CN101665968B - Process method for preparing ultra-hydrophobic surface by electrochemical method - Google Patents
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Abstract
The invention discloses a process method for preparing an ultra-hydrophobic surface by the electrochemical method. The process adopts two processing steps: forming the micro nanometer double-structure rough surface by first electrochemical etching and then oxalic acid anodic oxidation; and preparing the ultra-hydrophobic surface by modifying the surface with fluorosilane. The method is simple and practical, uses mature electrochemical etching and anodic oxidation technology, allows for easy mass production and avoids environmental pollution.
Description
Technical field
The invention belongs to metal finishing and modification technology field, particularly a kind of preparation method of super hydrophobic surface.
Background technology
Wetting property is a critical nature of solid surface, and its extensive studies application value is all arranged in a lot of fields.Wherein, solid surface comprises hydrophobic and wetting ability research to the wetting property research of water, and particularly super-hydrophobicity research has caused international and domestic investigator's extensive concern and interest in recent years.At present, there have been many reports to show and how realized superhydrophobic characteristic on various surfaces.In the middle of these methods, the thinking of realization mainly both ways: (1) makes originally that hydrophobic surface has suitable coarse structure; (2) has the finishing low surface energy material of coarse structure, as silicon fluoride etc.Become one of the focus of research work and emphasis of theoretical model research and how to prepare the microtexture that can be fit to produce super hydrophobic surface.1997, Barthllot finds lotus leaf surface and rough, exist nanometer and micron-sized dual microtexture, be the surperficial micrometer structure of mastoid process formation and the nanostructure that wax crystalls forms, the diameter of mastoid process is 5～15 μ m, the wax crystalls characteristic dimension is 20nm～500nm, and thinks that this is the not basic reason of sticking water of lotus leaf, and proposes " lotus leaf effect (Lotus Effect) " principle according to this phenomenon.People such as Jiang Lei are the basic reasons that causes surperficial strong-hydrophobicity according to the hierarchical structure that lotus leaf structural principle proposition micrometer structure combines with nanostructure also.
In the middle of the preparation method of numerous micro-nano superhydrophobic surface structures, comprise photolithography, micromachined method, distillation drilling method, template extrusion molding, chemical Vapor deposition process, plasma surface etching method or the like.The equipment that these methods have or needs are expensive, the course of processing of the needs complexity that has, the repeatability that has is not high or be difficult to large-area preparation, all exists the defective that some are difficult to overcome in a word, thereby is unfavorable for the real suitability for industrialized production and the needs of practical application.
The engineering metal material is in navigation, space flight, have a wide range of applications in pipeline transportation and other the many fields, the shell and the steamer that can be used as radar and aircraft as aluminium and alloy thereof, the cabin bodies of submarine etc., how constructing super hydrophobic surface on engineering metal has become a very promising research focus in recent years.In recent years, some occur and prepared the method for bionical super hydrophobic surface in the metallic surface, as Qian Baitai, people such as Shen Ziqiu utilize the dislocation corrosion agent at aluminium, copper, and the zinc surface corrosion is modified with silicon fluoride then, super hydrophobic surface (BaitaiQian, Ziqiu Shen, Langmuir2005 have been obtained, 21,9007-9009).And for example bending people such as Meng Nan has reported and utilizes chemical corrosion method to be modified at stainless steel in conjunction with the low surface energy material, copper alloy, super hydrophobic surface (Mengnan Qu, Bingwu Zhang, Shiyong Song have been prepared on the titanium alloy with micro nano structure, Li Chen, JunyanZhang, Xiaoping Cao, Adv.Funct.Mater.2007,17,593-596).The method of this chemical corrosion all must be used the material that some have severe corrosive; as hydrofluoric acid; nitric acid; hydrogen peroxide and destructive strong acid or strong alkaline substance or their mixing solutions or the like; the a large amount of uses of these materials will inevitably cause environmental pollution even threat to life safety; also can improve the cost of pollutent aftertreatment and FUTURE ENVIRONMENT protection in addition virtually, also will bring unfavorable factor simultaneously the security of scale production.
