CN113737237A - Method and device for preparing gradient coating by laser-assisted electrodeposition - Google Patents
Method and device for preparing gradient coating by laser-assisted electrodeposition Download PDFInfo
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- CN113737237A CN113737237A CN202110941303.3A CN202110941303A CN113737237A CN 113737237 A CN113737237 A CN 113737237A CN 202110941303 A CN202110941303 A CN 202110941303A CN 113737237 A CN113737237 A CN 113737237A
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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
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
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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
- C25D5/08—Electroplating with moving electrolyte e.g. jet electroplating
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Abstract
The invention discloses a method and a device for preparing a gradient coating by laser-assisted electrodeposition. The method can synchronously prepare the three-layer gradient structure of the base material, the remelted layer and the plating layer, eliminates the interface of the plating layer material and the base material, is beneficial to the combination of the plating layer and the base, improves the stripping phenomenon of the plating layer, and simultaneously can ensure the surface performance of the workpiece substrate. In addition, the device can realize the relative motion between the laser beam and the workpiece substrate, so that the heat accumulation effect of a plurality of pulse lasers can be utilized to induce instantaneous remelting on the surface of the workpiece.
Description
Technical Field
The invention relates to the technical field of composite special processing, in particular to a method and a device for preparing a gradient coating by laser-assisted electrodeposition, which are suitable for preparing a high-performance surface coating.
Background
The essence of the electrodeposition technology is reduction reaction, and the electrodeposition technology is mainly applied to the surface coating of a workpiece, and is used for modifying and modifying the surface coating to improve the surface performance. The single electrodeposition technology has the defects of low deposition rate, poor uniformity of a deposited layer, pinholes, pockmarks, internal stress and the like in the manufacturing process. The laser-assisted electrodeposition technology is used for assisting an electrochemical reaction process in an electrodeposition process by utilizing high energy density of a laser beam, and can improve the deposition rate and the coating performance.
The preparation of the gradient plating layer is studied at home and abroad, and in the Chinese patent 'a wear-resistant and corrosion-resistant Ni-Co-B-Sc gradient plating layer and a preparation method thereof', the pH value of electroplating solution is adjusted to 3-6, and the electroplating is carried out for a certain time according to the following current density steps: 0.1 to 0.3A/dm2、0.3～0.5A/dm2、0.5～0.7A/dm2、0.7～0.9A/dm2And (3) carrying out electroplating for 1-5 min at each current density, switching to the next level when the electroplating time is up, and switching to the first level when the electroplating time is last, so that a certain total electroplating time is circulated to finally obtain the coating with the gradient structure. In the Chinese patent 'a reduced graphene oxide-nickel base gradient plating layer and a preparation method thereof', graphene oxide is added in a plating solution, a functional gradient electroplating process is adopted, and the obtained gradient plating layer contains reduced graphene oxide, so that the capability of the plating layer in resisting corrosive substances can be effectively enhanced. The specific mode is that the first electroplating, the second electroplating and the third electroplating are carried out in sequence; the duty ratio of the first electroplating is 0.70-0.85, the duty ratio of the second electroplating is 0.55-0.60, and the duty ratio of the third electroplating is 0.20-0.40, so that the gradient coating is obtained.
The invention prepares the gradient plating layer by changing electrochemical parameters such as current density, duty ratio and the like. Although the plating with better functionality and compact surface can be obtained by changing a single electrochemical parameter, the parameter variable groups are more, the production efficiency is reduced in industrial production, and the cost is increased. For the coating, the ideal gradient coating should realize the complete gradient change of the composition and structure from the substrate to the coating surface, but the existing method for preparing the gradient coating has low bonding strength with the substrate and is easy to peel off under the influence of external force in practical application.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for preparing a gradient coating by laser-assisted electrodeposition, which can synchronously prepare a three-layer gradient structure of a substrate, a remelted layer and a coating, wherein the three-layer gradient structure is used for eliminating the interface of a coating material and a substrate material, is beneficial to the combination of the coating and the substrate and improves the coating peeling phenomenon. In addition, the device provided by the invention can realize the relative motion between the laser beam and the workpiece substrate, so that the heat accumulation effect of a plurality of pulse lasers can be utilized to induce instantaneous remelting on the surface of the workpiece.
