CN114875462A - Multilayer film structure coating and preparation method and preparation device thereof - Google Patents
Multilayer film structure coating and preparation method and preparation device thereof Download PDFInfo
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- CN114875462A CN114875462A CN202210661390.1A CN202210661390A CN114875462A CN 114875462 A CN114875462 A CN 114875462A CN 202210661390 A CN202210661390 A CN 202210661390A CN 114875462 A CN114875462 A CN 114875462A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011248 coating agent Substances 0.000 title claims description 33
- 238000000576 coating method Methods 0.000 title claims description 33
- 238000009713 electroplating Methods 0.000 claims abstract description 61
- 239000010410 layer Substances 0.000 claims abstract description 60
- 238000000034 method Methods 0.000 claims abstract description 54
- 238000007747 plating Methods 0.000 claims abstract description 53
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 49
- 238000005406 washing Methods 0.000 claims description 42
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 17
- 238000005086 pumping Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 239000011229 interlayer Substances 0.000 claims description 10
- 238000005273 aeration Methods 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 9
- 230000000737 periodic effect Effects 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 239000002356 single layer Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000010408 film Substances 0.000 description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- 238000010301 surface-oxidation reaction Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229910000531 Co alloy Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 229910007567 Zn-Ni Inorganic materials 0.000 description 1
- 229910007614 Zn—Ni Inorganic materials 0.000 description 1
- 239000003788 bath preparation Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Images
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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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
-
- 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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
-
- 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
- C25D5/16—Electroplating with layers of varying thickness
-
- 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
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a multilayer film structure plating layer, a preparation method and a preparation device thereof, belonging to the technical field of electroplating in material science. The invention can form a multi-layer film structure plating layer with periodically changed component contents of one or more alloy elements by controlling the on or off of the inflating and stirring device in the single-tank electroplating process, not only has stable electroplating solution performance and ensures that a single-layer film plating layer has better performance, but also does not need to add a plating tank and other treatment processes, is convenient to implement and is suitable for industrial production.
Description
Technical Field
The invention belongs to the technical field of electroplating in material science, and relates to a multilayer film structure plating layer, and a preparation method and a preparation device thereof.
Background
In recent years, much attention has been paid to the development of multilayer film structures. Compositionally modulated multilayer films are a novel material of periodic variation in composition or structure formed by alternating thin films (sublayers or sublayers) of multiple metals or alloys. Unlike the optimization and improvement of the process, the method is a method for bringing breakthrough in performance through the change of the material structure. Sublayers of different properties in a multilayer film structure play different roles in the overall construction. The preparation method of the component-modulated multilayer film is roughly divided into a magnetron sputtering method and an electroplating method, and the magnetron sputtering method has high requirements on equipment, long preparation time and high cost. The electroplating method is concerned by its simple equipment, easy operation, low production cost and high production efficiency. Most research results show that: the multi-layer film prepared by the components has better mechanical property and corrosion resistance than a single-layer film with the same thickness.
The process of electroplating the coating layer with the multilayer film structure is roughly divided into a double-groove process and a single-groove process. The method of periodically transferring the substrate between different plating solutions to realize alternate electrodeposition of different sub-layers is called a double-bath process. However, in the process of preparing a component-modulated multilayer film in two tanks, not only is the consumption of plating solutions increased, but also mutual contamination between plating solutions is likely to occur, and there is a possibility that surface oxidation, anodic dissolution and displacement reactions occur in the process of mutual transfer between two tanks in a sample. The single-bath process, i.e. the formation of sublayers of different alloy contents in the same bath by controlling the variation of parameters, has made most researchers more enthusiastic than the single-bath preparation method due to the limitations of the double-bath process and the simplicity of the single-bath process.
