的。
5)与五轴联动数控加工系统相结合，不仅能实现三维空间的成形制造，还可实现任意曲面的喷涂和表面强化，工作效率高、工艺简化。
附图说明
图1是本发明所述表面喷丸射流电沉积制造装置的结构示意图。
图2是阳极的一种实施例的结构示意图。
图3是阳极的另一种实施例的结构示意图。
附图标记说明如下：
1.电源，2.阴极导电基体，3.电流表，4.阀门，5.储存器，6.压力表，7.节流阀，8.溢流阀，9.加热器，10.搅拌器，11.过滤装置，12.液压泵，13.循环泵，14.过滤器，15.沉积槽，16.收集漏斗，17.支撑架，18.五轴联动数控加工机械手，19.回收器，20.数控装置，21.橡胶软管，22.储液槽，23.钛合金不溶性阳极，24.钢化玻璃罩，25.分岔管，26.沉积层。
具体实施方式
下面结合附图以及具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
本发明所述的三维表面喷丸射流电沉积制造方法，加工前对阴极导电基板表面进行研磨、除油、酸洗和水洗。固定阴极导电基板，将电源的正负极分别与阳极和阴极导电基板相连接，开启电源，可调节流量的液压泵持续的为酸性沉积液提供液体流动动力，沉积液在橡胶软管内的流动使硬质颗粒的储存器与橡胶软管的接口处形成负压，硬质颗粒被强力吸入，与沉积液充分混合，使喷出的硬质颗粒具有足够的冲击速度，并与沉积液形成射流从喷嘴中喷出形成射流，冲击到阴极导电基板上，所述硬质颗粒的冲击速度的大小应满足：硬质颗粒冲击沉积表面的作用力大于气动喷丸强化工艺中喷丸对工件的作用力。
沉积液喷出阳极时，由于阳极出口直径的缩小而获得高速高压液流，具体的，所述喷嘴处沉积液喷射速度5～10m/s。由于阳极的导电作用使沉积液发生电解，沉积液中的金属阳离子在阴极导电基板上获得电子还原成金属原子，并沉积出所需的零件形状。同时，硬质颗粒因本身相对质量较大，而具有较大的动量，冲击到阴极导电基板时会产生巨大的冲量，所述硬质颗粒冲击沉积表面的作用力能够超过喷丸强化工艺中喷丸对工件的作用力，从而达到冲击强化表面的目的，实现喷丸与电化学的复合沉积加工。
高速运动的硬质颗粒持续冲击沉积层去除沉积过程的内应力，并压缩沉积层提高了沉积强度，硬质颗粒随液流流动持续摩擦表面不仅有助于去除积瘤和凸起，改善表面的高低不平整度，也有利于排出以及析出气体，提高材料的致密度和光洁度，加之周期性的脉冲电源作用也有助于喷丸强化效果的实现，最终实现快速高效的沉积。
综上，本发明是通过将沉积液液流与硬质颗粒混合以高速射流方式的喷射沉积，其中，所述硬质颗粒为粒度大小均匀的微米级颗粒，所述沉积液为用于电沉积工艺的沉积液。沉积液以射流的方式喷向阴极基体实现了喷射电沉积的快速制造目的，构成了喷射电沉积制造系统；高速液流为硬质颗粒加速，使硬质颗粒获得比气动喷丸更大的冲击力，实现喷丸的表面强化目的。本发明将两者相结合实现了快速沉积的同时强化沉积层，实现喷丸强化与电化学复合沉积的快速制造，加工工艺得以简化，提高沉积效率，实现高质高效的电化学复合沉积加工，快速修复零件表面缺陷和增强表面性能。
如图1所示，实现上述三维表面喷丸射流电沉积制造方法的三维表面喷丸射流电沉积制造装置，包括：五轴联动数控加工系统、电沉积系统、液体循环系统、液压系统和硬质颗粒循环系统。
五轴联动数控加工系统包括五轴联动数控加工机械手和数控装置；所述数控装置用于控制机械手的空间角度和运动路径。