The present invention achieves the above-described object by the following technical means.
A method for preparing a gradient coating by laser-assisted electrodeposition is characterized in that a deposition layer is electrodeposited on a workpiece substrate by using pulse laser and electrochemical reaction, and the deposition layer on the surface of the workpiece substrate is remelted by using the heat of the pulse laser to obtain a remelted layer which is uniformly distributed.
Furthermore, when the remelted layer is obtained, the residual thermal stress of the pulse laser is utilized to induce the electrochemical reaction on the upper surface of the remelted layer to obtain a plating layer.
The device for preparing the gradient coating by laser-assisted electrodeposition comprises a laser irradiation system, a control system and an electrochemical processing system; the laser irradiation system is used for emitting pulse laser and irradiating the pulse laser on the electrochemical machining system; the control system is used for controlling the laser irradiation system and the electrochemical machining system; during laser machining and electrochemical reactions, the laser beam moves relative to the workpiece substrate.
Furthermore, a partition plate is arranged between the workpiece substrate and the anode substrate in the processing system.
Furthermore, the workpiece substrate, the anode substrate and the partition plate are attached to each other.
Further, the separator is made of corrosion-resistant insulating materials.
Further, the laser irradiation system comprises a pulse laser, a reflecting mirror and a focusing lens; the laser is emitted by a pulse laser, the transmission direction of the laser is changed by a reflecting mirror, the laser is focused by a focusing lens, and the focused laser beam irradiates on a workpiece substrate.
Further, the control system comprises a computer and a motion controller; the computer controls the pulse laser, the direct current pulse power supply and the motion controller; the motion controller controls the x-y-z three-axis motion platform.
Furthermore, the processing system comprises a direct current pulse power supply, a working tank, a workpiece substrate, an anode substrate, a partition plate and an x-y-z three-axis motion platform; the working groove is arranged on an x-y-z three-axis motion platform; the positive electrode of the direct current pulse power supply is connected with the anode substrate, and the negative electrode of the direct current pulse power supply is connected with the workpiece substrate; the workpiece substrate and the anode substrate are attached to the upper surface and the lower surface of the partition plate and are completely immersed in the deposition solution.
Has the advantages that:
1. the method can synchronously prepare the three-layer gradient structure of the base material, the remelted layer and the plating layer, eliminates the interface of the plating layer material and the base material, is beneficial to the combination of the plating layer and the base, improves the stripping phenomenon of the plating layer, and simultaneously can ensure the surface performance of the workpiece substrate.
2. The obtained remelted layer is the metallurgical bonding of the substrate and the deposited layer, and has uniform texture and high bonding force.
3. The device can realize the relative motion between the laser beam and the workpiece substrate, thereby utilizing the heat accumulation effect of a plurality of pulse lasers to cause instantaneous remelting on the surface of the workpiece.
4. The partition plate is arranged between the workpiece substrate and the anode substrate, prevents the back electrolysis of the workpiece substrate and the anode substrate, and facilitates the installation and the positioning of the workpiece substrate and the anode substrate.
5. The thickness of the coating is controllable, the components of the deposition solution or electrochemical parameters are changed to continuously prepare a new coating on the surface of the coating, and a multilayer gradient structure can be realized.
Drawings
FIG. 1 is a schematic diagram of an apparatus for preparing a gradient coating by laser-assisted electrodeposition according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of a gradient matrix-remelted layer-coating structure during processing;
fig. 3 is a schematic diagram of pulsed laser heat accumulation.
