CN105648490A - Super-hydrophobic surface without modification of low surface energy matter and preparation method thereof - Google Patents
Super-hydrophobic surface without modification of low surface energy matter and preparation method thereof Download PDFInfo
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- CN105648490A CN105648490A CN201610013538.5A CN201610013538A CN105648490A CN 105648490 A CN105648490 A CN 105648490A CN 201610013538 A CN201610013538 A CN 201610013538A CN 105648490 A CN105648490 A CN 105648490A
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- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 230000004048 modification Effects 0.000 title abstract description 6
- 238000012986 modification Methods 0.000 title abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910017709 Ni Co Inorganic materials 0.000 claims abstract description 27
- 229910003267 Ni-Co Inorganic materials 0.000 claims abstract description 27
- 229910003262 Ni‐Co Inorganic materials 0.000 claims abstract description 27
- 238000004070 electrodeposition Methods 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 239000002086 nanomaterial Substances 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 6
- 239000000956 alloy Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims description 37
- 238000007747 plating Methods 0.000 claims description 20
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 15
- 150000001875 compounds Chemical group 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005480 shot peening Methods 0.000 claims description 12
- 238000009713 electroplating Methods 0.000 claims description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000010431 corundum Substances 0.000 claims description 6
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 101710134784 Agnoprotein Proteins 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000008021 deposition Effects 0.000 claims description 4
- 239000011324 bead Substances 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003068 static effect Effects 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003592 biomimetic effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
Classifications
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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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a super-hydrophobic surface without modification of low surface energy matter and a preparation method thereof. Ni-Co alloy of a conical micro-nano structure deposits on the surface of metal in an electrochemical deposition mode, then a nanometer Ag film deposits on the surface of the Ni-Co micro-nano conical surface through a chemical reduction method, the super-hydrophobic surface is obtained after the metal is placed in air for 3-7 days, and modification of the low surface energy matter is not needed. The preparation process is simple, easy to operate and low in equipment requirement and cost, and a novel idea is provided for preparation of other super-hydrophobic surfaces.
Description
Technical field
The preparation method that the present invention relates to a kind of super hydrophobic surface modified without low-surface energy substance.
Background technology
Micron-nanometer composite construction special in organism can give its special surface characteristic, and typical have " leaf surface of plant of lotus leaf effect " (such as Folium Nelumbinis etc.) and the superhydrophobic characteristic of insect wing (such as Cicadae, butterfly's wing etc.) exactly. By substantial amounts of research it appeared that, although the microstructure on these surfaces of nature super hydrophobic surface is slightly different, but all have the structure of the micro-nano coarse microcosmic of binary, thus the particularity demonstrating super hydrophobic surface has direct correlation with the micro-nano coarse structure of binary and low-surface-energy material coating. Thus in low-surface energy substance, build rough surface and on coarse surface texture, modify the material of low-surface-energy, it is the necessary ways developing biomimetic super hydrophobic surface, and metal to be intrinsic hydrophilic, so it prepares the super hydrophobic surface two-dimentional coarse structure only by the compound micro-nano at surface construction, the material of recycling low-surface-energy is modified. Such as A.Safaee has reported the AgNO copper sheet cleaned up being put into low concentration3In solution after certain time, recycling stearic acid carries out surface modification, being successfully prepared out static contact angle is 156 ��, and roll angle is at the super-hydrophobic copper surface [A.Safaee.etal.AppliedSurfaceScience.2008,254.2493] of 4.1 ��. Larmour et al. puts into the AgNO of 0.01mol/L zinc paper tinsel or Copper Foil3The HAuCl of middle 20s or 0.004mol/L460s in solution, then recycles 1H, 1H, 2H, 2H-perfluor decyl mercaptan and carries out surface modification, successfully prepares zinc paper tinsel or the metal super-hydrophobic surface of Copper Foil [IainA.Larmour.Angew.Chem.2007,119.1740]. Same Cao et al. has also reported the [Ag (NH copper sheet cleaned up with hydrochloric acid being put into 0.03mol/L3)2] 6h in OH solution, the static contact angle copper surface [ZongweiCao.Chem.Commun, 2008,2692] more than 150 �� can be prepared. Thus utilize the report on super-hydrophobic surface that intermetallic chemical reduction reaction prepares Ag or Au nanometer of rete very common, but need not be artificial during preparation utilize low-surface energy substance to modify just can to reach super-hydrophobic report also rarely found.
