CN104878430A - Process method for preparing super-amphiphobic zinc surface - Google Patents
Process method for preparing super-amphiphobic zinc surface Download PDFInfo
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- CN104878430A CN104878430A CN201510182408.XA CN201510182408A CN104878430A CN 104878430 A CN104878430 A CN 104878430A CN 201510182408 A CN201510182408 A CN 201510182408A CN 104878430 A CN104878430 A CN 104878430A
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Abstract
The invention provides a process method for preparing a super-amphiphobic zinc surface. According to the process method, electrochemical etching and low-surface-energy material modification are combined; a metal zinc plate is cleaned by virtue of an organic solvent to remove oil and is mechanically polished to remove a surface oxide layer, the cleaned zinc plate is fixed on a positive electrode clamp to serve as a positive electrode, and a graphite plate with same area size with the zinc plate is fixed on a negative electrode clamp to serve as a negative electrode; a used electrochemical etching solution is a neutral salt solution with a proper concentration, constant current is introduced into two ends of the positive electrode and the negative electrode, and by controlling the machining time and machining current in the electrochemical etching process, a proper binary micro-nano coarse structure is machined on the surface of the zinc plate; after the binary micro-nano coarse structure produced by virtue of electrochemical etching is modified by virtue of the low-surface-energy material, the super-amphiphobic zinc surface can be obtained. The process method has the advantages of simplicity in operation, high efficiency, good environmental friendliness, low cost and the like and is expected to be applied to large-scale industrial production.
Description
Technical field
The invention belongs to field of metal surface treatment, relate to a kind of processing method preparing super two thin zinc surface.
Background technology
Metallic zinc and alloy thereof, as important engineering materials, have consequence in daily life and industrial and agricultural production, be applied to iron and steel, metallurgy, machinery, electrically, chemical industry, military affairs and medicine and other fields.At present, in numerous metal, the consumption of zinc in worldwide is only second to iron, aluminium and copper.The main application of zinc be as sacrificial anode to the metal protecting reductibility more weak from corrosion, therefore, if improve the erosion resistance of anode zinc to a certain extent, then also can increase the work-ing life of protected metal thereupon.At present, there is the erosion resistance that multiple method is used to improve zinc.Wherein, researchist finds, droplets contact angle and water droplet contact angle are all greater than super two thin zinc surfaces of 150 °, and because it has good waterproof and oilproof performance, therefore corrosion resistance nature is very strong.Therefore, prepare super-hydrophobic/super oleophobic surface and can improve its erosion resistance, expand the scope of application of zinc and zinc alloy simultaneously, have broad application prospects and important researching value.
At present, zinc and zinc alloy matrix are prepared super-hydrophobic method existing a lot, but but rarely have report about preparing zinc-base super-double-hydrophobic surface by the method for efficient, cheap and environmental protection.2005, Qian etc. were prepared on metallic copper, zinc and aluminum substrate by the modification of chemical etching and silicon fluoride and all prepare super hydrophobic surface (Qian, B.T.; Shen, Z.Q.Langmuir 2005,21,9007-9009), the working (machining) efficiency of the method is higher, but owing to employing strong acid, in reaction process, irritant smell produces, larger to the harm of operator and environment.2007, Guo etc. utilized hydrothermal method and stearylmercaptan to modify the method combined and prepare super-hydrophobic Zinc oxide coating (Guo, the M. that surface microstructure is nanometer shape; Diao, P.; Cai, S.M.Thin Solid Films 2007,515,7162-7166), the hydrophobic performance on gained surface is higher, but the method solution used has certain toxicity, can cause certain harm to operator and environment.2008, Meng etc. utilized a step chemical immersion method on Zinc Matrix, prepare super-double-hydrophobic surface (Meng, H.F.; Wang, S.T.; Xi, J.M.; Tang, Z.Y.; Jiang, L.J.Phys.Chem.C 2008,112,11454-11458), the method is simple to operate, but the required reaction times reaches 10 days.2009, Liu etc. utilized a step solution soaking method to prepare super hydrophobic surface (Liu, H.Q. respectively on zinc, steel and silicon substrate; Szunerits, S.; Pisarek, M.; Xu, W.G.; Boukherroub, R.ACS Applied Materials & Interfaces, 2009,9,2086-2091), the method eliminates the step of low surface energy process, but working (machining) efficiency is lower, needs to react 1-3 days.2011, Wang etc. utilized constant potential electrolysis method to prepare based superhydrophobic thin films (Wang, P. at pure zinc surface; Zhang, D.; Qiu, R.; Hou, B.R.Corrosion Science 2011,53,2080-2086), and demonstrate this film there is good Corrosion Protection.But the working (machining) efficiency of the method is lower, and the surface of preparing machinery poor-performing and being very susceptible to damage.In the same year, the method that Xu etc. utilize electroless plating and stearylmercaptan to modify prepares super-hydrophobic Ag films (Xu, W.G. on Zinc Matrix surface; Ning, T.; Yang, X.C.; Lu, S.X.AppliedSurface Science 2011,257,4801-4806); Tao etc. prepare super hydrophobic surface (Tao, N. by the method for electroless plating in zinc surface one step; Xu, W.G.; Lu, S.X.Journal of Colloid and InterfaceScience 2011,361,388-396).The working (machining) efficiency of these two kinds of methods is higher, but required reagent is expensive, and the super hydrophobic surface poor mechanical properties obtained.2015, Canadian scientist Brassard etc. utilized electrochemical deposition method to go out zinc film at depositing on surface of steel, then modified rear surface through low surface energy and presented super-hydrophobicity (Brassard, J.D.; Sarkar, D.K.; Perron, J.Audibert-Hayet, A.; Melot, D.Journal of Colloid and Interface Science 2015,447,240-247), prepared super hydrophobic surface possesses anti-freeze and antiseptic property preferably, but the associativity of the super-hydrophobic zinc film prepared of the method and matrix is poor.Therefore, use a kind of efficient, environmental protection, economic method prepares stable Zinc Matrix super-double-hydrophobic surface and just seem particularly important.
