CN106498458A - A kind of automatically cleaning corrosion resistant plate and its production method - Google Patents
A kind of automatically cleaning corrosion resistant plate and its production method Download PDFInfo
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- CN106498458A CN106498458A CN201611256696.XA CN201611256696A CN106498458A CN 106498458 A CN106498458 A CN 106498458A CN 201611256696 A CN201611256696 A CN 201611256696A CN 106498458 A CN106498458 A CN 106498458A
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- stainless steel
- steel base
- corrosion resistant
- resistant plate
- automatically cleaning
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- 238000004140 cleaning Methods 0.000 title claims abstract description 43
- 238000005260 corrosion Methods 0.000 title claims abstract description 38
- 230000007797 corrosion Effects 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 84
- 239000010935 stainless steel Substances 0.000 claims abstract description 84
- 238000000576 coating method Methods 0.000 claims abstract description 73
- 239000011248 coating agent Substances 0.000 claims abstract description 70
- 239000010949 copper Substances 0.000 claims abstract description 68
- 238000007747 plating Methods 0.000 claims abstract description 66
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 64
- 229910052802 copper Inorganic materials 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010276 construction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 19
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 229910000831 Steel Inorganic materials 0.000 claims description 15
- 239000010959 steel Substances 0.000 claims description 15
- 210000001595 mastoid Anatomy 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 11
- 230000001680 brushing effect Effects 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 7
- 238000009713 electroplating Methods 0.000 claims description 7
- 239000011159 matrix material Substances 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 230000017531 blood circulation Effects 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 229910001651 emery Inorganic materials 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 241001614291 Anoplistes Species 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 238000007517 polishing process Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 230000035508 accumulation Effects 0.000 claims description 2
- 238000009825 accumulation Methods 0.000 claims description 2
- 210000000481 breast Anatomy 0.000 claims 1
- 230000031709 bromination Effects 0.000 claims 1
- 238000005893 bromination reaction Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 claims 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 239000002344 surface layer Substances 0.000 claims 1
- 229910001868 water Inorganic materials 0.000 abstract description 10
- 238000007385 chemical modification Methods 0.000 abstract description 7
- 239000007769 metal material Substances 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910001431 copper ion Inorganic materials 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 229910002651 NO3 Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000003075 superhydrophobic effect Effects 0.000 description 6
- 230000003666 anti-fingerprint Effects 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000003068 static effect Effects 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003518 caustics Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000003670 easy-to-clean Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- -1 alkyl trimethyl ammonium bromides Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D5/04—Electroplating with moving electrodes
- C25D5/06—Brush or pad plating
-
- 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
- C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
Landscapes
- 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)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
The present invention relates to a kind of automatically cleaning corrosion resistant plate and its production method, the automatically cleaning corrosion resistant plate includes stainless steel base, the stainless steel base surface has copper coating, the copper coating has multiple regularly arranged construction units, the construction unit includes a three-level hierarchy, and it is distributed in multiple submicron order bulge-structures of copper coating basal surface, the surface of the submicron order bulge-structure has the nanoscale grainiess that multiple stratiforms are piled up.The present invention adopts a step technique of brush plating, traditional organic coating is replaced using electrodeposited coating, the automatically cleaning corrosion resistant plate without any surface chemical modification is constructed, so as to further expand the range of application of metal material, such as corrosion protection, micro-fluidic system and oil-water separation etc..
Description
Technical field
The present invention relates to metal engineering Material Field, particularly a kind of corrosion resistant plate with self-cleaning function, and should
The production method of corrosion resistant plate.
Background technology
Every field of the metal engineering material throughout our productive lifes, is also a weight of super-hydrophobic boundary material research
Point, wherein, is with a wide range of applications with special infiltrating metal material, such as surface is anticorrosive, oil-water separation interface,
Liquid transmission, microfluidic device etc..Generally, the surface of solids build super-hydrophobic coat method include sol-gal process,
Layer-by-1ayer methods, electrochemical deposition method, electrostatic spray etc..