Summary of the invention
The preparation method that the present invention provides a kind of super hydrophobic surface modified without low-surface energy substance is simply effective, with low cost.
The technical scheme is that a kind of metal super-hydrophobic surface modified without low-surface energy substance, method first with electrochemical deposition has taper micro-nano structure Ni-Co alloy in metal surface deposition, then chemical reduction method is recycled, deposit Ag nanometer of rete at Ni-Co micro-nano poppet surface, place in atmosphere 3��7 days and adsorbed the metal super-hydrophobic surface that namely acquisition modifiies without low-surface energy substance by carbon hydrogen element.
The method of the metal super-hydrophobic surface modified without low-surface energy substance that preparation is described, method first with electrochemical deposition has taper micro-nano structure Ni-Co alloy in metal surface deposition, then chemical reduction method is recycled, deposit Ag nanometer of rete at Ni-Co micro-nano poppet surface, place in atmosphere 3��7 days and adsorbed the metal super-hydrophobic surface that namely acquisition modifiies without low-surface energy substance by carbon hydrogen element.
The method preparing the metal super-hydrophobic surface modified without low-surface energy substance, concretely comprises the following steps:
(1) surface preparation: metal sample is carried out high-energy shot process, ultrasonic cleaning dry for standby subsequently;
(2) electrochemical deposition: with pure nickel plate for anode, metal sample is negative electrode, puts in electroplate liquid, obtains Ni-Co micro-nano compound structure by being electrochemically-deposited in sample surfaces, and after taking-up, deionized water cleans, and cold wind is standby after drying up;
(3) electronation: the sample electroplated is put into AgNO3Solution, obtains Ag nanometer of rete at Ni-Co micro-nano compound structure surface reduction, and the sample deionized water after chemical plating cleans up rear cold wind and dries up;
(4) sample is rested on humidity 50-80%, in the open environment of temperature 20-35 DEG C, after 3-7 days, namely obtain the metal super-hydrophobic surface modified without low-surface energy substance.
In step (1) when bead, shot-peening order number is 300-400 order, and stream pressure is 0.5-1MPa, and injecting time is 0.5-2min; Described shot-peening is any one in Brown Alundum, corundum and quartz or appoints several mixture.
Electroplate liquid described in step (2) is 150-300g/LNiCl2��6H2O��30-60g/LCoCl2��6H2O��25-40g/LH3BO3With 50-130mL/L ethylenediamine, electroplate liquid pH is 3.5-4.5, and during plating, temperature controls at 55��65 DEG C, and cathode-current density controls at 1��5A/dm2, electroplating time 8��15min.
AgNO described in step (3)3Concentration is 2��4mmol/L, and the temperature of chemical plating is 25��35 DEG C, and the time is 120��200s.
Beneficial effect:
(1) present invention utilizes traditional, comparatively ripe plating and electronation technology, and technique is simple, equipment requirements is low; Method first with electrochemical deposition deposits the Ni-Co with micro-nano structure needle-like in metal surface, then the method for recycling chemical replacement reaction is preferentially preparing silverskin on the top of the Ni-Co of micro-nano needle-like by chemical reduction reaction, can prepare super-hydrophobic surface only placing in atmosphere 3��7 days without low-surface energy substance surface modification.