The reference numbers are as follows:
1-a pulsed laser; 2-a mirror; 3-a focusing lens; 4-a working groove; 5-a throttle valve; 6-a filter; 7-a micropump; 8-a liquid storage tank; a 9-x-y-z three-axis motion platform; 10-an anode substrate; 11-a separator; 12-a workpiece substrate; 13-a direct current pulse power supply; 14-a motion controller; 15-a computer; 16-an ammeter; 17-a laser beam; 18-a deposition layer; 19-remelting layer; 20-plating; 21-bracket.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "axial," "radial," "vertical," "horizontal," "inner," "outer," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the present invention and for simplicity in description, and are not intended to indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
In the present invention, unless otherwise expressly specified or limited, the terms "mounted," "connected," "secured," and the like are to be construed broadly and can, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood by those skilled in the art according to specific situations.
A method for preparing gradient coating by laser-assisted electrodeposition is characterized in that a deposition layer 18 is electrodeposited on a workpiece substrate 12 by using pulse laser and electrochemical reaction, and the deposition layer 18 on the surface of the workpiece substrate 12 is remelted by using the heat of the pulse laser to obtain a remelted layer 19 which is uniformly distributed.
Wherein, the residual thermal stress of the pulse laser is utilized to induce the electrochemical reaction on the upper surface of the remelted layer 19 to obtain the plating layer 20 at the same time of obtaining the remelted layer 19.
The device for preparing the gradient coating by laser-assisted electrodeposition comprises a laser irradiation system, a control system and an electrochemical processing system; the laser irradiation system is used for emitting pulse laser and irradiating the pulse laser on the electrochemical machining system; the control system is used for controlling the laser irradiation system and the electrochemical machining system; during laser machining and electrochemical reaction, the laser beam 17 moves relative to the workpiece substrate 12.
Wherein a partition plate 11 is arranged between the workpiece substrate 12 and the anode substrate 10 in the processing system. The workpiece substrate 12 and the anode substrate 10 are bonded with the separator 11. The partition plate 11 is made of corrosion-resistant insulating material.
With reference to fig. 1, 2 and 3, the laser irradiation system includes a pulse laser 1, a mirror 2 and a focusing lens 3; the laser is emitted by a pulse laser 1, the transmission direction is changed by a reflector 2, and then the laser is focused by a focusing lens 3, and a focused laser beam 17 irradiates on a workpiece substrate 12; the control system comprises a computer 15 and a motion controller 14; the computer 15 controls the pulse laser 1, the direct current pulse power supply 13 and the motion controller 14; the motion controller 14 controls the x-y-z three-axis motion platform 9; the electrochemical machining system comprises a direct current pulse power supply 13, a working tank 4, a workpiece substrate 12, an anode substrate 10, a partition plate 11 and an x-y-z three-axis motion platform 9; the working groove 4 is arranged on an x-y-z three-axis motion platform 9; the positive electrode of the direct current pulse power supply 13 is connected with the anode substrate 10, and the negative electrode of the direct current pulse power supply is connected with the workpiece substrate 12; the workpiece substrate 12 and the anode substrate 10 are attached to the upper and lower surfaces of the separator 11 and are completely immersed in the deposition solution.
The working fluid circulating system comprises a liquid storage tank 8, a micro pump 7, a filter 6 and a throttle valve 5; the inlet of the micro pump 7 is connected with the liquid storage tank 8, the outlet is connected with the working tank 4, and the filter 6 and the throttle valve 5 are connected in series in a loop. In the electrochemical reaction process, the micro pump works to ensure the uniform concentration of the solution in the working tank.
The gradient coating with a remelted layer 19 structure is obtained on the surface of a workpiece by utilizing the thermal effect of laser and electrodeposition reaction, the anode and the cathode of a direct current power supply 13 are respectively connected with an anode substrate 10 and a workpiece substrate 12, and an electrodeposition loop is formed by connecting an ammeter 16 in series; laser beams 17 emitted by the laser 1 are focused by the optical path transmission system and the focusing lens 3 and irradiated on the surface of the workpiece substrate 12, and instantaneous remelting is initiated on the surface of the workpiece by utilizing the heat accumulation effect of a plurality of pulse lasers while electrodeposition reaction is induced in a laser irradiation area to form a deposition layer 18, so that the components of the deposition layer 18 and the components of the substrate 12 are mixed to obtain a remelted layer 19. After the laser irradiation is finished, the residual heat continuously induces electrochemical deposition on the surface of the remelting layer 19, and a three-layer gradient structure of the base material 12, the remelting layer 19 and the coating 20 is realized.
