CN113897654A - Coaxial laser-assisted micro-arc oxidation device and method - Google Patents
Coaxial laser-assisted micro-arc oxidation device and method Download PDFInfo
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- CN113897654A CN113897654A CN202111330852.3A CN202111330852A CN113897654A CN 113897654 A CN113897654 A CN 113897654A CN 202111330852 A CN202111330852 A CN 202111330852A CN 113897654 A CN113897654 A CN 113897654A
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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- C—CHEMISTRY; METALLURGY
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- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
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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
- C25D5/02—Electroplating of selected surface areas
- C25D5/024—Electroplating of selected surface areas using locally applied electromagnetic radiation, e.g. lasers
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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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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Abstract
The invention discloses a coaxial laser-assisted micro-arc oxidation device and a method, wherein the device adopts a coaxial laser-assisted mode on the basis of a scanning micro-arc oxidation technology, breaks through the technical bottlenecks of a lateral laser-assisted micro-arc oxidation method in a laser-assisted mode and a laser beam, enables parallel laser beams and electrolyte to have the same path, effectively avoids the problems of refraction of laser on the liquid level of the electrolyte, deformation of a light spot area and the like, simultaneously does not need to consider the interference of the electrolyte in a water-guided laser mode on the laser light path and energy, and realizes accurate control; the action area of the parallel laser beam is larger and uniform, so that the technical defect of slow film forming process of scanning type micro-arc oxidation is overcome, the arcing voltage and energy consumption are reduced, and the high-efficiency and high-quality scanning type micro-arc oxidation processing method is effectively realized; the device provided by the invention has the characteristics of simple structure, convenience in operation and high efficiency, and is favorable for the future large-scale industrialized production requirement.
Description
Technical Field
The invention relates to the technical field of titanium alloy surface modification, in particular to a coaxial laser-assisted micro-arc oxidation device and method, which are suitable for solving the problems of low film forming speed and low processing efficiency in a scanning micro-arc oxidation process so as to improve the film forming quality and efficiency.
Background
Titanium and titanium alloy are widely applied to the fields of medical instruments, chemical equipment, aerospace, automobile manufacturing and the like due to the characteristics of light weight, high strength, good toughness, corrosion resistance and the like. However, this type of alloy and its composite material are prone to wear and corrosion in the use environment, and need to be surface-strengthened to provide more excellent functional properties.
The micro-arc oxidation technology is also called plasma electrolytic oxidation, is a surface modification technology for growing ceramic film layers on the surfaces of valve metals such as aluminum, magnesium, titanium and the like in situ, and has the characteristics of simple process and environmental protection. The working area of the micro-arc oxidation technology breaks through the current and Faraday voltage limitation in the anodic oxidation reaction, the ceramic layer is more compact in the high-voltage high-current reaction process, the bonding strength with metal is high, and the ceramic layer has better corrosion resistance and wear resistance.
The traditional micro-arc oxidation technology takes a workpiece as an anode and takes the stainless steel inner wall of an electrolyte tank as a cathode. The workpiece is connected with the positive electrode of a power supply, the part to be processed is immersed into the electrolyte, the electrolyte tank or the auxiliary electrode is used as the negative electrode of the power supply, then micro-arc oxidation is carried out to prepare the ceramic membrane, the workpiece is wholly or partially immersed into the electrolyte, when the size of the processed workpiece is large, in order to ensure that a uniform electric field is generated in the processing process, the size of the corresponding electrolyte tank which needs to contain the electrolyte is also large, the electrolyte is large, the requirement on the power supply is improved, the energy consumption is high, the cost is high, and the application field of the technology is greatly limited.
At present, a great deal of research is carried out on the scanning type micro-arc oxidation technology in China. The film forming mechanism and the process of the method are preliminarily explored, but the scanning micro-arc oxidation technology overcomes the size limitation of the traditional micro-arc oxidation processing workpiece, but the film forming efficiency and the film quality of the method are low, so that the actual production requirement cannot be met when the large workpiece area is scanned. Therefore, the potential advantages of the technology in film forming efficiency and quality are still to be further explored.