When a multilayer film is prepared by a single-groove process, how to instantly regulate and control process parameters to prepare a sublayer with obvious interlayer characteristic difference is the key and difficult point of the whole single-groove process. At present, most researchers only regulate and control different current densities during electroplating to prepare a multilayer film with interlayer difference, but the method has limited regulation and control parameters and the problem that the characteristic difference between sublayers is not obvious enough.
Disclosure of Invention
In view of the above, the present invention provides a multi-layer structure plating layer, a method and an apparatus for preparing the same, so as to solve the problem of insignificant difference in interlayer characteristics of the conventional multi-layer structure plating layer.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing the multi-layer film structure plated layer features that a single-slot electroplating method is used, and the alloy plated layer is deposited in electroplating liquid by periodically and intermittently introducing air-inflating stirrer, and the stirring speed of electroplating liquid is changed by inflating or not inflating to obtain sub-layers with certain interlayer characteristics difference.
Optionally, the substrate is subjected to the following steps in sequence before electroplating: polishing, washing, ultrasonic cleaning, alkaline washing for removing oil, washing, acid washing and washing; and drying the substrate after electroplating.
Optionally, the process parameters of the ultrasonic cleaning are as follows: ultrasonically cleaning in absolute ethyl alcohol for 10 min.
Optionally, the process parameters of the alkaline cleaning oil removal are as follows: treating in alkaline washing liquid at 70-90 ℃ for 5-10 minutes; the alkaline solution is one or more of sodium hydroxide solution and sodium carbonate solution.
Optionally, the pickling process parameters are as follows: soaking the substrate in acid washing solution with the temperature of 23 +/-1 ℃ for 5-10 s, wherein the acid washing solution is dilute sulfuric acid with the concentration of 5-10%.
Optionally, the periodic intermittent introduction of the pumping agitation during electroplating comprises the steps of: firstly, carrying out electrodeposition for 6-280 s under the condition of inflating and stirring; then, gas pumping and stirring are cancelled, and electrodeposition is carried out for 5-235 s; and circulating the operations until the total deposition time is 4-433 min.
Optionally, the plating current density is 1-5A-dm 2 。
A multilayer film structure plating layer is prepared by the method.
Optionally, the sub-layer thickness of the multilayer film structure coating is in a nanometer-submicron order.
Optionally, the thickness of the sub-layer of the multi-layer film structure coating is 50-500 nm.
Optionally, the thickness of the multilayer film structure coating is 4-50 um.
The utility model provides a preparation facilities of multilayer film structure cladding material, includes plating bath and the agitating unit that inflates, and the agitating unit that inflates includes that the level sets up in the plating bath and sets up the gas pocket board of a plurality of inflation holes, is equipped with the air duct below the gas pocket board, and the other end of air duct stretches out the plating bath and links to each other with the air supply, still includes the automatically controlled module of inflating that links to each other with the air duct in order to realize that periodic intermittent type inflates in the plating bath.
The invention has the beneficial effects that:
1. the electroplating solution adopting the multilayer film structure plating layer has stable performance, and the obtained plating layer has fine crystals, no pinholes and no defect in appearance; the bonding strength between the plating layer and the substrate material and among the sub-layers of the plating layer is high; the multi-layer film structure coating has better mechanical property and corrosion resistance compared with a single-layer film coating with the same thickness.
2. The method has the advantages that the operation is simple, the multilayer film structure coating with the periodically-changed component content of one or more alloy elements in the coating can be formed in a single groove by controlling the opening or closing of the inflating and stirring device in the electroplating process, and the implementation is convenient.
3. The cost is low, a plating bath and other treatment processes are not required to be newly added, the multilayer film structure plating with good performance can be obtained only by controlling the opening or closing of the inflating stirring device in the electroplating process in an intelligent way through a program, and other additional cost is not increased, so that the method is suitable for industrial production.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
FIG. 1 is a schematic structural diagram of a device for preparing a multilayer film structure coating:
FIG. 2 is an SEM photograph of a multi-layer film structure coating layer of example 2;
FIG. 3 is a schematic diagram of the pumping state as a function of electrodeposition time period.