The specific implementation method of the invention is as follows:
drawing a motion path model and inputting the motion path model into the computer 15;
performing surface pretreatment on the workpiece substrate 12;
attaching a workpiece substrate 12 and an anode substrate 10 to two surfaces of a separator 11 oppositely and parallelly, attaching the workpiece substrate 12 to the upper surface of the separator 11 and connecting the workpiece substrate with the cathode of an electrochemical power supply 13, and attaching the anode substrate 10 to the lower surface of the separator 11 and connecting the lower surface of the separator 11 with the anode of the electrochemical power supply 13;
installing the bracket of the clapboard 11 in the working tank 4 and connecting an ammeter 16 in series in the electrochemical loop; installing the working groove 4 on an x-y-z motion platform 9, and adjusting the height of the x-y-z three-axis motion platform 9 to focus laser on the surface of a workpiece substrate 12;
the lower ends of the workpiece substrate 12 and the anode substrate 10 are immersed in the deposition solution, when the power is on, the workpiece substrate 12 and the anode substrate 11 form an electrochemical loop in the deposition solution, and the micro pump 7 is started to circularly change the solution, so that the concentration of the solution in the working tank 4 is ensured to be uniform;
turning on an electrochemical power supply 13 to set electrochemical voltage parameters, wherein in an electrodeposition gold test, when the electrochemical voltage is less than 3v, the parameters meet the condition that no electrochemical deposition reaction occurs without laser irradiation, and electrodeposition can occur under laser irradiation with appropriate parameters, such as localized deposition when the laser single pulse energy is greater than 4.5 uj;
starting the pulse laser 1, setting a movement path and laser parameters, and accelerating the electrodeposition reaction in an irradiation area by using the thermal effect of laser to induce a deposition layer 18; simultaneously, the heat accumulation of a plurality of pulse lasers enables the surface of the workpiece to be instantaneously remelted, so that a cladding 20 is formed by inducing electrochemical deposition by utilizing residual thermal stress after a remelted layer 19 which is uniformly distributed is obtained; after continuous processing, a three-layer gradient structure of substrate 18-remelted layer 19-plating layer 20 is obtained.
And (3) closing the laser, adjusting the electrical parameters and continuing electrodeposition, and increasing the thickness of the coating 20.
And changing the components of the deposition solution or electrochemical parameters to continuously prepare a new coating on the surface of the coating, thereby realizing a multilayer gradient structure.
It should be noted that when laser is added to induce electrochemical deposition, the original electrochemical parameters do not need to be adjusted. When the required metal of the target coating is different, the electrochemical parameter and the laser parameter are different. The scheme takes gold electroplating as an example, for example, when the electrochemical voltage is 2.4v, no electrodeposition reaction occurs, and after laser is added, the electrochemical deposition reaction can occur with the laser single pulse energy of 5uj, wherein the laser pulse frequency is not more than 2 Mhz.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made in the above embodiments by those of ordinary skill in the art without departing from the principle and spirit of the present invention.
Claims (9)
1. A method for preparing a gradient coating by laser-assisted electrodeposition is characterized in that a deposition layer (18) is electrodeposited on a workpiece substrate (12) by utilizing pulse laser and electrochemical reaction, and the deposition layer (18) on the surface of the workpiece substrate (12) is remelted by utilizing the heat of the pulse laser to obtain a remelted layer (19).