Disclosure of Invention
Aiming at the defects of the background technology, the invention provides a coaxial laser-assisted micro-arc oxidation device and a method, the device adopts a coaxial laser-assisted mode on the basis of a scanning micro-arc oxidation technology, breaks through the defects of the prior art, realizes the processing of large-size workpieces or complex-profile workpieces, solves the problems of area effect and point discharge in the traditional processing device, reduces the limitation of the workpiece size on the power output power, and induces and strengthens the micro-arc oxidation process of a designated area through the cooperative control of laser energy between electrodes.
The invention not only expands the size requirement of the processed workpiece, does not need a larger electrolytic bath and a high-power supply, but also can reduce the micro-arc oxidation arcing voltage and energy consumption by the coaxial auxiliary irradiation of the parallel laser beams, so that the micro-arc oxidation is easier to carry out, the action area is larger and uniform, the time for the surface of the workpiece to enter the micro-arc oxidation film-forming stage is favorably shortened, and the local strengthening or repairing treatment with low energy consumption, high efficiency and high quality is really realized.
The technical scheme of the invention is as follows:
a coaxial laser-assisted micro-arc oxidation device comprises: the device comprises an optical fiber laser interface, a scanning type micro-arc oxidation spray head, a power supply, a circulating pump and a collecting tank;
the scanning type micro-arc oxidation spray head comprises: the device comprises an optical lens, a lens clamping groove, an electrolyte storage tank, a light-liquid separation tube, a connecting plate and an electrolyte nozzle;
the optical lens is arranged at the top of the electrolyte storage tank and is fixedly sealed by the lens clamping groove;
the connecting plate connects the electrolyte storage tank with the electrolyte nozzle (by using a bolt), the connecting plate is provided with channel holes (four) which are communicated with the electrolyte storage tank and the electrolyte nozzle, the center of the connecting plate is also provided with a positioning hole of the light-liquid separation tube, and one end of the connecting plate is provided with a cathode connecting ring;
the light-liquid separation tube is vertically inserted into a positioning hole in the center of the connecting plate;
the top of the scanning type micro-arc oxidation spray head is provided with a fixed clamping groove for positioning an optical fiber laser interface;
the upper part of the electrolyte storage tank is provided with an electrolyte water inlet, and a closed electrolyte circulating system is formed by the circulating pump and the collecting tank.
In the apparatus according to the present invention, the liquid crystal display device,
the scanning type micro-arc oxidation nozzle is divided into two parts: the middle of the electrolyte storage tank is connected with the electrolyte nozzle through a connecting plate, one end of the connecting plate is connected with the negative electrode of a power supply, and when the spray head is filled with electrolyte from a water inlet, the storage tank and the top of the nozzle are provided with corresponding built-in holes, so that the interior of the whole spray head is communicated and used as a cathode;
the top of the scanning type micro-arc oxidation spray head is provided with a fixed clamping groove for positioning an optical fiber laser interface and restraining a parallel laser beam output light path; the fiber laser interface enables the parallel laser beams output by the fiber laser interface to accurately penetrate through the light-liquid separation tube through the fixed clamping groove, and the fiber laser interface is contacted with the electrolyte at the injection port until the parallel laser beams are focused on the surface of a workpiece, so that the coaxial auxiliary effect of the parallel laser beams on the micro-arc oxidation process is realized; the light-liquid separation pipe side end is equipped with ring groove fixed, forms the stable light path passageway of keeping apart electrolyte, avoids the unstable flow of the inside electrolyte of shower nozzle to the interference of laser, realizes the accurate control to laser energy.
A method for carrying out coaxial laser-assisted micro-arc oxidation by using the device disclosed by the invention comprises the following steps of:
(1) carrying out abrasive paper grinding and polishing, cleaning and pretreatment on a workpiece (titanium alloy) to be treated, and naturally drying for later use;
(2) the micro-arc oxidation electrolyte is configured in the collecting tank, a circulating pump is started, the electrolyte flows into the water inlet and is filled in the electrolyte storage tank, the jet flow speed is adjusted to be 0.5-2 mm/s, the electrolyte can stably flow out of the nozzle and is jetted to the surface of a workpiece, and stable circulation is achieved;
micro-arc oxidation of electrolyteComprises the following components: 15-20 g/L Na2SiO3、3～4g/L NaOH、3～4g/L Na2HPO4The solvent is deionized water;
(3) placing the workpiece on a processing table and connecting the workpiece with the positive electrode of a power supply, adjusting the distance between a nozzle and the workpiece to be 6-10 mm, connecting the nozzle with the negative electrode of the power supply through a connecting plate, simultaneously opening a micro-arc oxidation power supply and a laser switch, and carrying out coaxial laser-assisted micro-arc oxidation;
the laser power is 100-150W; the micro-arc oxidation adopts a constant current mode, the forward current is 2-2.5A, and the ratio of positive current to negative current is 2: 1, the duty ratio is 20-30%, the frequency is 500-750 Hz, the temperature of the electrolyte is maintained at 20-25 ℃, and the reaction time is set to be 3-5 min.