Reference numerals are as follows: the device comprises a power supply 1, an electroplating bath 2, an air inflating hole 3, an air duct 4 and an air inflating electric control module 5.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Wherein the showings are for the purpose of illustrating the invention only and not for the purpose of limiting the same, and in which there is shown by way of illustration only and not in the drawings in which there is no intention to limit the invention thereto; to better illustrate the embodiments of the present invention, some parts of the drawings may be omitted, enlarged or reduced, and do not represent the size of an actual product; it will be understood by those skilled in the art that certain well-known structures in the drawings and descriptions thereof may be omitted.
The same or similar reference numerals in the drawings of the embodiments of the present invention correspond to the same or similar components; in the description of the present invention, it should be understood that if there is an orientation or positional relationship indicated by terms such as "upper", "lower", "left", "right", "front", "rear", etc., based on the orientation or positional relationship shown in the drawings, it is only for convenience of description and simplification of description, but it is not an indication or suggestion that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and therefore, the terms describing the positional relationship in the drawings are only used for illustrative purposes, and are not to be construed as limiting the present invention, and the specific meaning of the terms may be understood by those skilled in the art according to specific situations.
Referring to fig. 1 to 3, a method for preparing a multi-layer film structure coating, which uses a single-tank electroplating method, uses a metal material as a base material, and deposits an alloy coating in an electroplating solution by periodically and intermittently introducing aeration stirring during electroplating, and changes the stirring rate of the electroplating solution by aeration or non-aeration conditions to obtain sub-layers with a certain interlayer characteristic difference, so as to prepare a multi-layer film structure coating with periodic layer-shaped components.
Optionally, the substrate is subjected to the following steps in sequence before electroplating: polishing, washing, ultrasonic cleaning, alkaline washing for removing oil, washing, acid washing and washing; drying the substrate after electroplating; the technological parameters of ultrasonic cleaning are as follows: ultrasonically cleaning in absolute ethyl alcohol for 10 min; the technological parameters of alkali washing oil removal are as follows: treating in alkaline washing liquid at 70-90 ℃ for 5-10 minutes; the alkaline washing solution is one or more of a sodium hydroxide solution and a sodium carbonate solution; the technological parameters of acid washing are as follows: soaking the substrate in a pickling solution at 23 +/-1 ℃ for 5-10 s, wherein the pickling solution is dilute sulfuric acid with the concentration of 5-10%; the current density of electroplating is 1-5A/dm 2 (ii) a The periodic intermittent introduction of the pumping agitation during electroplating comprises the following steps: firstly, carrying out electrodeposition for 6-280 s under the condition of inflating and stirring; then, gas pumping and stirring are cancelled, and electrodeposition is carried out for 5-235 s; and circulating the operations until the total deposition time is 4-433 min.
The invention also provides a multilayer film structure coating which is prepared by the method and consists of bright sublayers and dark sublayers which are alternately superposed, wherein the component contents of alloy elements of the bright sublayers and the dark sublayers are different so as to ensure that the sublayer characteristics of the multilayer film structure coating are periodically changed, the bright sublayers and the dark sublayers are respectively obtained by stirring with air and stirring without air during electroplating, the thickness of the sublayer of the multilayer film structure coating is nano-scale to submicron scale, preferably, the thickness of the sublayer is 50-500 nm, and the thickness of the multilayer film structure is 4-50 um.
The invention also provides a device for preparing the multilayer film structure coating, which is used for preparing the multilayer film structure and comprises an electroplating bath 2 and an inflating and stirring device, wherein the electroplating bath 2 is powered by a power supply 1, the inflating and stirring device comprises a gas hole plate which is horizontally arranged in the electroplating bath 2 and is provided with a plurality of inflating holes 3, a gas guide pipe 4 is arranged below the gas hole plate, the other end of the gas guide pipe 4 extends out of the electroplating bath 2 to be connected with a gas source, and the device also comprises an inflating electric control module 5 connected with the gas guide pipe to realize periodic intermittent inflation in the electroplating bath. The preparation device can form a multi-layer film structure coating with periodically changed component contents of one or more alloy elements on a substrate by intelligently controlling the opening or closing of the inflating and stirring device in the electroplating process through a program.