Corrosion resistant plate is applied to the every field of our productive lifes as engineering foundation material, but due to rustless steel tool
There is higher surface free energy, be typical intrinsic hydrophilic material, nearly all liquid is all easily in its surface spreading, and moistens
Wet stainless steel surfaces, so as to affect the attractive in appearance of its surface, or even corrosion stainless steel surfaces, affect its performance.So, stainless
The preparation of steel super hydrophobic surface generally needs to build coarse structure on stainless steel base, and using low-surface-energy material (for example
Various organic fluorocompounds) carry out surface chemical modification to reduce the surface free energy of stainless steel material to rough surface.
, typically in one layer of organic chemical modification layer of surface-coated of product, such as, China is specially for traditional automatically cleaning product
Profit application CN102618104A discloses a kind of anti-fingerprint paint, anti-fingerprint stainless steel plate and preparation method thereof, is in rustless steel
Plate surface coats a kind of anti-fingerprint paint so as to surface anti-soil, anti-fingerprint, with self-cleaning function；Chinese patent application
CN103276393A discloses a kind of preparation method of stainless steel base surface nitrogen-doped titanium dioxide porous membrane, in rustless steel
Matrix surface nitrogen-doped titanium dioxide porous membrane, to realize stainless photocatalytic self-cleaning and photo-catalyst；Chinese special
Profit application CN103862745A discloses a kind of antibacterial composite stainless steel plate easy to clean, one layer of tool of meltallizing on stainless steel base two sides
There is the nanometer titanium dioxide coating from ability easy to clean so as to good self-cleaning function and antibacterial effect.
However, relative to stainless steel surfaces, the heat stability of Organic chemical layer and mechanical stability are poor, exceedingly odious
Easily destroyed in environment, in turn resulted in the forfeiture of stainless steel surfaces super-hydrophobicity.Additionally, chemical modification layer can also affect not
The intrinsic property of rust Steel material, such as surface conductivity etc..
Therefore, the super-hydrophobic stainless steel surfaces for not having any surface chemical modification, particularly self-cleaning surface are prepared no matter
It is in terms of theoretical research, or in terms of practical application, all there is critically important realistic meaning.
Content of the invention
The present invention is intended to provide a kind of adopting step technique of brush plating production, without any surface chemical modification, tool
There is the stainless steel metal sheet material of self-cleaning surface, organic chemistry is coated with to solve the needs of prior art presence in stainless steel surfaces
Layer, consequently, it is possible to affect the problem of rustless steel intrinsic property.
For achieving the above object, concrete scheme of the invention is as follows：
A kind of automatically cleaning corrosion resistant plate, including stainless steel base, the stainless steel base surface has copper coating, the copper coating
There are multiple regularly arranged construction units, the construction unit to include a three-level hierarchy, the three-level hierarchy
Including micron order mastoid process structure, submicron order bulge-structure and nanometer-size die structure；The surface of the micron order mastoid process structure
There are multiple stratiforms to pile up for the submicron order bulge-structure that there are multiple stratiforms to pile up, the surface of the submicron order bulge-structure
Nanoscale grainiess；The construction unit also includes the raised knot of the multiple submicron orders for being distributed in copper coating basal surface
Structure, the surface of the submicron order bulge-structure have the nanoscale grainiess of multiple stratiforms accumulations.
Further, the construction unit includes a three-level hierarchy and is distributed in two Asias of copper coating basal surface
Micron order bulge-structure.
Further, the width of the single three-level hierarchy is 0.4-1.9 μm, is highly 1-2.5 μm, two neighboring
The spacing of the three-level hierarchy is 1.5-4.5 μm.
Further, the copper coating is formed by the liquid plating of crossing of following component：Copper sulfate 200-300 g/L, ammonium nitrate
24-36 g/L, citric acid 2.5-4 g/L, cetyl trimethylammonium bromide 0.6-5 g/L, balance of deionized water.
Further, the stainless steel base is 200 series or 300 series stainless steel plates.