The invention relates to a novel method for coaxial laser synchronous composite micro-arc oxidation, namely scanning micro-arc oxidation composite treatment is carried out by adopting a mode of coaxial parallel laser beams to irradiate electrolyte. According to the scanning process of the laser and the nozzle, the laser and the nozzle can be divided into three areas (a laser irradiation area and a micro-arc oxidation strengthening area, a micro-arc oxidation area and an anodic oxidation area, as shown in fig. 3). The composite strengthening area can form an oxide layer with a larger area and uniformity under the action of parallel laser beams, and the film forming efficiency is greatly improved.
And (3) innovativeness analysis:
the device is innovative in that a mode of combining coaxial laser assistance and electrolyte spraying is adopted, and the problems that the conventional micro-arc oxidation device is high in energy consumption, large workpieces cannot be processed, and local repair on site is difficult to achieve are effectively solved. The device breaks through the technical defects of a lateral laser-assisted micro-arc oxidation method in a laser-assisted mode and a laser beam, enables the parallel laser beam and the electrolyte to be in the same path, effectively avoids the problems of refraction of the laser on the liquid surface of the electrolyte, deformation of a light spot area and the like, simultaneously does not need to consider the interference of the electrolyte in a water-guided laser mode on a laser light path and energy, and realizes accurate control. The action area of the parallel laser beam is larger and uniform, the technical defect of slow film forming process of scanning type micro-arc oxidation is overcome, the arcing voltage and energy consumption are reduced, and the high-efficiency and high-quality scanning type micro-arc oxidation processing method is effectively realized. The processing device has the characteristics of simple structure, convenience in operation and high efficiency, and is favorable for the future large-scale industrial production requirement.
The device provides a new laser-assisted micro-arc oxidation composite strengthening method. The titanium alloy material is subjected to coaxial parallel laser beam irradiation and micro-arc oxidation synchronous composite treatment, the area can be divided into an I-laser irradiation + micro-arc oxidation strengthening area, a II-micro-arc oxidation area and a III-anodic oxidation area according to the composite action area of laser irradiation and a cathode nozzle, the laser irradiation can influence the formation of a dielectric layer in the early-stage anodic oxidation stage of the I area, and the area is induced to rapidly enter the micro-arc oxidation discharge and film forming stage and even can influence the surface structure and the stress state of the base material. The strengthening effect of the laser can also enable the II area to generate plasma, reduce the breakdown voltage and accelerate the electrochemical reaction, thereby improving the film forming efficiency and quality and reducing the energy consumption.
Compared with the prior micro-arc oxidation device and technology, the invention has the following advantages:
a. through the restraint of the inner-flushing liquid type tubular scanning cathode, the discharge is concentrated in a relatively narrow space between the end part of the cathode and the surface of the anode, and the current density which is hundreds of times higher than that of the conventional micro-arc oxidation is obtained, so that the micro-arc oxidation film is formed by the partial discharge breakdown, and the occurrence of point discharge and area effect is effectively avoided.
b. The laser irradiation can preheat the electrolyte, accelerate the electrochemical reaction process, obviously reduce the micro-arc oxidation arcing breakdown voltage, enter the film forming stage in advance and reduce the energy consumption.
c. The laser energy is properly increased to directly act on the surface of the matrix, the microstructure and the surface stress state of the base material are changed, so that the surface electrochemical property of the base material is changed, the mechanical property of the processed base material is improved, the synergistic composite reinforcement of laser surface reinforcement and micro-arc oxidation can be realized, and the light emitting starting and stopping time can be controlled according to different requirements, so that the laser acts on a specific stage of the micro-arc oxidation process.
d. The coaxial laser irradiation avoids the refraction phenomenon generated by laser and the sprayed electrolyte liquid column during lateral irradiation, guarantees the regularity of a laser action area, and is convenient for subsequent area overlapping processing. And the action area of the parallel laser beam is larger and more uniform, and the film forming efficiency is greatly improved.
e. The light-liquid separation mode can effectively avoid the interference of the unstable flowing of the electrolyte on a laser light path and the absorption of the electrolyte on laser energy when water is conducted to laser, and the accurate control on the laser light path and the energy is realized.