The multilayer film structure plating layer is formed by periodically and intermittently introducing aeration stirring in the electroplating solution to deposit an alloy plating layer in the electroplating process, changing the stirring speed of the electroplating solution through aeration or non-aeration conditions to obtain a sublayer with certain interlayer characteristic difference, and preparing the multilayer film structure plating layer with periodic layers. The preparation method has the advantages of simple operation, easily controlled process parameters and good repeatability, and the prepared plating layer has fine crystals, no pinholes, no defect in appearance, clear interface between multiple layers of films, uniform thickness, smooth and flat surface, certain interlayer characteristic difference of sublayers, high bonding strength between the plating layer and a base material and between the plating layer and each sublayer, and can be used for obtaining materials with stronger mechanical and corrosion resistance.
Example 1
In this embodiment, a zinc-nickel plating layer with a multilayer film structure is electroplated on the surface of a Q235 steel substrate.
The preparation method of the multilayer film structure plating layer in the embodiment comprises the following steps: ultrasonic cleaning, alkaline cleaning and oil removing, water washing, acid washing, water washing, electroplating, water washing and drying. The specific operation is as follows:
soaking the substrate in 80 ℃ alkaline solution (comprising 15g/L of sodium hydroxide solution and 15g/L of sodium carbonate solution) for 10 minutes to remove oil, then soaking in 10% dilute sulfuric acid for 5 seconds to remove a surface oxidation film, and washing with deionized water.
The alloy plating solution used in this example was composed of the following components in the following content ranges: 200g/L of nickel sulfate, 120g/L of zinc sulfate, 71g/L of sodium sulfate and 0.02g/L of lauryl sodium sulfate; the pH value of the plating solution is 3.2, and the temperature of the plating solution is 50 ℃.
In this example, the current density was constant at 1A/dm 2 Controlling the gas-pumping state at different time according to the process schematic diagram of FIG. 3, turning on the gas-pumping stirring device in the electroplating solution immediately after electrifying, and electrodepositing for 28 s; then closing the gas-pumping stirring device in the electroplating solution, and performing electrodeposition for 24 s; the above operations are continuously circulated, the total deposition time is 34min and 40s, and the zinc-nickel coating with the total thickness of about 4 μm, the same thickness of each sublayer is 50nm, and the number of layers is 80.
After the plating is finished, a plating layer with good binding force, uniformity and excellent corrosion resistance is obtained. The corrosion performance of the plated samples was evaluated by the neutral salt spray test of GB/T2423.17 standard, and the results are shown in Table 1:
table 1 example 1 neutral salt spray test results
| Test specimen | Thickness (μm) | Average Ni content (%) | First red rust time |
| Q235 steel | - | 0 | ＜0.5h |
| Zn-Ni single layer film coating | 4 | 14.56％ | 362h |
| Multilayer film plating of example 1 | 4 | 14.37％ | 593h |
Example 2
In this embodiment, a multi-layer nickel-copper plating layer is electroplated on the surface of a Q235 steel substrate.
The preparation method of the multilayer film structure plating layer in the embodiment comprises the following steps: ultrasonic cleaning, alkaline cleaning and oil removing, water washing, acid washing, water washing, electroplating, water washing and drying. The specific operation is as follows:
soaking the substrate in 80 ℃ alkaline solution (comprising 15g/L of sodium hydroxide solution and 15g/L of sodium carbonate solution) for 10 minutes to remove oil, then soaking in 5% dilute sulfuric acid for 10 seconds to remove a surface oxidation film, and washing with deionized water.