电沉积系统包括电源、阴极导电基体和阳极，所述阳极为钛合金不溶性阳极。电源的正极与钛合金不溶性阳极相连，负极与阴极导电基板相连，三者之间串联电流表，用于检测电流大小。所述阳极固定于五轴联动机械手上、并位于阴极导电基体上方。所述阴极导电基体固定在支撑架上。
所述液体循环系统包括储液槽、沉积槽、过滤器、循环泵，所述沉积槽位于阴极导电基体下方、并通过管道与储液槽连接，所述循环泵、过滤器设置在沉积槽与储液槽之间的管道上，所述循环泵将过滤后的溶液输送到储液槽中；储液槽通过橡胶软管与阳极连通。
所述液压系统设置在储液槽和橡胶软管之间，包括依次连接的过滤装置、液压泵、节流阀、压力表，以及设在节流阀与储液槽之间的溢流阀，所述液压泵与过滤装置之间通过不锈钢管连接，液压系统其余装置之间通过不锈钢管或橡胶软管连接，所述过滤装置置于储液槽中，所述液压泵抽取过滤装置中的溶液，所述节流阀、溢流阀和压力表与液压泵的出口连接，调节输出流量大小。
硬质颗粒循环系统包括收集漏斗、回收器、储存器，所述储存器用于存储硬质颗粒，通过管道与橡胶软管或阳极连通，所述收集漏斗置于阴极导电基体下方，以收集沉积后的硬质颗粒，所述回收器连接在收集漏斗与储存器之间，用于将收集漏斗中的硬质颗粒输送到储存器。
本发明所述的三维表面喷丸射流电沉积制造装置：
(1)建立电化学电沉积系统及五轴联动数控加工系统：
电沉积系统中电源的正极与钛合金不溶性阳极相连，作为电沉积电流回路的阳极；电源的负极与阴极导电基体相连，作为电沉积回路的阴极，再将电流表串联于电路中，检测电流大小。钛合金不溶性阳极固定于五轴联动数控加工机械手上，钛合金不溶性阳极的输入端口与通过橡胶软管与储液槽相连。阴极导电基体放置于支撑架上并定位夹紧；数控机械手与数控装置相连接，通过数控装置中的程序设定，控制数控机械手的空间角度和运动路径，以实现喷丸射流电沉积的三维空间加工成形。
(2)建立喷丸射流电沉积复合加工系统：
设置液体循环系统、硬质颗粒循环系统，液压循环系统为液体循环系统、硬质颗粒循环系统提供动力，实现硬质颗粒与沉积液的混合，并获得射流力。
本发明所述三维表面喷丸射流电沉积装置工作时：液压泵12经不锈钢管通过过滤装置11抽取储液槽22中的沉积液，由节流阀7节流和溢流阀8的溢流后，经压力表6的测压后进入橡胶软管21，由于沉积液高速流动，储存器5的管口处产生负压，硬质颗粒被高压吸入橡胶软管管道，通过阀门4的开关即可实现混合后的沉积液在管道内的流动与停止；当沉积液流经钛合金不溶性阳极23时，经电源1的电解作用由喷口喷出，在阴极导电基2体上还原出金属晶体，得到沉积层26；未参与沉积的沉积液收集到沉积槽15中，经过滤器14过滤后由循环泵13重新返回到储液槽22中，实现再次循环利用。冲击沉积层后的硬质颗粒透过支撑架17由收集漏斗16汇聚收集，通过回收器19返回到储存器5中，实现再次利用，整个过程可持续加工，实现高速高效加工成形。
较佳地，所述三维表面喷丸射流电沉积制造装置的储液槽中还设有搅拌器和加热器；所述加热器带有温度传感器，对沉积液的充分混合和温度起到调节作用。所述电源采用可调脉冲电源，频率范围0.5～2MHz、峰值电压2～15V、脉冲宽度30～500ns。所述液压泵为变量泵，工作压力10bar以上，额定流量不小于10L/min。所述阳极直径3～5mm。
根据实际加工要求，调节脉冲电源的输出电压、脉冲宽度、波形和脉冲频率；调节节流阀阀门，控制液压泵的输出流量；调节储液器阀门开口大小，控制沉积液中硬质颗粒的含量；待输出流量稳定后，通过数控装置控制机械手与阴极导电基体的距离，实现最佳沉积效果。
