CN104911644A - Preparation method of superhydrophobic galvanizing coating on steel surface - Google Patents
Preparation method of superhydrophobic galvanizing coating on steel surface Download PDFInfo
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- CN104911644A CN104911644A CN201510178128.1A CN201510178128A CN104911644A CN 104911644 A CN104911644 A CN 104911644A CN 201510178128 A CN201510178128 A CN 201510178128A CN 104911644 A CN104911644 A CN 104911644A
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- steel
- electrodeposition
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- superhydrophobic
- galvanizing coating
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Abstract
The invention discloses a preparation method of a superhydrophobic galvanizing coating on a steel surface and belongs to the field of electrodeposition. The method is as below: first putting steel matrix into a zinc sulfate aqueous solution without leveler or brightener and conducting a two-step electrodeposition treatment: first, carrying out electrodeposition on steel matrix surface to obtain a rough structure with large size; and second, carrying out electrodeposition on the microstructure with large size to obtain a fine structure with small size, thus forming a micro-nano rough structure; and then conducting fluorination treatment on the steel sample containing galvanizing coating with micro-nano rough structure to reduce the surface energy, and obtain a superhydrophobic functional surface. The contact angle of distilled water with the functional surface exceeds 150 DEG, and a roll angle is less than 10 DEG, thereby reaching superhydrophobicity. The superhydrophobic galvanizing coating surface not only has corrosion resistance of a traditional galvanizing coating, but also has self-cleaning properties, thereby opening up a novel field of application for electrodeposition process. The method has the advantages of easy operation, low cost, no restriction in matrix shape and easiness to popularization and usage.
Description
Technical field
The present invention relates to the preparation method of super-hydrophobic zinc coating on a kind of steel surface, be specifically related to steel matrix surface two step electrodeposition process and low energy modification, and then realize the super-hydrophobicity of steel surface.
Background technology
Found by some investigators from the secret of " lotus leaf effect ", super-hydrophobicity causes the great interest of people and pays close attention to widely, and super hydrophobic surface has important effect in daily life and industrial and agricultural production, as: there are hydrophobic tableware, textiles, ship, solar panel etc.For this reason, increasing people starts to probe into various method to prepare super hydrophobic surface, and find that the method key factor preparing super hydrophobic surface is two kinds: a kind of is the roughness improving hydrophobic material surface, another kind carries out low energy modification to the surface with coarse structure, wherein, the latter is the method commonly used the most.
Have at present much about the report of method for preparing super-hydrophobic surface.But the matrix that most methods relates to is a few materials such as cotton fibre, glass, silicon chip, Mg-based hydrogen storage, Al and Alalloy, and in steel matrix, the preparation of super hydrophobic surface is relatively less.In addition, many preparation methods, as orientation etching, gas/liquid deposits mutually, mould plate technique, collosol and gel etc., and there is the problems such as preparation condition harshness, required cost are higher, the popularization and the big area that limit these methods use.
Traditional electrodeposition technology is mostly the outward appearance improving body material, and give the physical and chemical performance etc. that material surface is certain, the surface formed mostly needs smooth.Super hydrophobic surface needs micro-nano coarse structure usually, so, do not add smoothing agent and brightening agent in electroplate liquid and contribute on the contrary forming fine coarse structure.In addition, different electro-deposition process parameters can obtain different surface micro-structures.Zinc, usually used as the anodic coating of some metallic substance, provides mechanical protection and electro-chemical protection to matrix metal.If prepare super hydrophobic surface on zinc coating, the super hydrophobic surface obtained not only has solidity to corrosion, also has certain self-cleaning property simultaneously, can expand the range of application of electrolytic coating further.Nano-plating ([day] ， Du side rut, Chemical Industry Press, 2006,9) reports the pattern of Several Thiourea Derivatives on Zinc Plate Surface under different galvanic deposit parameter, and draws: electrodeposition time extends (coating is thicker), and the micro-bulge of coating is thicker.Therefore, realize micron and nanometer composite structure with two step galvanic deposit: the first step adopts the galvanic deposit of long period to form larger-size microstructure, second step adopts the galvanic deposit of short period to form the less microstructure of size in original larger-size microstructure.