Summary of the invention
The invention provides a kind of simple efficient, economic and processing method of the super two thin zinc surface of the preparation of environmental protection, the method is first based on method for electrochemical machining, zinc surface is constructed the micro-nano coarse structure of suitable binary, and the Perfluorocaprylic Acid then by having low surface energy is modified and is obtained ultra-amphosphobic.
The technical solution used in the present invention comprises the steps:
(1) by metal zine plate cleaning oil removing, then carry out mechanical polishing, re-use deionized water ultrasonic cleaning, dry up;
(2) zine plate cleaned up to be fixed on anode clamp and as anode, will to be fixed on cathode fixture with anode graphite cake of the same area and as negative electrode; The electrolytic solution adopted is 0.01mol/L ~ 0.1mol/LNaCl and 0.01mol/L ~ 0.1mol NaNO
3mixing neutral aqueous solution;
(3) flow through the electric current of anode and cathode by adjustable DC Energy control, carry out electro-chemical machining with constant current mode, the process period of zinc surface is about 20min, and current density is 0.10A/cm
2~ 0.20A/cm
2.
(4) zine plate after electro-chemical machining is put into Perfluorocaprylic Acid ethanolic soln and carry out low surface energy modification, after taking-up, be drying to obtain super two thin zinc surface.The concentration of Perfluorocaprylic Acid ethanolic soln is more preferably greater than 0.01mol/L, and the modification time should be greater than 30min.
The present invention has the following advantages compared with existing super hydrophobic surface technology of preparing:
(1) super two thin zinc surfaces that processing method of the present invention obtains not only are greater than 160 ° to the contact angle of water droplet, and effects on surface can be lower droplets contact angle be greater than 150 °, oil droplet and water droplet are all no more than 10 ° in the roll angle of material surface, and namely surface is with the hydrophobic of excellence and oleophobic performance.
(2) super-double-hydrophobic surface prepared by has satisfactory stability in atmosphere, and place the several months in external environment after, its surperficial ultra-amphosphobic is almost unchanged.
(3) super two thin zinc surfaces that processing method of the present invention obtains have good erosion resistance, and the corrosion resistance nature of protocorm is significantly strengthened, and the placement in the sodium chloride aqueous solution of 3% one month, surface hardly corrosion phenomenon occurs.
(4) electrolytic solution used is neutral salts solution, little to the harm of environment and operator.
(5) electrolytic solution cost is low and can reuse.
Accompanying drawing explanation
Fig. 1 is the experimental installation schematic diagram of embodiment 1.
Fig. 2 is super two thin zinc surfaces prepared by embodiment 1.
Fig. 3 is the enlarged photograph of water droplet and n-Hexadecane drop in Fig. 2.
In figure: 1 direct supply, 2 anode clamps, 3 anode zine plates, 4 magnetic stirring apparatuss, 5 magnetic rotor, 6 negative electrode graphite cakes, 7 beakers, 8 cathode fixtures.
Embodiment
Embodiment 1
(1) first by the zine plate that is of a size of 40mm × 30mm, (actual finish size is 30mm × 30mm, redundance plays clamping and electric action) use washes of absolute alcohol oil removing, then mechanical polishing is carried out, remove the zone of oxidation of zinc surface, re-use ultrasonic cleaning 3min, and dry up with blower for subsequent use.
(2) zine plate cleaned up to be fixed on anode clamp and as anode, by the graphite cake that is of a size of 40mm × 30mm, (actual effective dimensions is 30mm × 30mm, redundance plays clamping and electric action) to be fixed on cathode fixture and as negative electrode, the spacing between anode and cathode is 30mm.After anode and cathode is clamping, is placed on and fills 0.05mol/L NaCl and 0.05mol/L NaNO
3in the beaker of mixed electrolytic solution, anode and cathode and adjustable DC power supply are connected.