Drawings
FIG. 1 is a schematic view of a coaxial laser-assisted micro-arc oxidation apparatus according to the present invention; the optical fiber laser device comprises a 1-Z-direction fixing plate, a 2-optical fiber laser interface, a 3-X-direction fixing plate, a 4-fixing clamping groove, a 5-lens clamping groove, a 6-electrolyte storage groove, a 7-optical-liquid separation pipe, an 8-connecting plate, a 9-cathode connecting ring, a 10-support, an 11-power supply, a 12-circulating pump, a 13-collecting tank, a 14-electrolyte nozzle and a 15-optical lens.
FIG. 2 is a schematic diagram of a connecting plate of the coaxial laser-assisted micro-arc oxidation device of the present invention.
FIG. 3 is a schematic diagram of a laser synchronous composite micro-arc oxidation area.
Fig. 4 is a polarization curve before and after the TC4 titanium alloy composite strengthening treatment in example 1.
Detailed Description
The invention will be further described by means of specific embodiments with reference to the attached drawings, but the scope of protection of the invention is not limited thereto.
A coaxial laser-assisted micro-arc oxidation apparatus, as shown in fig. 1, comprising: the device comprises an optical fiber laser interface 2, a scanning micro-arc oxidation nozzle, a power supply 11, a circulating pump 12 and a collecting tank 13;
the scanning type micro-arc oxidation spray head comprises: an optical lens 15, a lens clamping groove 5, an electrolyte storage tank 6, a light-liquid separation tube 7, a connecting plate 8 and an electrolyte nozzle 14;
the optical lens 15 is arranged at the top of the electrolyte storage tank 6 and is fixedly sealed by the lens clamping groove 5;
the connecting plate 8 connects the electrolyte storage tank 6 with the electrolyte nozzle 14 by using a bolt, four channel holes are arranged on the connecting plate 8 to communicate the electrolyte storage tank 6 with the electrolyte nozzle 14, a positioning hole of the light-liquid separation tube 7 is also arranged in the center of the connecting plate 8, and a cathode connecting ring 9 is arranged at one end of the connecting plate 8;
the light-liquid separation tube 7 is vertically inserted into a positioning hole in the center of the connecting plate 8;
the top of the scanning type micro-arc oxidation spray head is provided with a fixed clamping groove 4 for positioning the optical fiber laser interface 2;
an electrolyte water inlet is formed in the upper portion of the electrolyte storage tank 6, and a closed electrolyte circulating system is formed by the circulating pump 12 and the collecting tank 13.
Example 1
A method for performing coaxial laser assisted micro-arc oxidation using the apparatus shown in fig. 1, the method comprising the steps of:
1. workpiece pretreatment: the TC4 titanium alloy is processed into a rectangular sample plate with the thickness of 45mm multiplied by 30mm multiplied by 2mm through wire cutting, the sample is polished by sand paper of 240 meshes, 400 meshes, 800 meshes and 1200 meshes, a surface oxidation film is removed, the surface of a workpiece is smooth and flat, then the workpiece is placed in an alcohol solution for ultrasonic cleaning for 15-20 min, and the workpiece is taken out after cleaning is finished, washed by deionized water and naturally dried.
2. Electrolyte circulation: the micro-arc oxidation electrolyte is configured in the electrolyte collecting tank, a circulation switch is turned on, the electrolyte flows into the electrolyte storage tank from a water inlet and is filled in the electrolyte storage tank, the jet flow speed is adjusted to be 1mm/s, the electrolyte can stably flow out from a nozzle and is jetted to the surface of a workpiece, and a stable circulation system is realized;
the electrolyte comprises the following components: 20g/L Na2SiO3、3g/L NaOH、4g/L Na2HPO4And the solvent is deionized water.