The alloy plating solution used in this example was composed of the following components in the following content ranges: the nickel-cobalt alloy plating solution used in this example was composed of the following components in the following content ranges: 150g/L of nickel sulfate, 25g/L of nickel chloride, 30g/L of copper sulfate, 40g/L of sodium citrate, 40g/L of boric acid, 1g/L of saccharin sodium and 0.01g/L of sodium dodecyl sulfate; the pH value of the plating solution is 5.2, and the temperature of the plating solution is 40 ℃.
In this example, the current density was constant at 3A/dm 2 Controlling the gas-pumping state at different time according to the process schematic diagram of FIG. 3, turning on the gas-pumping stirring device in the electroplating solution immediately after electrifying, and electrodepositing for 61 s; then closing the gas-pumping stirring device in the electroplating solution, and electrodepositing for 52 s; the above operations are continuously cycled, and the total deposition time is 47min5s, so that the total thickness of the deposited film is about 10 μm, and each sub-layer is thickThe nickel-copper plating layers have the same degree of 200nm and 50 layers.
Example 3
In this embodiment, a multi-layer nickel-cobalt plating layer is electroplated on the surface of a Q235 steel substrate.
The preparation method of the multilayer film structure plating layer in the embodiment comprises the following steps: ultrasonic cleaning, alkaline cleaning and oil removing, water washing, acid washing, water washing, electroplating, water washing and drying. The specific operation is as follows:
soaking the substrate in 80 ℃ alkaline solution (comprising 15g/L of sodium hydroxide solution and 15g/L of sodium carbonate solution) for 10 minutes to remove oil, then soaking in 5% dilute sulfuric acid for 10 seconds to remove a surface oxidation film, and washing with deionized water.
The alloy plating solution used in this example consisted of the following composition in the following content ranges: the nickel-cobalt alloy plating solution used in this example was composed of the following components in the following content ranges: 210g/L of nickel sulfate, 50g/L of nickel chloride, 60g/L of boric acid, 20g/L of cobalt chloride and 0.03g/L of sodium dodecyl sulfate; the pH value of the plating solution is 4.1, and the temperature of the plating solution is 50 ℃.
In this example, the current density was constant at 5A/dm 2 Controlling the pumping states at different time according to the process schematic diagram of FIG. 3, powering on to immediately open the pumping stirring device in the electroplating solution, and electrodepositing for 83 s; then closing the gas-pumping stirring device in the electroplating solution, and electrodepositing for 67 s; the above operations are continuously circulated, the total deposition time is 125min, and the nickel-cobalt coating with the total thickness of about 50 μm, the same thickness of each sublayer is 500nm, and the number of layers is 100.
The invention adopts a single-groove electroplating method, takes metal materials as a matrix, and intelligently controls the opening or closing of an inflating stirring device in the electroplating process through a program to form a multilayer film structure coating with periodically changed component contents of one or more alloy elements in the coating and certain interlayer characteristic difference of each sublayer. The preparation method of the multilayer film structure coating is simple and easy to implement and has lower cost. In addition, the multilayer film structure plating layer has the characteristic of a layered structure, and each sublayer has a certain interlayer characteristic difference. The thickness of the independent sub-layer of the multilayer film structure coating is nano-scale to submicron scale, specifically 50nm to 500nm, the total thickness is within the range of 4 um to 50um, and the thickness can be adjusted according to actual requirements.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. A preparation method of a multilayer film structure coating is characterized by comprising the following steps: the single-groove electroplating method is adopted, the alloy plating layer is deposited in the electroplating solution by periodically and intermittently introducing aeration stirring during electroplating, and the stirring speed of the electroplating solution is changed by aeration or non-aeration conditions to obtain a sublayer with a certain interlayer characteristic difference so as to prepare the multi-layer film structure plating layer with periodic layered components.