The present invention also provides the production method of the automatically cleaning corrosion resistant plate, comprises the following steps：
A. stainless steel base pretreatment：
Grinding process is carried out to the stainless steel base with the emery cloth of model 600#, 2000# successively, to remove the stainless base steel
The oxide layer in body surface face, obtains the surface of flat smooth；
The above-mentioned stainless steel base through obtained by grinding process is finely polished with diamond paste, until described stainless
The surface of steel matrix reaches mirror effect；
Be 1800W with acetone in ultrasonic power, cleaning frequency in the ultrasound wave service sink of 28kHz to above-mentioned through fine polishing
Process obtained stainless steel base to be cleaned, until removing the greasy dirt on the stainless steel base surface；
Deionized water removes the acetone of the above-mentioned stainless steel base remained on surface obtained through ultrasound wave cleaning, and blows rapidly
Dry；
B. Brush Plating prepares copper coating：
Coating process is carried out to the stainless steel base described in step A through pretreatment using brush electroplating device, the Brush Plating sets
Standby negative electrode is the stainless steel base through pretreatment, and anode is plated pen；
Liquid will be crossed the surface to the stainless steel base through pretreatment is flowed from brush plating groove by blood circulation；
The plated pen moves reciprocatingly along the surface of the stainless steel base through pretreatment；
In the copper-depositing on surface coating of the stainless steel base through pretreatment, the copper coating has multiple regularly arranged
Construction unit, the construction unit include a three-level hierarchy, the three-level hierarchy include micron order mastoid process structure,
Submicron order bulge-structure and nanometer-size die structure；The construction unit also includes the multiple Asias for being distributed in copper coating basal surface
Micron order bulge-structure；
C. finished product is obtained：
Priority dehydrated alcohol and deionized water deposit the stainless steel base of copper coating repeatedly described in rinsing step B；
Dried up, dried with high pressure air rifle, finished product.
Further, the plating solution includes following component：Copper sulfate 200-300 g/L, ammonium nitrate 24-36 g/L, Fructus Citri Limoniae
Sour 2.5-4 g/L, cetyl trimethylammonium bromide 0.6-5 g/L, balance of deionized water.
Further, the technological parameter of the brush electroplating device is：2.5 V of brushing plating voltage, 0.6 Aa/mm of electric current density,
25 DEG C of brush plating temperature；
Optional, the pH for crossing liquid is 3.0, and the liquid that crosses passes through blood circulation from brush plating groove with the flow velocity stream of 20 L/min
Surface to the stainless steel base；
Optional, the plated pen with the translational speed of 1.5 m/min, 2.5 Kpa contact pressure along the stainless steel base
Surface move reciprocatingly, the brush plating time be 40 min.
Further, the width of the single three-level hierarchy in the copper coating is 0.4-1.9 μm, is highly 1-2.5 μ
M, the spacing of the single three-level hierarchy is 1.5-4.5 μm.
Further, there are multiple stratiforms to pile up submicron order bulge-structure, institute on the surface of the micron order mastoid process structure
The yardstick for stating submicron order is 100-600 nm；
Optional, the surface of the submicron order bulge-structure has a nanometer-size die structure that multiple stratiforms are piled up, and described receives
The yardstick of meter level is 20-50 nm.
Wherein, the effect for crossing each composition in liquid for preparing copper coating of the invention is as follows：
Copper sulfate is the main component in Brush Plating plating solution, provides metal copper ion (Cu for Brush Plating deposition process2+).
Ammonium nitrate is main chelating agent in Brush Plating plating solution, can be with the metal copper ion (Cu in plating solution2+) combine shape
Into complex ion, to reduce metal copper ion (Cu2+) sedimentation potential, while it can also improve copper sulfate in deionized water
Dissolubility.
Citric acid is metal copper ion (Cu in Brush Plating plating solution2+) auxiliary complex-former.