Summary of the invention
The object of the present invention is to provide a kind of process method for preparing ultra-hydrophobic surface by electrochemical method of using.
The present invention is by two step treatment process methods, and promptly first electrochemical etching is constructed micro-nano dual structure uneven surface by oxalic acid anodizing again, modifies by surperficial silicon fluoride then to prepare super hydrophobic surface.
The present invention utilizes the electrolyte solution of simple and practical and environmental protection in two steps aluminium and alloy surface thereof to be carried out etching respectively, produce the shape characteristic of different roughness respectively, promptly utilize the sodium chloride solution etching to produce the platform-like projection of 5～15 μ m, oxalic acid anodizing then produces upright nano wire or nano level projection, thereby constitutes the microtexture of micro-nano pair of yardstick.Such architecture basics is added the low surface energy modification just can produce the super-hydrophobic effect of similar lotus leaf, thereby gives the high-performance of aluminium and alloy surface " automatically cleaning " thereof.
A kind of process method for preparing ultra-hydrophobic surface by electrochemical method of using is characterized in that this method may further comprise the steps:
A, employing sodium chloride solution are made ionogen, adopt stereotype to be the reaction negative electrode, and aluminium flake or aluminium alloy plate are anode, are to carry out reactive ion etching fine aluminium or aluminium alloy under the 4-10V room temperature at voltage, obtain having the aluminium and the alloy surface thereof of micron order uneven surface;
B, adopt oxalic acid solution to make ionogen, negative electrode is a stereotype, has the aluminium and the alloy surface thereof of micron order uneven surface in the oxidation voltage of 50-80V and 10 ℃ of following anodic oxidations, obtains having the aluminum or aluminum alloy on micro-nano dual microtexture surface;
C, the aluminum or aluminum alloy that will have a micro-nano dual microtexture surface soak in the ethanolic soln of ten difluoro heptyl propyl trimethoxy silicanes, and be at room temperature dry, obtains super hydrophobic surface through after the heat treated again.
We can obtain the vesicular uneven surface by the A step, and about 5 microns of hole size is the platform-like projection of about 10 μ m between the hole.
We can produce the nanometer projection of axial alumina nanowires or the 50～100nm of 50～100nm by the B step.
Method of the present invention is not used to comprise strong acid, deep-etching and dangerous reagent; Can produce very significantly nanostructure at aluminium and aluminum alloy surface by above method.
Aluminium of the present invention and aluminium alloy super hydrophobic surface have very significantly hierarchy, and its micron pattern is the projection about yardstick 5-10 micron, and nanotopography is axial nano wire (aluminium substrate) or the nano-dotted projection (aluminium alloy) on the micron projection.
Super hydrophobic surface of the present invention has very excellent hydrophobicity energy, and (the aluminium super hydrophobic surface: water contact angle is 165.4 not only to have the static contact angle of very high water; Aluminium alloy super hydrophobic surface contact angle is 162.6 °), and its roll angle of what is more important very little (all less than 2 °).This makes water droplet be very easy to roll on its surface, thereby has excellent automatically cleaning characteristic, long-term the pollution-free of surface that keep.
Super hydrophobic surface of the present invention has good stability, with its its surface super-hydrophobic no change after placing the several months under air and the room temperature condition.
Aluminium of the present invention and alloy super hydrophobic surface thereof have micro-nano pair of microcosmic composite structure of similar lotus leaf surface, and this is the architecture basics that constitutes its ultra-hydrophobicity, modify in conjunction with the low surface energy material more just can have superhydrophobic characteristic.
The present invention and existing super-hydrophobic technology of preparing have following advantage:
(1) preparation method is simple and practical, need not cost and complex equipment, and large-area preparation very easily.
(2) have quite low roll angle (≤2 °), water droplet very easily rolls on this surface, and ultralow roll angle is particularly important to surperficial ultra-hydrophobicity.
(3) aluminium and alloy thereof be in aviation, navigation, and every field such as national defence and air conditioner refrigerating industry all are important engineering metallic substance very, thereby this method has broad application prospects in above-mentioned every field.