3. Micro-arc oxidation treatment: and (3) placing the workpiece on the surface of a processing table and connecting the workpiece with the positive electrode of a power supply, adjusting the distance between a nozzle opening and the workpiece to be 10mm, and connecting the nozzle with the negative electrode of the power supply through a connecting plate. The micro-arc oxidation adopts a constant current mode, the forward current is 2A, and the ratio of positive current to negative current is 2: 1, duty ratio of 20%, frequency of 500Hz, electrolyte temperature maintained at about 20 ℃, and reaction time set to 3 min.
4. Parallel laser assistance: and (3) after the device and electrical parameters are adjusted in the step (3), turning on the red light of the laser, checking and aligning the red light with a nozzle opening, adjusting the laser focal length, setting the laser power to be 150W, simultaneously turning on the micro-arc oxidation power supply and the laser switch, taking out the sample after the reaction is finished, washing the sample with deionized water, and naturally drying the sample to obtain the coaxial laser-assisted micro-arc oxidation coating.
The corrosion resistance test result of the composite reinforced coating shows that after the surface of the composite micro-arc oxidation surface is reinforced by the laser, the self-corrosion potential is increased from-0.234V to-0.168V, and the self-corrosion current density is increased from 4.78 multiplied by 10-7Down to 2.458 × 10-7A/cm2The corrosion resistance is obviously improved.
TABLE 1 electrochemical parameters before and after TC4 titanium alloy composite strengthening treatment
Claims (4)
1. A coaxial laser-assisted micro-arc oxidation device is characterized by comprising: the device comprises an optical fiber laser interface, a scanning type micro-arc oxidation spray head, a power supply, a circulating pump and a collecting tank;
the scanning type micro-arc oxidation spray head comprises: the device comprises an optical lens, a lens clamping groove, an electrolyte storage tank, a light-liquid separation tube, a connecting plate and an electrolyte nozzle;
the optical lens is arranged at the top of the electrolyte storage tank and is fixedly sealed by the lens clamping groove;
the connecting plate connects the electrolyte storage tank with the electrolyte nozzle, a channel hole is arranged on the connecting plate and is communicated with the electrolyte storage tank and the electrolyte nozzle, a positioning hole of the light-liquid separation tube is also arranged in the center of the connecting plate, and a cathode connecting ring is arranged at one end of the connecting plate;
the light-liquid separation tube is vertically inserted into a positioning hole in the center of the connecting plate;
the top of the scanning type micro-arc oxidation spray head is provided with a fixed clamping groove for positioning an optical fiber laser interface;
the upper part of the electrolyte storage tank is provided with an electrolyte water inlet, and a closed electrolyte circulating system is formed by the circulating pump and the collecting tank.
2. A method for coaxial laser assisted micro-arc oxidation using the device of claim 1, comprising the steps of:
(1) carrying out abrasive paper grinding and polishing, cleaning and pretreatment on a workpiece to be treated, and naturally drying for later use;
(2) the micro-arc oxidation electrolyte is configured in the collecting tank, a circulating pump is started, the electrolyte flows into the water inlet and is filled in the electrolyte storage tank, the jet flow speed is adjusted to be 0.5-2 mm/s, the electrolyte can stably flow out of a nozzle and can be sprayed to the surface of a workpiece, and stable circulation is achieved;
(3) and (3) placing the workpiece on a processing table and connecting the workpiece with the positive electrode of a power supply, adjusting the distance between a nozzle and the workpiece to be 6-10 mm, connecting the nozzle with the negative electrode of the power supply through a connecting plate, and simultaneously opening a micro-arc oxidation power supply and a laser switch to perform coaxial laser-assisted micro-arc oxidation.
3. The method of claim 2, wherein in step (2), the micro-arc oxidation electrolyte comprises: 15-20 g/L Na2SiO3、3～4g/L NaOH、3～4g/L Na2HPO4And the solvent is deionized water.
4. The method as claimed in claim 2, wherein in the step (3), the laser power is 100-150W, the micro-arc oxidation is performed in a constant current mode, the forward current is 2-2.5A, and the ratio of positive current to negative current is 2: 1, the duty ratio is 20-30%, the frequency is 500-750 Hz, the temperature of the electrolyte is maintained at 20-25 ℃, and the reaction time is set to be 3-5 min.
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