Cetyl trimethylammonium bromide (CTAB) is a kind of cationic surface active agent, and it can adsorb easily
As the surface of the stainless steel base of negative electrode, and the surface of the moistening stainless steel base, so as to attached to stainless steel base surface
Near metal copper ion (Cu2+) repulsive interaction is produced, reduce metal copper ion (Cu in Brush Plating plating solution with this2+) deposition
Speed, reaches the purpose of control coating surface morphology and crystal structure.With the rising of CTAB concentration, in plating solution, copper ion is heavy
Product speed slows down, and when CTAB concentration is 3 g/L, the apparent of copper coating prepared by Brush Plating of the present invention reaches optimum.
The width of the single three-level hierarchy obtained by the present invention is 0.4-1.9 μm, is highly 1-2.5 μm, adjacent two
The spacing of individual three-level hierarchy is 1.5-4.5 μm.In the range of the dimension limitation of the present invention, with single three-level hierarchy
Width, height increase, the present invention obtained by automatically cleaning stainless steel surface wettability be gradually converted into by hydrophobicity super
Hydrophobic.When single three-level hierarchy size beyond the present invention restriction scope when, the hydrophobicity of stainless steel surface can be by
Decrescence weak.
The present invention was mainly used for using the gauze of model 600# in the step of carrying out pretreatment to stainless steel base
The oxide layer on stainless steel base surface is removed, is mainly used for polishing using the gauze of model 2000#, to obtain flat smooth
Stainless steel base surface.
The brushing plating voltage of brush electroplating device is set to 2.5V in the step of Brush Plating prepares copper coating by the present invention, this
It is because：Under the brushing plating voltage, the electric current distribution of cathode surface is uniform, and the copper ion in plating solution freely can spread
And be uniformly deposited on matrix surface, so as to define opposed flattened metal surface.If changing brushing plating voltage, relatively low
Brushing plating voltage under, the electric current distribution of cathode surface is uneven, can cause copper ion in the plating solution near cathode surface
Free diffusing receives certain restriction.Due to point discharge effect, the copper ion of localized clusters is preferentially raised in matrix surface
Where deposit, so as to define coarse metal surface.
The brush plating time is defined as 40 min in the step of Brush Plating prepares copper coating by the present invention, and reason is：This
The structure size of the bright three-level hierarchy for constituting copper coating is relevant with the brush plating time, and the brush plating time is longer, the three-level classification knot
The size of structure is bigger.With width, the height increase of three-level hierarchy, the wettability of the copper coating surface for being formed can be gradually
It is converted into by hydrophobicity super-hydrophobic；When the single three-level hierarchy width be 0.4-1.9 μm, highly for 1-2.5 μm when, this
The hydrophobic performance of the obtained copper coating surface of invention reaches most preferably；Beyond the structure size restriction scope when, copper coating table
The hydrophobicity in face gradually can weaken.The brush plating time is defined as 40 min by the present invention, can form width for 0.4-1.9 μm, highly
For 1-2.5 μm of three-level hierarchy, so as to form the copper coating with optimal hydrophobic performance.
The beneficial effects of the present invention is：The present invention adopts a step technique of brush plating, has using electrodeposited coating replacement is traditional
Organic coating, constructs the automatically cleaning corrosion resistant plate without any surface chemical modification, so as to further expand metal material
Range of application, such as corrosion protection, micro-fluidic system and oil-water separation etc..
Using the processing technology of the present invention, 40 min of brush plating under conditions of brushing plating voltage is 2.5V, the present invention can be made
Obtained copper coating have unique class Folium Nelumbinis three-level hierarchy, i.e. micron order mastoid process structure, submicron order bulge-structure and
Nanometer-size die structure tertiary structure, the tertiary structure are superimposed successively step by step, to form copper coating of the present invention.Rustless steel of the present invention
On plate, the three-level hierarchy of copper coating has automatically cleaning effect, can make base material that there is the spy for being difficult to adsorb corrosive substance
Property, the stainless steel product diversification of this area such that it is able to greatly improve stainless comprehensive performance, is made, more to meet
The use requirement of client, improves the competitiveness of enterprise.
Description of the drawings
Fig. 1 is 2 copper coating surface structural representation of the embodiment of the present invention；
Fig. 2 is that 2 brush electroplating device of the embodiment of the present invention uses schematic diagram.