2. The method for preparing a multilayer film structured coating according to claim 1, wherein: the matrix is sequentially subjected to the following steps before electroplating: polishing, washing, ultrasonic cleaning, alkali washing for removing oil, washing, acid washing and washing; and drying the substrate after electroplating.
3. The method for preparing a multilayer film structured coating according to claim 1, wherein: the technological parameters of ultrasonic cleaning are as follows: ultrasonically cleaning in absolute ethyl alcohol for 10 min.
4. The method for preparing a multilayer film structured coating according to claim 1, wherein: the technological parameters of alkali washing oil removal are as follows: treating in alkaline washing liquid at 70-90 ℃ for 5-10 minutes; the alkaline solution is one or more of sodium hydroxide solution and sodium carbonate solution.
5. The method for preparing a multilayer film structured coating according to claim 1, wherein: the technological parameters of acid washing are as follows: soaking the substrate in acid washing solution with the temperature of 23 +/-1 ℃ for 5-10 s, wherein the acid washing solution is dilute sulfuric acid with the concentration of 5-10%.
6. The method of claim 1, wherein the step of depositing the multilayer film structure further comprises: the periodic intermittent introduction of the pumping agitation during electroplating comprises the following steps: firstly, carrying out electrodeposition for 6-280 s under the condition of inflating and stirring; then, gas pumping and stirring are cancelled, and electrodeposition is carried out for 5-235 s; and circulating the operations until the total deposition time is 4-433 min.
7. The method for preparing a multilayer film structured coating according to claim 1, wherein: the current density of electroplating is 1-5A/dm 2 。
8. A multilayer film structure plating layer is characterized in that: prepared by the process as claimed in any one of claims 1 to 7.
9. The multilayer film structured coating of claim 8, wherein: the thickness of the sub-layer of the multi-layer film structure coating is 50-500 nm, and the thickness of the multi-layer film structure coating is 4-50 um.
10. A preparation device of a multilayer film structure coating is characterized in that: the electroplating bath air-inflating device comprises an electroplating bath and an air-inflating stirring device, wherein the air-inflating stirring device comprises an air hole plate which is horizontally arranged in the electroplating bath and is provided with a plurality of air-inflating holes, an air guide pipe is arranged below the air hole plate, the other end of the air guide pipe extends out of the electroplating bath and is connected with an air source, and the electroplating bath air-inflating device also comprises an air-inflating electric control module which is connected with the air guide pipe and is used for inflating the electroplating bath periodically and intermittently.
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| JPS58193397A (en) * | 1982-04-30 | 1983-11-11 | Matsushita Electric Works Ltd | Composite plating method |
| CN102277604A (en) * | 2010-06-10 | 2011-12-14 | 中国科学院金属研究所 | Electroplated Ni stacking membrane and its preparation method |
| CN104120461A (en) * | 2013-04-28 | 2014-10-29 | 上海宝钢工业技术服务有限公司 | Method for preparing gradient alloy plating layer on surface of thin strip continuous casting crystallization roller and plating solution |
| CN112410852A (en) * | 2020-10-30 | 2021-02-26 | 中冶赛迪技术研究中心有限公司 | Nano composite electroplating equipment and electroplating process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58193397A (en) * | 1982-04-30 | 1983-11-11 | Matsushita Electric Works Ltd | Composite plating method |
| CN102277604A (en) * | 2010-06-10 | 2011-12-14 | 中国科学院金属研究所 | Electroplated Ni stacking membrane and its preparation method |
| CN104120461A (en) * | 2013-04-28 | 2014-10-29 | 上海宝钢工业技术服务有限公司 | Method for preparing gradient alloy plating layer on surface of thin strip continuous casting crystallization roller and plating solution |
| CN112410852A (en) * | 2020-10-30 | 2021-02-26 | 中冶赛迪技术研究中心有限公司 | Nano composite electroplating equipment and electroplating process |
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