(4) be not only applicable to plane engineering metal material surface and be applicable to the crooked pipeline inwall, thereby make it aspect pipeline transportation of liquid and the microfluid research huge application potential arranged.
(5) need not strong acid and strong base and acid with strong oxidizing property, thereby improved the security of producing greatly, and produce discharge and can not pollute, help in the industrial production environment protection to environment.
Embodiment
Embodiment 1
The orthogonal aluminium flake (purity is 99.9%) of 6cm * 2cm was used ethanol and acetone ultrasonic cleaning respectively 10 minutes, and rinse well with deionized water, with the aluminium flake electrochemical etching in the sodium chloride solution of 0.06M after handling, with the stereotype is negative electrode, aluminium flake is an anode, volts DS is 4V, and temperature is 22 ℃, reacts 3 hours.After the aluminium flake taking-up, cleaned 10 minutes in deionized water for ultrasonic, remove the alumina particle of surface attachment.Then this aluminium flake is carried out anodic oxidation in the oxalic acid aqueous solution of 0.3M, it is 60 volts that institute adds volts DS, is 10 ℃ with thermostatic bath control reaction soln temperature, reacts 2 hours, has obtained having the micro-nano dual structure that is similar to lotus leaf surface on the aluminium flake surface.Afterwards this surface being carried out the low surface energy material modifies: this aluminium flake was soaked 20 minutes in ethanolic soln (1wt%) lining of ten pre-configured difluoro heptyl propyl trimethoxy silicanes, then 110 ℃ of thermal treatments 2 hours, naturally cooling, the contact angle that detects surface and water is 165.4 °, water droplet rolls very easily in the above, roll angle≤2 °.
Embodiment 2
The orthogonal aluminum alloy sheet of 6cm * 2cm (is contained minor amount of silicon, magnesium) use ethanol and acetone ultrasonic cleaning 10 minutes respectively, and rinse well with deionized water, with the aluminum alloy sheet electrochemical etching in the sodium chloride solution of 0.08M after handling, with the stereotype is negative electrode, and aluminium flake is an anode, and volts DS is 8V, temperature is 22 ℃, reacts 2.5 hours.After the aluminum alloy sheet taking-up, cleaned 10 minutes in deionized water for ultrasonic.Then this aluminum alloy sheet is carried out anodic oxidation in the oxalic acid solution of 0.3M, it is 75V that institute adds volts DS, with thermostatic bath control reaction soln temperature is 10 ℃, reacts 2 hours, has obtained having the micro-nano dual structure that is similar to lotus leaf surface on the aluminum alloy sheet surface.Afterwards this surface being carried out the low surface energy material modifies: this aluminum alloy sheet was soaked 1 hour in ethanolic soln (1wt%) lining of ten pre-configured difluoro heptyl propyl trimethoxy silicanes, then 120 ℃ of thermal treatments 1 hour, naturally cooling, the contact angle that detects surface and water is 162.6 °, water droplet rolls very easily in the above, roll angle≤2 °.
Claims (1)
1. use process method for preparing ultra-hydrophobic surface by electrochemical method for one kind, it is characterized in that this method may further comprise the steps:
A, employing sodium chloride solution are made ionogen, adopt stereotype to be the reaction negative electrode, and aluminium flake or aluminium alloy plate are anode, are to carry out the reactive ion etching aluminum or aluminum alloy under the 4-10V room temperature at voltage, obtain having the aluminium and the alloy surface thereof of micron order uneven surface;
B, adopt oxalic acid solution to make ionogen, negative electrode is a stereotype, has the aluminium and the alloy surface thereof of micron order uneven surface in the oxidation voltage of 50-80V and 10 ℃ of following anodic oxidations, obtains having the aluminum or aluminum alloy on micro-nano dual microtexture surface;
C, the aluminum or aluminum alloy that will have a micro-nano dual microtexture surface soak in the ethanolic soln of ten difluoro heptyl propyl trimethoxy silicanes, and be at room temperature dry, obtains super hydrophobic surface through after the heat treated again.
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| KR101569460B1 (en) | 2013-02-08 | 2015-11-16 | 국민대학교 산학협력단 | superamphiphobic structure and method of manufacturing the same |
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