Specific embodiment
Embodiments of the invention are described below in detail, are shown in the drawings, wherein same or similar label from start to finish
Represent same or similar element or the element with same or like function.Embodiment below with reference to Description of Drawings is
Exemplary, the example of the embodiment is intended to for explaining the present invention, and is not considered as limiting the invention.Embodiment
In unreceipted particular technique or condition person, according to the technology or condition described by document in the art or according to the description of product
Book is carried out.Agents useful for same or the unreceipted production firm person of instrument, be can pass through city available from conventional products.
Embodiment 1：A kind of automatically cleaning corrosion resistant plate and its production method
The automatically cleaning corrosion resistant plate that the present embodiment 1 is provided includes the stainless steel base of 200 series, and plating is in the stainless base steel
The copper coating in body surface face, the copper coating include following component：Copper sulfate（CuSO4•5H2O）200g/L, ammonium nitrate（NH4NO3）
24g/L, citric acid（C6H807•H2O）2.5g/L, cetyl trimethylammonium bromide（CTAB）0.6g/L, surplus using go from
Sub- water is used as solvent.
With reference to Fig. 2, the technique for preparing the automatically cleaning corrosion resistant plate of the present embodiment 1 is comprised the following steps：
A. pretreatment is carried out to the surface of stainless steel base 1：
First the surface of stainless steel base 1 is polished with the emery cloth of model 600#, to remove the oxygen on 1 surface of stainless steel base
Change layer；The surface of stainless steel base 1 is polished with the emery cloth of model 2000# again, obtains flat smooth surface；
The above-mentioned stainless steel base 1 through obtained by polishing, polishing is finely polished with diamond paste, until not
The surface of rust steel matrix 1 reaches mirror effect；
Be 1800W with acetone in ultrasonic power, cleaning frequency in the ultrasound wave service sink of 28kHz to above-mentioned through fine polishing
Process obtained stainless steel base 1 to be cleaned, to remove the greasy dirt for being attached to 1 surface of stainless steel base；
Deionized water removes the acetone of above-mentioned 1 remained on surface of stainless steel base obtained through ultrasound wave cleaning, and blows rapidly
Dry.
B. plating solution is prepared：
Copper sulfate（CuSO4•5H2O）200g/L, ammonium nitrate（NH4NO3）24g/L, citric acid（C6H807•H2O）2.5g/L, ten
Six alkyl trimethyl ammonium bromides（CTAB）0.6g/L, surplus is using deionized water as solvent.
C. copper coating is prepared with brush electroplating device：
Coating process is carried out to the stainless steel base 1 obtained by step A using brush electroplating device, using stainless steel base 1 as the moon
Pole, using plated pen 5 as anode.Arranging technique of brush plating parameter is：2.5 V of brushing plating voltage, 0.6 Aa/mm of electric current density, brush plating
25 DEG C of temperature；
By plating solution obtained in step B 6 by blood circulation using 20 L/min flow velocitys continuously flow from brush plating groove 7 to as
1 surface of stainless steel base of negative electrode；
The anode of plated pen of ining succession 5 with 1.5 m/min of translational speed, 2.5 Kpa of contact pressure, along 1 table of negative electrode stainless steel base
Face moves reciprocatingly, and the brush plating time is 40 min；
In 1 copper-depositing on surface coating of stainless steel base：Under given 2.5 V of brushing plating voltage, 40 min of brush plating, in plating solution 6
Metal copper ion（Cu2+）Deposited on the surface of negative electrode stainless steel base 1 layer by layer.In 6 complexing agent nitric acid of plating solution
The specific physical chemical reaction of ammonium and surfactant cetyl trimethylammonium bromide, and the physics between brush plating anode and cathode
Under disturbance, 1 surface of stainless steel base deposits the copper coating being made up of the construction unit of many irregular alignments, the copper coating table
Compare flat smooth in face.
With the rising of brushing plating voltage, the diameter of copper film surface micrometre-grade mastoid process structure can be gradually reduced with height, and micro-
Spacing between meter level mastoid process structure then first reduces and increases afterwards, and the hydrophobicity of products obtained therefrom also gradually weakens.Therefore, the present embodiment
1 limits brushing plating voltage as 2.5 V.