(2) matrix is required low by the method for the invention, can be prepared on metal or other conductive material;
(3) high-energy shot pre-treatment can not only improve the adhesion of Ni-Co alloy and matrix during plating, simultaneously also in the degree of roughness that to a certain degree improve surface;
(4) by plating solution formula, electroplating technology, electronation formula and technique, can Effective Regulation surface micro-nano structure;
(5) compared with the surface of individually plating or electronation, the sample that after the plating that the present invention adopts, again prepared by electronation silverskin, not only contact angle may be up to 158 ��, and roll angle is also less than 5 ��, it is shown that excellent low adherent super-hydrophobic.Independent electroplated Ni-Co sample surfaces, after standing 3-7 days in air, the maximum static contact angle of sample water droplet can reach more than 150 ��, but roll angle is consistently greater than 50 ��, it is shown that high-adhesiveness. Individually adopting electronation silverskin technology of preparing of the present invention, sample surfaces contact angle is consistently less than 90 ��.
(6) sample prepared by the method for the invention only needs to place certain time in atmosphere, can be adsorbed by carbon hydrogen element, it is thus achieved that super-hydrophobicity, it is not necessary to low-surface energy substance is modified, from conventional super hydrophobic surface technology of preparing different, it is to avoid the organic use of low-surface-energy.
Accompanying drawing illustrates:
Fig. 1 is the scanning electron microscopic picture in embodiment 1 after the process of sample high-energy shot.
Fig. 2 is the scanning electron microscopic picture in embodiment 1 after sample electrochemical deposition Ni-Co.
Fig. 3 is the scanning electron microscopic picture of sample electronation silverskin rear surface composite construction in embodiment 1.
Fig. 4 is local energy spectrum analysis in embodiment 1.
Fig. 5 is the form that in embodiment 2, sample stands air rear surface 5 �� L water droplet.
Detailed description of the invention
The preparation method of the described super hydrophobic surface modified without low-surface energy substance, comprises the following steps:
(1) surface preparation: metal sample is carried out high-energy shot process, shot-peening order number is 300-400 order, stream pressure is 0.5-1MPa, injecting time is 0.5-2min, described shot-peening can be one or both and mixture above in Brown Alundum, corundum and quartz, clean 5-10min with the NaOH solution of 3-10g/L, acetone, ethanol and deionized water successively 20kHz frequency ultrasound respectively subsequently, dry 30min for 150 DEG C, standby;
(2) electrochemical deposition: with pure nickel plate for anode, metal sample is negative electrode, put in electroplate liquid, adjust electroplating bath components proportioning, pH value, temperature, cathode-current density and electroplating time, Ni-Co micro-nano compound structure is obtained at sample surfaces, after taking-up, deionized water cleans, and cold wind is standby after drying up;
(3) electronation silverskin: the sample electroplated is put into AgNO3Solution, controls the temperature of broad liquid and the time of chemical plating, covers Ag nanometer of rete on Ni-Co micro-nano compound structure surface, and the sample deionized water after chemical plating cleans up rear cold wind and dries up;
(4) sample is rested on humidity 50-80%, in the open environment of temperature 20-35 DEG C, after 3-7 days, the metal super-hydrophobic surface modified without low-surface energy substance can be obtained.
Electroplate liquid described in step 2 is 150-300g/LNiCl2��6H2O��30-60g/LCoCl2��6H2O��25-40 g/LH3BO3With 50-130mL/L ethylenediamine, utilizing dilute hydrochloric acid to regulate pH value of solution is 3.5-4.5, and during plating, temperature controls at 55��65 DEG C, and cathode-current density controls at 1��5A/dm2, electroplating time 8��15min.
AgNO described in step 33Concentration is 2��4mmol/L, temperature 25��35 DEG C, time 120��200s.