2. The method for preparing a gradient coating by laser-assisted electrodeposition as claimed in claim 1, wherein the remelted layer (19) is obtained while an electrochemical reaction is induced on the upper surface of the remelted layer (19) by the residual thermal stress of the pulsed laser to obtain the coating (20).
3. The device for preparing the gradient coating by laser-assisted electrodeposition according to any one of claims 1 to 2, comprising a laser irradiation system, a control system and an electrochemical processing system; the laser irradiation system is used for emitting pulse laser and irradiating the pulse laser on the electrochemical machining system; the control system is used for controlling the laser irradiation system and the electrochemical machining system; characterized in that the laser beam (17) is moved relative to the workpiece substrate (12) during the laser machining and the electrochemical reaction.
4. The apparatus for preparing a gradient coating by laser-assisted electrodeposition as claimed in claim 3, wherein a separator (11) is provided between the workpiece substrate (12) and the anode substrate (10) in the electrochemical machining system.
5. The apparatus for the method of laser-assisted electrodeposition for producing a gradient coating according to claim 3, wherein the workpiece substrate (12) and the anode substrate (10) are bonded to the separator (11).
6. The apparatus for the method of laser-assisted electrodeposition for producing a gradient coating according to claim 3, wherein the separator (11) is a corrosion-resistant insulating material.
7. The apparatus for the method of laser-assisted electrodeposition for producing gradient coatings according to claim 3, characterized in that the laser irradiation system comprises a pulsed laser (1), a mirror (2) and a focusing lens (3); laser is emitted by a pulse laser (1), the transmission direction of the laser is changed by a reflector (2), the laser is focused by a focusing lens (3), and a focused laser beam (17) is irradiated on a workpiece substrate (12).
8. The apparatus for the method of laser-assisted electrodeposition for producing a gradient coating according to claim 3, wherein the control system comprises a computer (15) and a motion controller (14); the computer (15) controls the pulse laser (1), the direct current pulse power supply (13) and the motion controller (14); the motion controller (14) controls the x-y-z three-axis motion platform (9).
9. The apparatus for preparing gradient coating by laser-assisted electrodeposition according to claim 3, wherein the processing system comprises a direct current pulse power supply (13), a working tank (4), a workpiece substrate (12), an anode substrate (10), a partition plate (11) and an x-y-z three-axis motion platform (9); the working groove (4) is arranged on an x-y-z triaxial moving platform (9); the positive electrode of the direct current pulse power supply (13) is connected with the anode substrate (10), and the negative electrode of the direct current pulse power supply is connected with the workpiece substrate (12); the workpiece substrate (12) and the anode substrate (10) are attached to the upper surface and the lower surface of the partition plate (11) and are completely immersed in the deposition solution.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110941303.3A CN113737237B (en) | 2021-08-17 | 2021-08-17 | Method and device for preparing gradient coating by laser-assisted electrodeposition |
| PCT/CN2022/110471 WO2023020300A1 (en) | 2021-08-17 | 2022-08-05 | Method and device for preparing gradient plating by means of laser-assisted electrodeposition |
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| CN202110941303.3A CN113737237B (en) | 2021-08-17 | 2021-08-17 | Method and device for preparing gradient coating by laser-assisted electrodeposition |
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| CN113737237A true CN113737237A (en) | 2021-12-03 |
| CN113737237B CN113737237B (en) | 2022-10-28 |
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Cited By (3)
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| CN114990640A (en) * | 2022-05-24 | 2022-09-02 | 深圳大学 | Laser-guided electrochemical deposition 3D printing device and method |
| CN114990650A (en) * | 2022-05-30 | 2022-09-02 | 江苏大学 | Method and device for preparing functional gradient coating by laser tuning current waveform |
| WO2023020300A1 (en) * | 2021-08-17 | 2023-02-23 | 江苏大学 | Method and device for preparing gradient plating by means of laser-assisted electrodeposition |
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Also Published As
| Publication number | Publication date |
|---|---|
| CN113737237B (en) | 2022-10-28 |
| WO2023020300A1 (en) | 2023-02-23 |
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