D. finished product is obtained：
Priority dehydrated alcohol and deionized water copper coating repeatedly obtained by rinsing step C；
Dried up, dried with high pressure air rifle, finished product.
Experimental result：
By observation, the stainless steel base surface of the present embodiment 1 has the copper coating being made up of many construction units, but arranges not
Rule, the construction unit include a three-level hierarchy and are distributed in two submicron orders projection knots of copper coating basal surface
Structure.
Affected by solution concentration, the present embodiment 1 constitutes the highly relatively low of the construction unit of copper coating, the copper for therefore being formed
Coating surface compares flat smooth.
In the present embodiment 1, the size of the three-level hierarchy is：About 0.4 μm of width, about 1 μm of height, two neighboring micron
The spacing of level mastoid process structure is 1.5-4.5 μm.
In weak hydrophobicity, the static contact angle of the copper coating surface water droplet is about 125 ° to the copper coating of the present embodiment 1.
Embodiment 2：A kind of automatically cleaning corrosion resistant plate and its production method
The automatically cleaning corrosion resistant plate that the present embodiment 2 is provided includes the stainless steel base 1 of 200 series, and plating is in the rustless steel
The copper coating on 1 surface of matrix, the copper coating include following component：Copper sulfate（CuSO4•5H2O）260g/L, ammonium nitrate
（NH4NO3）30g/L, citric acid（C6H807•H2O）3g/L, cetyl trimethylammonium bromide（CTAB）3g/L, surplus are adopted
Deionized water is used as solvent.
The processing step of automatically cleaning corrosion resistant plate of the present embodiment 2 is prepared with reference to embodiment 1, difference is, the present embodiment 2
The liquid that crosses for being adopted is：Copper sulfate（CuSO4•5H2O）260g/L, ammonium nitrate（NH4NO3）30g/L, citric acid（C6H807•H2O）
3g/L, cetyl trimethylammonium bromide（CTAB）3g/L, surplus is using deionized water as solvent.
Experimental result：
With reference to Fig. 1, by observation, 2 stainless steel base of the present embodiment, 1 surface defines and is uniformly distributed, and separate structure
Unit, the profile and sharpness of border of the construction unit are visible.The construction unit includes a three-level hierarchy and is distributed in copper
Two submicron order bulge-structures 3 of coating basal surface.The three-level hierarchy includes micron order mastoid process structure 2, submicron order
Bulge-structure 3 and nanometer-size die structure 4, wherein, single micron order mastoid process structure 2 has the submicron that many stratiforms are piled up
Level bulge-structure 3, the submicron order bulge-structure 3 has the nanometer-size die structure 4 that many stratiforms are piled up, so as to form tool
There is the copper coating of many class Folium Nelumbinis three-level hierarchies.
In the present embodiment 2, the structure size of the single three-level hierarchy is：Width（With reference to W2 in Fig. 1）For 0.4-
1.9 μm, highly（With reference to H in Fig. 1）For 1-2.5 μm, the spacing of the two neighboring three-level hierarchy（With reference to W1 in Fig. 1）For
1.5-4.5μm.
The copper coating hydrophobic performance of the present embodiment 2 is good, about 150 ° of the static contact angle of the copper coating surface water droplet.
Embodiment 3：A kind of automatically cleaning corrosion resistant plate and its production method
The automatically cleaning corrosion resistant plate that the present embodiment 3 is provided includes the stainless steel base of 300 series, and plating is in the stainless base steel
The copper coating in body surface face, the copper coating include following component：Copper sulfate（CuSO4•5H2O）300g/L, ammonium nitrate（NH4NO3）
36g/L, citric acid（C6H807•H2O）4g/L, cetyl trimethylammonium bromide（CTAB）5g/L, surplus adopt deionized water
As solvent.