The present invention by simple two step electrodeposition process at steel matrix surface construction micro nano structure, and in conjunction with low energy modify, formed super hydrophobic surface.This surface not only has solidity to corrosion, also has certain self-cleaning property simultaneously, and technological process is simple, and cost is low, and practicality is comparatively strong, suits large area to popularize.
Summary of the invention
The object of the present invention is to provide the preparation method of super-hydrophobic zinc coating on a kind of simple steel surface.
Common realization is modified by two step galvanic deposit zinc layers and low energy in super hydrophobic functional surface in steel matrix of the present invention.
A preparation method for super-hydrophobic zinc coating on steel surface, is characterized in that the method comprises following step successively:
1) use the metallographic liquid honing steel curved beam of 600#-2000# surface to smooth successively, to improve the bonding force on galvanic deposit zinc layers and steel matrix surface, ultrasonic cleaning is also dry, and zinc sample also uses the metallographic liquid honing of 600#-2000# surface to smooth successively simultaneously;
2) by steel curved beam good for above-mentioned polishing oil removing 15min (60 DEG C) in alkaline wash, then acid-wash activation 10s (room temperature) in pickle solution, rinse and drying with a large amount of clear water fast;
3) steel curved beam of above-mentioned acid-wash activation is negative electrode, and the pure zine plate of having polished is anode, carries out two step galvanic deposit in zinc sulfate solution, obtains micro-nano coarse structure surface, sees Fig. 1;
4) steel curved beam containing coarse structure zinc coating is put in Perfluorocaprylic Acid ethanol solution soak certain hour, put into culture dish after taking-up, dry at ambient temperature and obtain super hydrophobic surface.
5) step 1) in steel curved beam used be X90 pipe line steel;
6) step 2) alkaline wash used is NaOH (30g/L), Na
2cO
3(20g/L), Na
3pO
4(20g/L) and Na
2siO
3(10g/L) mixed aqueous solution formed; Pickle solution to be volume fraction be 10% H
2sO
4the aqueous solution;
7) step 3) described in electroplate liquid be the ZnSO of 180-260g/L
4﹒ 7H
2(volume fraction is the H of 10% to the O aqueous solution
2sO
4regulate the pH ≈ 4 of electroplate liquid, not containing smoothing agent and brightening agent);
8) step 3) described in electroplating technological parameter as follows: temperature of electroplating solution is 15-75 DEG C; The current density of the first step galvanic deposit is 2-6A/dm
2, electrodeposition time is 15-40min; After arriving the time set, fast electric current is adjusted to 9-11A/dm
2carry out second step galvanic deposit, electrodeposition time is 1-20min; Reaction terminates a large amount of clear water of rear quick use and rinses removal remained on surface liquid and drying;
9) step 5) described in the concentration of Perfluorocaprylic Acid dehydrated alcohol be 0.005-0.02mol/L, soak time is 3-13 days.
The present invention forms larger-size coarse structure through the first step galvanic deposit at steel surface, then on original microstructure basis, forms the relatively little coarse structure of size through second step galvanic deposit, thus forms micron and nanometer composite structure; Finally carry out low energy modification with Perfluorocaprylic Acid ethanol solution, obtain super hydrophobic surface.Distilled water is dripped to the steel surface processed and carry out contact angle determination, this surface is greater than 150 ° with the contact angle of water.
The present invention has the following advantages:
1) method used is traditional electrodeposition technology, and required equipment is cheap, does not have particular requirement to the shape and size of sample;
2) raw material is cheaply easy to get.Take steel as raw material, modify through two step galvanic deposit and low energy, prepare super hydrophobic surface;
3) all technological processs are carried out all in the solution, and simple to operate, suit large area to popularize;
4) super hydrophobic surface obtained by also extends to other metallic surfaces, and thus the scope of application comparatively extensively, in industry and life has broad application prospects.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described.