沉积液经钛合金不溶性阳极上的喷口高速喷出，在阴极导电基板上获得电子发生还原反应得到金属纳米层。由于在射流中心区域的电流密度较大，因而能够获得定域性较高的沉积效果，通过对沉积区沉积层的累加堆积可获得所需的三维形状。
对已经腐蚀生锈或氧化的金属表面，能够在高速硬质颗粒的冲击下除锈除杂而露出金属导电层，在金属表层继续沉积涂镀，加强与基体的结合强度，同时由于硬质颗粒的冲击作用强化了基体的机械性能，在除杂涂镀的同时实现了喷丸强化，简化工艺提高了工作效率。
在五轴联动机械手上可同时安装多个喷嘴实现复合沉积和轮换沉积，也可配置复合沉积液实现多晶共相沉积，提高基体的性能。
阳极可采用前混合式结构或后混合式结构；两种结构在使用功能上基本相同，但两种结构在不同场合上各有优势。
具体的，前混合式结构的阳极如图2所示，由钛合金不溶性阳极23和橡胶软管21直接相连接，钛合金不溶性阳极外有一圈起保护作用的钢化玻璃罩24包围，结构上相对简单，适合于比重相对较大的硬质颗粒。由于硬质颗粒与沉积液混合较早，两者混合相对比较均匀，更利于在阳极喷嘴处流体的喷射。但采用前混合式结构的设备一般比较笨重，适用于不经常更换工作场地的大型设备。
后混合式结构的阳极如图3所示，钛合金不溶性阳极23上设置了分岔管25，两者材质相同，采用螺纹连接和密封，钛合金不溶性阳极23外有一圈起保护作用的钢化玻璃罩24包围。由于硬质颗粒在工具阳极处与沉积液相混合，硬质颗粒的吸入方式一般采用负压式吸入，工具阳极由于硬质颗粒的突然吸入，易对钛合金不溶性阳极23产生磨损。因此，采用后混合式结构的阳极时，适用于硬质颗粒的比重相对较轻的情况，后混合式的设备也相对轻便，适合经常更换工作场所的移动设备上。
实现喷丸射流电沉积具体过程如下：
(1)配制电沉积所需的沉积液。选择主盐晶体，将其溶解于蒸馏水中直至达到饱和状态，添加适量添加剂、缓冲剂、活化剂和络合剂等，以提高沉积层的加工效果和导电性。
(2)对阴极导电基板2的表面进行研磨、除油、酸洗和水洗清洁处理，用夹具将阴极导电基板准确定位夹紧；硬质颗粒直径500～800μm均可，但是无论选择哪种颗粒都要保证该种颗粒大小相近，且在使用前要经过酸洗去杂质且要烘焙处理。
(3)通过数控装置20控制数控机械手18的高度和角度，使钛合金不溶性阳极的喷嘴与沉积层的距离保持在2～3mm之间；
(4)沉积前，开启搅拌器10，使沉积液混合充分，开启加热器9，使温度恒定在40～50℃；
(5)启动液压泵12，调节节流阀7和溢流阀8，液压泵的工作压力10bar以上，额定流量大于10L/min，钛合金不溶性阳极23的喷嘴和分岔管直径3～5mm，保证硬质颗粒有足够的速度冲击到沉积区域。
(6)开启电源1及各个阀门开始喷丸射流沉积制造，沉积时调节阀门4开口大小，使喷嘴处沉积液的喷射速度达到5～10m/s，实时控制数控机械手18与沉积层的的高度、角度和移动速度，实现三维空间成形加工；在实施表面涂镀和涂层强化处理时，喷嘴的扫描速度为0.5～1m/s。
(7)开启循环泵13，使沉积液循环利用；开启回收器19，使硬质颗粒重复利用，达到固液循环，加工过程持续进行。
由于沉积中要保证沉积液足够的压力和速度，因此本装置中选用前段增压部分的不锈钢管和后段输送部分的橡胶软管直径15～25mm，且保证二者内壁光滑。