The processing step of automatically cleaning corrosion resistant plate of the present embodiment 3 is prepared with reference to embodiment 1, difference is, the present embodiment 3
The liquid that crosses for being adopted is：Copper sulfate（CuSO4•5H2O）300g/L, ammonium nitrate（NH4NO3）36g/L, citric acid（C6H807•H2O）
4g/L, cetyl trimethylammonium bromide（CTAB）5g/L, surplus is using deionized water as solvent.
Experimental result：
By observation, the stainless steel base surface of the present embodiment 3 has the copper coating being made up of many construction units, but arranges not
Rule, the construction unit include a three-level hierarchy and are distributed in two submicron orders projection knots of copper coating basal surface
Structure.
Affected by solution concentration, the present embodiment 3 constitutes the highly relatively low of the construction unit of copper coating, the copper for therefore being formed
Coating surface compares flat smooth.
In the present embodiment 3, the size of the three-level hierarchy is：About 0.4-1.9 μm of width, about 1-2.5 μm of height are adjacent
The spacing of two micron order mastoid process structures is 1.5-4.5 μm.
The copper coating hydrophobic performance of the present embodiment 3 is better than embodiment 1, more slightly worse than the embodiment 2 of most preferred embodiment, the copper plating
About 130 ° of the static contact angle of layer surface water droplet.
Embodiment 1-3 is compared with the anticorrosive testing result of comparative example 1-3：
Comparative example 1：Choose the 200 series stainless steel plates that surface texture does not deal with, numbering A.
Comparative example 2：With comparative example 1, numbering B.
Comparative example 3：Choose the 300 series stainless steel plates that surface texture does not deal with, numbering C.
The corrosion resistant plate of one piece embodiment 1-3 is chosen respectively, and numbering is A ', B ', C ', under equal conditions, with comparative example
A, B, C corrosion resistant plate of 1-3 carries out neutral salt spray test, after 72 hours, Comparability test result：
The surface of A, B, C corrosion resistant plate occurs in that obvious rust spot, spot corrosion area are about 1%；A ', B ', C ' surfaces do not have rust spot.
It can be seen that, the three-level hierarchy of the copper coating of stainless steel surface of the present invention has automatically cleaning effect, can make base
Material has the characteristic for being difficult to adsorb corrosive substance, so as to improve the comprehensive performance of corrosion resistant plate.
Although specifically showing and describing the present invention in conjunction with preferred embodiment, those skilled in the art should be bright
In vain, in the spirit and scope of the present invention limited without departing from appended claims, in the form and details can be right
The present invention makes a variety of changes, and is protection scope of the present invention.
Claims (10)
1. a kind of automatically cleaning corrosion resistant plate, including stainless steel base, it is characterised in that there is copper to plate on the stainless steel base surface
Layer, the copper coating have multiple regularly arranged construction units, and the construction unit includes a three-level hierarchy, described
Three-level hierarchy includes micron order mastoid process structure, submicron order bulge-structure and nanometer-size die structure；The micron order breast
The surface of lug structure has the submicron order bulge-structure that multiple stratiforms are piled up, and the surface of the submicron order bulge-structure has
The nanoscale grainiess that multiple stratiforms are piled up；The construction unit also includes the multiple sub-micros for being distributed in copper coating basal surface
Meter level bulge-structure, the surface of the submicron order bulge-structure have the nanoscale grainiess of multiple stratiforms accumulations.
2. a kind of automatically cleaning corrosion resistant plate according to claim 1, it is characterised in that the construction unit includes three
Level hierarchy and two submicron order bulge-structures for being distributed in copper coating basal surface.
3. a kind of automatically cleaning corrosion resistant plate according to claim 1, it is characterised in that the single three-level hierarchy
Width is 0.4-1.9 μm, is highly 1-2.5 μm, and the spacing of the two neighboring three-level hierarchy is 1.5-4.5 μm.
4. a kind of automatically cleaning corrosion resistant plate according to claim 1, it is characterised in that the copper coating is by following component
Cross liquid plating to form：Copper sulfate 200-300 g/L, ammonium nitrate 24-36 g/L, citric acid 2.5-4 g/L, cetyl trimethyl
Ammonium bromide 0.6-5 g/L, balance of deionized water.