Embodiment 1
(1) surface preparation: metal sample is carried out high-energy shot process, shot-peening order number is 400 orders, stream pressure is 0.5MPa, injecting time is 2min, described shot-peening can be one or both and mixture above in Brown Alundum, corundum and quartz, clean 5min with the NaOH solution of 3g/L, acetone, ethanol and deionized water successively 20kHz frequency ultrasound respectively subsequently, dry 30min for 150 DEG C, standby;
(2) electrochemical deposition: with pure nickel plate for anode, metal sample is negative electrode, puts in electroplate liquid, and electroplate liquid is 300g/LNiCl2��6H2O��60g/LCoCl2��6H2O��25g/LH3BO3With 130mL/L ethylenediamine, utilizing dilute hydrochloric acid to regulate pH value of solution is 4, and during plating, temperature controls at 60 DEG C, and cathode-current density controls at 2A/dm2, electroplating time 10min, obtain Ni-Co micro-nano compound structure at sample surfaces, after taking-up, deionized water cleans, and cold wind is standby after drying up;
(3) electronation silverskin: the sample electroplated is put into AgNO3Solution, AgNO3Concentration is 3mmol/L, temperature 25 DEG C, time 200s. Cover Ag nanometer of rete on Ni-Co micro-nano compound structure surface, the sample deionized water after chemical plating cleans up rear cold wind and dries up;
(4) sample is rested on humidity 80%, in the open environment that temperature is 35 DEG C, after 3 days, the metal super-hydrophobic surface modified without low-surface energy substance can be obtained.
Embodiment 2
(1) surface preparation: metal sample is carried out high-energy shot process, shot-peening order number is 400 orders, stream pressure is 0.75MPa, injecting time is 1min, described shot-peening can be one or both and mixture above in Brown Alundum, corundum and quartz, clean 5min with the NaOH solution of 7g/L, acetone, ethanol and deionized water successively 20kHz frequency ultrasound respectively subsequently, dry 30min for 150 DEG C, standby;
(2) electrochemical deposition: with pure nickel plate for anode, metal sample is negative electrode, puts in electroplate liquid, and electroplate liquid is 150g/LNiCl2��6H2O��20g/LCoCl2��6H2O��40g/LH3BO3With 50mL/L ethylenediamine, utilizing dilute hydrochloric acid to regulate pH value of solution is 4.5, and during plating, temperature controls at 55 DEG C, and cathode-current density controls at 5A/dm2, electroplating time 8min, obtain Ni-Co micro-nano compound structure at sample surfaces, after taking-up, deionized water cleans, and cold wind is standby after drying up;
(3) electronation silverskin: the sample electroplated is put into AgNO3Solution, AgNO3Concentration is 2mmol/L, temperature 30 DEG C, time 160s. Cover Ag nanometer of rete on Ni-Co micro-nano compound structure surface, the sample deionized water after chemical plating cleans up rear cold wind and dries up;
(4) sample is rested on humidity 65%, in the open environment that temperature is 30 DEG C, after 5 days, the metal super-hydrophobic surface modified without low-surface energy substance can be obtained.
Embodiment 3
(1) surface preparation: metal sample is carried out high-energy shot process, shot-peening order number is 400 orders, stream pressure is 1MPa, injecting time is 0.5min, described shot-peening can be one or both and mixture above in Brown Alundum, corundum and quartz, clean 10min with the NaOH solution of 10g/L, acetone, ethanol and deionized water successively 20kHz frequency ultrasound respectively subsequently, dry 30min for 150 DEG C, standby;
(2) electrochemical deposition: with pure nickel plate for anode, metal sample is negative electrode, puts in electroplate liquid, and electroplate liquid is 220g/LNiCl2��6H2O��45g/LCoCl2��6H2O��30g/LH3BO3With 90mL/L ethylenediamine, utilizing dilute hydrochloric acid to regulate pH value of solution is 3.5, and during plating, temperature controls at 65 DEG C, and cathode-current density controls at 1A/dm2, electroplating time 15min, obtain Ni-Co micro-nano compound structure at sample surfaces, after taking-up, deionized water cleans, and cold wind is standby after drying up;
(3) electronation silverskin: the sample electroplated is put into AgNO3Solution, AgNO3Concentration is 4mmol/L, temperature 30 DEG C, time 120s. Cover Ag nanometer of rete on Ni-Co micro-nano compound structure surface, the sample deionized water after chemical plating cleans up rear cold wind and dries up;
(4) sample is rested on humidity 50%, in the open environment that temperature is 30 DEG C, after 7 days, the metal super-hydrophobic surface modified without low-surface energy substance can be obtained.