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。

Claims (7)

  1. 一种三维表面喷丸射流电沉积制造方法，其特征在于，包含以下步骤：
    (1)先对阴极导电基板表面进行研磨、除油、酸洗和水洗，然后固定阴极导电基板，将电源的正负极分别与阳极和阴极导电基板相连接，开启电源；
    (2)采用可调节流量的液压泵为酸性沉积液加速，并将沉积液与粒度大小均匀的微米级硬质颗粒充分混合，再以流动的沉积液产生的负压为硬质颗粒提供动力，使硬质颗粒混入沉积液，使喷出的硬质颗粒具有足够的冲击速度，并与沉积液形成射流从喷嘴中喷出形成射流，冲击到阴极导电基板上，所述硬质颗粒的冲击速度的大小应满足：硬质颗粒冲击沉积表面的作用力大于气动喷丸强化工艺中喷丸对工件的作用力；
    (3)沉积液在阴极导电基板上电解沉积；同时硬质颗粒冲击沉积表面的瞬间冲量，使沉积层的晶粒排列规则形成亚晶粒，平整沉积层表面凸起的尖端部分，及时去除阴极氢气泡和杂质，抑制结瘤和针孔麻点的产生；
    (4)通过五轴联动数控加工系统调整喷嘴的空间喷射角度，持续沉积形成所需要的三维空间形状；
    (5)收集未沉积的沉积液和硬质颗粒，并循环使用。
  2. 根据权利要求1所述的制造方法，其特征在于，所述步骤(2)中，所述喷嘴处沉积液喷射速度5～10m/s。
  3. 一种三维表面喷丸射流电沉积制造装置，其特征在于，包括：五轴联动数控加工系统、电沉积系统、液体循环系统、液压系统和硬质颗粒循环系统，
    所述五轴联动数控加工系统包括五轴联动数控加工机械手和数控装置，所述数控装置用于控制机械手的空间角度和运动路径；
    所述电沉积系统包括电源、阴极导电基体和阳极，所述电源的负极与正极分别与阴极导电基体和阳极相互连接，所述阳极固定于五轴联动机械手上、并位于阴极导电基体上方；
    所述液体循环系统包括储液槽、沉积槽、过滤器、循环泵，所述沉积槽位于阴极导电基体下方、并通过管道与储液槽连接，所述循环泵、过滤器设置在沉积槽与储液槽之间的管道上；储液槽通过橡胶软管与阳极连通；
    所述液压系统设置在储液槽和橡胶软管之间，包括依次连接的过滤装置、液压泵、节流阀、压力表，以及设在节流阀与储液槽之间的溢流阀，所述液压泵与过滤装置之间通过不锈钢管连接；所述过滤装置置于储液槽中；
    所述硬质颗粒循环系统包括收集漏斗、回收器、储存器，所述收集漏斗置于阴极导电基体下方，所述回收器连接在收集漏斗与储存器之间，所述储存器通过管道与橡胶软管或阳极连通。
  4. 根据权利要求3所述的喷丸射流电沉积制造装置，其特征在于，所述储液槽中还设有搅拌器和加热器；所述加热器带有温度传感器。
  5. 根据权利要求3所述的喷丸射流电沉积制造装置，其特征在于，所述阳极内径3～5mm。
  6. 根据权利要求3所述的喷丸射流电沉积制造装置，其特征在于，所述电源为可调脉冲电源，频率范围0.5～2MHz、峰值电压2～15V、脉冲宽度30～500ns；所述液压泵为变量泵，工作压力10bar以上，额定流量不小于10L/min；所述不锈钢管和橡胶软管内径15～25mm，且二者内壁光滑。
  7. 根据权利要求3所述的喷丸射流电沉积制造装置，其特征在于，所述硬质颗粒直径500～800μm，且要经过酸洗去杂质和烘焙处理。
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