5. a kind of automatically cleaning corrosion resistant plate according to claim 1, it is characterised in that the stainless steel base for 200 is
Row or 300 series stainless steel plates.
6. the production method of the automatically cleaning corrosion resistant plate described in a kind of any one of claim 1-5, it is characterised in that including following
Step：
A. stainless steel base pretreatment：
Grinding process is carried out to the stainless steel base with the emery cloth of model 600#, 2000# successively, to remove the stainless base steel
The oxide layer in body surface face, obtains the surface of flat smooth；
The above-mentioned stainless steel base through obtained by grinding process is finely polished with diamond paste, until described stainless
The surface of steel matrix reaches mirror effect；
Be 1800W with acetone in ultrasonic power, cleaning frequency in the ultrasound wave service sink of 28kHz to above-mentioned through fine polishing
Process obtained stainless steel base to be cleaned, until removing the greasy dirt on the stainless steel base surface；
Deionized water removes the acetone of the above-mentioned stainless steel base remained on surface obtained through ultrasound wave cleaning, and blows rapidly
Dry；
B. Brush Plating prepares copper coating：
Coating process is carried out to the stainless steel base described in step A through pretreatment using brush electroplating device, the Brush Plating sets
Standby negative electrode is the stainless steel base through pretreatment, and anode is plated pen；
Liquid will be crossed the surface to the stainless steel base through pretreatment is flowed from brush plating groove by blood circulation；
The plated pen moves reciprocatingly along the surface of the stainless steel base through pretreatment；
In the copper-depositing on surface coating of the stainless steel base through pretreatment, the copper coating has multiple regularly arranged
Construction unit, the construction unit include a three-level hierarchy, the three-level hierarchy include micron order mastoid process structure,
Submicron order bulge-structure and nanometer-size die structure；The construction unit also includes the multiple Asias for being distributed in copper coating basal surface
Micron order bulge-structure；
C. finished product is obtained：
Priority dehydrated alcohol and deionized water deposit the stainless steel base of copper coating repeatedly described in rinsing step B；
Dried up, dried with high pressure air rifle, finished product.
7. the production method of a kind of automatically cleaning corrosion resistant plate according to claim 6, it is characterised in that the plating solution includes
Following component：Copper sulfate 200-300 g/L, ammonium nitrate 24-36 g/L, citric acid 2.5-4 g/L, cetyl trimethyl bromination
Ammonium 0.6-5 g/L, balance of deionized water.
8. the production method of a kind of automatically cleaning corrosion resistant plate according to claim 6, it is characterised in that the Brush Plating sets
Standby technological parameter is：2.5 V of brushing plating voltage, 0.6 Aa/mm of electric current density, 25 DEG C of brush plating temperature；
Optional, the pH for crossing liquid is 3.0, and the liquid that crosses passes through blood circulation from brush plating groove with the flow velocity stream of 20 L/min
Surface to the stainless steel base；
Optional, the plated pen with the translational speed of 1.5 m/min, 2.5 Kpa contact pressure along the stainless steel base
Surface move reciprocatingly, the brush plating time be 40 min.
9. the production method of a kind of automatically cleaning corrosion resistant plate according to claim 6, it is characterised in that in the copper coating
Single three-level hierarchy width be 0.4-1.9 μm, be highly 1-2.5 μm, the spacing of the single three-level hierarchy
For 1.5-4.5 μm.
10. the production method of a kind of automatically cleaning corrosion resistant plate according to claim 6, it is characterised in that：The micron order
There are multiple stratiforms to pile up submicron order bulge-structure on the surface of mastoid process structure, and the yardstick of the submicron order is 100-600
nm；
Optional, the surface of the submicron order bulge-structure has a nanometer-size die structure that multiple stratiforms are piled up, and described receives
The yardstick of meter level is 20-50 nm.
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| CN112802909A (en) * | 2021-01-18 | 2021-05-14 | 浙江中聚材料有限公司 | Easy-to-clean solar photovoltaic back plate and preparation process thereof |
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