Table 1 is static contact angle and the roll angle data that in embodiment 3, sample stands air sample in 7 days.
| Place natural law/sky | Static contact angle/�� | Roll angle/�� |
| 1 | <5 | - |
| 2 | 143.5��5 | - |
| 3 | 158.1��1.0 | 2.8��0.9 |
| 4 | 158.3��0.8 | 2.4��0.9 |
| 5 | 158.5��0.6 | 2.3��0.7 |
| 6 | 158.2��1.2 | 2.5��1.0 |
| 7 | 158.8��0.5 | 2.2��0.5 |
Claims (6)
1. the metal super-hydrophobic surface modifiied without low-surface energy substance, it is characterized in that, method first with electrochemical deposition has taper micro-nano structure Ni-Co alloy in metal surface deposition, then chemical reduction method is recycled, deposit Ag nanometer of rete at Ni-Co micro-nano poppet surface, place in atmosphere 3 ~ 7 days and adsorbed the metal super-hydrophobic surface that namely acquisition modifiies without low-surface energy substance by carbon hydrogen element.
2. the method for the metal super-hydrophobic surface modified without low-surface energy substance described in preparation claim 1, it is characterized in that, method first with electrochemical deposition has taper micro-nano structure Ni-Co alloy in metal surface deposition, then chemical reduction method is recycled, deposit Ag nanometer of rete at Ni-Co micro-nano poppet surface, place in atmosphere 3 ~ 7 days and adsorbed the metal super-hydrophobic surface that namely acquisition modifiies without low-surface energy substance by carbon hydrogen element.
3. the method for the metal super-hydrophobic surface that preparation as claimed in claim 2 modifiies without low-surface energy substance, it is characterised in that concretely comprise the following steps:
(1) surface preparation: metal sample is carried out high-energy shot process, ultrasonic cleaning dry for standby subsequently;
(2) electrochemical deposition: with pure nickel plate for anode, metal sample is negative electrode, puts in electroplate liquid, obtains Ni-Co micro-nano compound structure by being electrochemically-deposited in sample surfaces, and after taking-up, deionized water cleans, and cold wind is standby after drying up;
(3) electronation: the sample electroplated is put into AgNO3Solution, obtains Ag nanometer of rete at Ni-Co micro-nano compound structure surface reduction, and the sample deionized water after chemical plating cleans up rear cold wind and dries up;
(4) sample is rested on humidity 50-80%, in the open environment of temperature 20-35 DEG C, after 3-7 days, namely obtain the metal super-hydrophobic surface modified without low-surface energy substance.
4. the method for the metal super-hydrophobic surface that preparation as claimed in claim 3 modifiies without low-surface energy substance, it is characterised in that in step (1) when bead, shot-peening order number is 300-400 order, and stream pressure is 0.5-1MPa, and injecting time is 0.5-2min; Described shot-peening is any one in Brown Alundum, corundum and quartz or appoints several mixture.
5. the method for the metal super-hydrophobic surface that preparation as claimed in claim 3 modifiies without low-surface energy substance, it is characterised in that the electroplate liquid described in step (2) is 150-300g/LNiCl2��6H2O��30-60g/LCoCl2��6H2O��25-40g/LH3BO3With 50-130mL/L ethylenediamine, electroplate liquid pH is 3.5-4.5, and during plating, temperature controls at 55 ~ 65 DEG C, and cathode-current density controls at 1 ~ 5A/dm2, electroplating time 8 ~ 15min.
6. the method for the metal super-hydrophobic surface that preparation as claimed in claim 3 modifiies without low-surface energy substance, it is characterised in that the AgNO described in step (3)3Concentration is 2 ~ 4mmol/L, and the temperature of chemical plating is 25 ~ 35 DEG C, and the time is 120 ~ 200s.
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