Fig. 1 is the SEM photo of the super-hydrophobic zinc coating of X90 pipe line steel in the embodiment of the present invention;
Fig. 2 is the contact angle of water droplet on the super-hydrophobic Several Thiourea Derivatives on Zinc Plate Surface of X90 pipe line steel, and size is 152.36 °.
Embodiment
Below in conjunction with embodiment, the present invention is described further, the following stated, only to preferred embodiment of the present invention, not do other forms of restriction to the present invention, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed to the Equivalent embodiments of equal change.Everyly do not depart from the present invention program's content, according to technical spirit of the present invention to any simple modification made for any of the above embodiments or equivalent variations, all drop in protection scope of the present invention.
A preparation method for super-hydrophobic zinc coating on steel surface, is specifically completed by following step:
1, with metallographic liquid honing smooth X90 pipe line steel and the pure zine plate specimen surface of 600#-2000#, then acetone, dehydrated alcohol, distilled water ultrasonic cleaning also drying in 5 minutes respectively;
2, with insulation tape stick do not need electroplate pipe line steel specimen surface, then steel curved beam is carried out successively alkali cleaning oil removing 15min (60 DEG C, the Na of NaOH, 20g/L of 30g/L
2cO
3, 20g/L Na
3pO
4, 10g/L Na
2siO
3composition mixed aqueous solution), (room temperature, volume fraction is the H of 10% to acid-wash activation 10s
2sO
4), wash and rapid drying with a large amount of clear water after taking-up;
3, the above-mentioned pipe line steel sample handled well is negative electrode, and pure zine plate is anode, at the ZnSO of 240g/L
4﹒ 7H
2in the O aqueous solution, (volume fraction is the H of 10%
2sO
4regulate the pH ≈ 4 of electroplate liquid) to electroplate, temperature of electroplating solution is 25 DEG C, and current density is 4A/dm
2, electrodeposition time is 30min, after arriving the time set, fast electric current is adjusted to 9A/dm
2carry out second step galvanic deposit, electrodeposition time is 3min; Reaction terminates a large amount of clear water of rear quick use and rinses removal remained on surface liquid and drying; Its surface topography presents micro-nano coarse structure, sees Fig. 1;
4, pipe line steel sample step 3 obtained is put in the Perfluorocaprylic Acid ethanol solution of 0.01mol/L and is soaked 11 days, puts into culture dish, dry at ambient temperature and obtain super hydrophobic surface after taking-up.After measured, the static contact angle of this surface and distilled water is 152.36 °, sees Fig. 2, and roll angle is less than 10 °.
Claims (4)
1. the preparation method of super-hydrophobic zinc coating on steel surface, is characterized in that the method comprises following two steps successively: 1) carry out two step electrodeposition process to steel surface, steel surface obtains the zinc coating of micro-nano coarse structure; 2) sample surface being contained micro-nano coarse structure zinc coating carries out low energy modification.
2. preparation method according to claim 1, two step electrodeposition process is characterized in that: the steel polished smooth successively after alkali cleaning, pickling as negative electrode, the pure zine plate polished smooth as anode, at the ZnSO of 180-260g/L
4﹒ 7H
2(volume fraction is the H of 10% to the O aqueous solution
2sO
4regulate the pH ≈ 4 of electroplate liquid) in carry out two step electrodeposition process, reaction terminates a large amount of clear water of rear use and rinses and remove remained on surface liquid and dry.
3. method according to claim 2, is characterized in that: temperature of electroplating solution is 15-75 DEG C; The current density of the first step galvanic deposit is 2-6A/dm
2, electrodeposition time is 15-40min; After arriving the time set, fast electric current is adjusted to 7-11A/dm
2carry out second step galvanic deposit, electroplating time is 1-20min; Reaction terminates a large amount of clear water of rear quick use and rinses removal remained on surface liquid and drying.