(3) electric current flowing through anode by adjustable DC Energy control is 1.5A, and the metal of workpiece surface electrochemical dissolution will occur, and along with the carrying out of processing, workpiece surface is corroded gradually, finally obtains the zinc surface with the micro-nano coarse structure of binary.After completion of processing, by zinc surface ultrasonic cleaning in deionized water.
(4) the zinc sample with the micro-nano coarse structure of binary being put into concentration is that the Perfluorocaprylic Acid ethanolic soln of 0.02mol/L soaks 60min, 80 DEG C of baking oven inner drying 20min are put it into after taking-up, naturally cool to room temperature after taking-up, can super-double-hydrophobic surface be obtained.N-Hexadecane drop is 152 ° at the contact angle of zinc surface, and roll angle is 8 °; Water droplet is 160 ° at the contact angle of zinc surface, and roll angle is 3 °.
Claims (2)
1. prepare a processing method for super two thin zinc surface, it is characterized in that comprising the following steps:
(1) by metal zine plate cleaning oil removing, then carry out mechanical polishing, re-use deionized water ultrasonic cleaning, dry up;
(2) zine plate cleaned up to be fixed on anode clamp and as anode, will to be fixed on cathode fixture with anode graphite cake of the same area and as negative electrode; The electrolytic solution adopted is 0.01mol/L ~ 0.1mol/LNaCl and 0.01mol/L ~ 0.1mol NaNO
3mixing neutral aqueous solution;
(3) flow through the electric current of anode and cathode by adjustable DC Energy control, carry out electro-chemical machining with constant current mode, the process period of zinc surface is about 20min, and current density is 0.10A/cm
2~ 0.20A/cm
2.
(4) zine plate after electro-chemical machining is put into Perfluorocaprylic Acid ethanolic soln and carry out low surface energy modification, after taking-up, be drying to obtain super two thin zinc surface.
2. a kind of processing method preparing super two thin zinc surface according to claim 1, it is characterized in that, the concentration of Perfluorocaprylic Acid ethanolic soln is greater than 0.01mol/L, and the modification time is greater than 30min.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568330A (en) * | 2016-01-08 | 2016-05-11 | 中国石油大学(华东) | Preparing method of super-amphiphobic surface with scale preventing performance |
| CN106987875A (en) * | 2017-03-03 | 2017-07-28 | 四川农业大学 | A kind of preparation method of super-hydrophobic superoleophobic material |
| CN107190295A (en) * | 2017-07-14 | 2017-09-22 | 中国科学院宁波材料技术与工程研究所 | A kind of super-double-hydrophobic surface of conductive material and preparation method thereof |
| CN109112599A (en) * | 2018-08-22 | 2019-01-01 | 大连理工大学 | A kind of preparation method obtaining sliding porous surface on aluminum substrate |
| CN110964923A (en) * | 2019-12-24 | 2020-04-07 | 中南大学 | Device and method for deep replacement copper extraction under multi-field coupling |
| CN113430486A (en) * | 2021-06-22 | 2021-09-24 | 哈尔滨工程大学 | Liquid phase plasma electrolytic infiltration device and method |
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| CN102965720A (en) * | 2012-11-04 | 2013-03-13 | 大连理工大学 | Method for preparing aluminum-base super-amphiphobic surface |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105568330A (en) * | 2016-01-08 | 2016-05-11 | 中国石油大学(华东) | Preparing method of super-amphiphobic surface with scale preventing performance |
| CN106987875A (en) * | 2017-03-03 | 2017-07-28 | 四川农业大学 | A kind of preparation method of super-hydrophobic superoleophobic material |
| CN106987875B (en) * | 2017-03-03 | 2019-05-07 | 四川农业大学 | A kind of preparation method of super-hydrophobic-superoleophobic material |
| CN107190295A (en) * | 2017-07-14 | 2017-09-22 | 中国科学院宁波材料技术与工程研究所 | A kind of super-double-hydrophobic surface of conductive material and preparation method thereof |
| CN109112599A (en) * | 2018-08-22 | 2019-01-01 | 大连理工大学 | A kind of preparation method obtaining sliding porous surface on aluminum substrate |
| CN110964923A (en) * | 2019-12-24 | 2020-04-07 | 中南大学 | Device and method for deep replacement copper extraction under multi-field coupling |
| CN110964923B (en) * | 2019-12-24 | 2023-09-19 | 中南大学 | Device and method for extracting copper by deep replacement under multi-field coupling |
| CN113430486A (en) * | 2021-06-22 | 2021-09-24 | 哈尔滨工程大学 | Liquid phase plasma electrolytic infiltration device and method |
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