4. preparation method according to claim 1, the feature that low energy is modified is: the steel curved beam obtained containing zinc coating is put in 0.005-0.02mol/L Perfluorocaprylic Acid ethanol solution and soaked 3-13 days, put into after taking-up in culture dish, dry at ambient temperature and obtain super hydrophobic surface.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256342A (en) * | 2015-10-19 | 2016-01-20 | 华南理工大学 | Copper-based super-hydrophobic surface and preparation method thereof |
| CN105386090A (en) * | 2015-11-09 | 2016-03-09 | 广东工业大学 | Method for manufacturing ultra-oleophobic metal surface with recessed micropores |
| CN105586616A (en) * | 2016-01-18 | 2016-05-18 | 苏州市华婷特种电镀有限公司 | Process for pretreating part to be plated in electroplating process |
| CN107675223A (en) * | 2017-09-19 | 2018-02-09 | 南京理工大学 | The method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template |
| CN108301024A (en) * | 2018-02-28 | 2018-07-20 | 北京科技大学 | A method of preparing surface hydrophobicity structure coating |
| CN110029380A (en) * | 2019-04-11 | 2019-07-19 | 太原理工大学 | A kind of preparation method of carbon steel surface super hydrophobic zinc-iron composite coating |
| CN110453257A (en) * | 2019-08-16 | 2019-11-15 | 山东科技大学 | A kind of super-hydrophobic Zn-PTFE composite electrodeposition layer and preparation method |
| CN111534841A (en) * | 2020-04-14 | 2020-08-14 | 北京航空航天大学 | Reversible wetting of electric field induced liquid metal on metal substrate and application |
| CN113215627A (en) * | 2021-05-10 | 2021-08-06 | 中国石油大学(华东) | Method for preparing super-hydrophobic zinc sulfide coating on surface of stainless steel |
| CN114807947A (en) * | 2022-05-23 | 2022-07-29 | 四川晟实科技有限公司 | Preparation method of stainless steel hydrophobic wear-resistant nano-film for organic analytical instrument |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105256342A (en) * | 2015-10-19 | 2016-01-20 | 华南理工大学 | Copper-based super-hydrophobic surface and preparation method thereof |
| CN105386090A (en) * | 2015-11-09 | 2016-03-09 | 广东工业大学 | Method for manufacturing ultra-oleophobic metal surface with recessed micropores |
| CN105586616A (en) * | 2016-01-18 | 2016-05-18 | 苏州市华婷特种电镀有限公司 | Process for pretreating part to be plated in electroplating process |
| CN107675223A (en) * | 2017-09-19 | 2018-02-09 | 南京理工大学 | The method that petal-shaped zinc super hydrophobic surface is prepared using plant leaf blade template |
| CN108301024A (en) * | 2018-02-28 | 2018-07-20 | 北京科技大学 | A method of preparing surface hydrophobicity structure coating |
| CN110029380B (en) * | 2019-04-11 | 2020-05-01 | 太原理工大学 | Preparation method of super-hydrophobic zinc-iron composite coating on surface of carbon steel |
| CN110029380A (en) * | 2019-04-11 | 2019-07-19 | 太原理工大学 | A kind of preparation method of carbon steel surface super hydrophobic zinc-iron composite coating |
| CN110453257A (en) * | 2019-08-16 | 2019-11-15 | 山东科技大学 | A kind of super-hydrophobic Zn-PTFE composite electrodeposition layer and preparation method |
| CN111534841A (en) * | 2020-04-14 | 2020-08-14 | 北京航空航天大学 | Reversible wetting of electric field induced liquid metal on metal substrate and application |
| CN111534841B (en) * | 2020-04-14 | 2021-07-30 | 北京航空航天大学 | Reversible wetting of electric field induced liquid metal on metal substrate and application |
| CN113215627A (en) * | 2021-05-10 | 2021-08-06 | 中国石油大学(华东) | Method for preparing super-hydrophobic zinc sulfide coating on surface of stainless steel |
| CN114807947A (en) * | 2022-05-23 | 2022-07-29 | 四川晟实科技有限公司 | Preparation method of stainless steel hydrophobic wear-resistant nano-film for organic analytical instrument |
| CN114807947B (en) * | 2022-05-23 | 2024-04-12 | 四川晟实科技有限公司 | Preparation method of stainless steel hydrophobic wear-resistant nano film for organic analytical instrument |
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