CN105063738B - Preparation method of durable underwater ultra oleophobic surface of titanium alloy matrix - Google Patents
Preparation method of durable underwater ultra oleophobic surface of titanium alloy matrix Download PDFInfo
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Abstract
The invention discloses a preparation method of a durable underwater ultra oleophobic surface of a titanium alloy matrix, and belongs to the technical field of surface treatments of metallic materials. The preparation method comprises the following steps: performing electro chemical etching on the surface of a titanium alloy piece under a constant current density in a neutral electrolyte consisting of NaCl and H2O2 so as to prepare micron-grade concave pits and a cavity structure; after the electro chemical etching is completed, putting the titanium alloy piece into deionized water so as to perform ultrasonic cleaning; and taking out the titanium alloy piece after the ultrasonic cleaning, and placing the taken titanium alloy piece into water so as to obtain the underwater ultra oleophobic surface of the titanium alloy matrix. A contact angle between the prepared underwater ultra oleophobic surface on the titanium alloy matrix and dichloromethane in the water is 158.9 degrees, a rolling angle is smaller than 10 degrees, and the surface has good characteristics of underwater durability and corrosion resistance. The method is simple in technology, low in cost and pollution-free to environment and can be used for underwater oil pollution resistance and underwater corrosion resistance of the titanium alloy surface.
Description
Technical field
The present invention relates to a kind of preparation method on titanium alloy substrate durability superoleophobic surface under water, belongs to metal material table
Face processing technology field.
Background technology
Gu under water superoleophobic surface is referred in oil/water/three-phase system, oil droplet contact angle thereon is more than 150 degree, rolling
Surface of the dynamic angle less than 10 degree.Under normal circumstances, common superoleophobic surface does not have superoleophobic characteristic under water, once it is placed at
In water, the surface will lose superoleophobic property, become oil-wetted surface.Under water superoleophobic surface is because with automatically cleaning in water, grease proofing
The characteristic such as dirty, corrosion-resistant, therefore compared with common superoleophobic surface, under water superoleophobic surface has been expanded in ship in superoleophobic surface
The application in the fields such as oceangoing ship, oceanographic equipment oil-stain-preventing, oil-water separation.
In general, two key factors for preparing superoleophobic surface under water are hydrophilic chemical composition and micro/nano level
Coarse structure, therefore, in atmosphere the surface with Superhydrophilic by construct coarse structure can be used for superoleophobic table under water
The preparation in face.The patent application of Application No. 200710303779.4 discloses a kind of underwater ultra-oleophobic polyalcohol membrane and its preparation
Method, using fish scale as template, by the monomer solution in-situ polymerization of polydimethylsiloxane and polymer successively figuration, obtains
Polymeric film with fish scale structure, the composite membrane is more than 150 degree to the contact angle of oil under water.Application No.
200910012618.9 patent application discloses a kind of using two kinds of technologies of self assembly and heterogeneous nucleation, first soaks glass substrate
Bubble is in the acetic acid solution of shitosan, then is immersed in the sodium hydroxide solution of nano silicon, obtained rough surface knot
Structure is both greater than 170 degree with the contact angle of hexadecane, chloroform under water.In addition Application No. 201210230606.5,
201310027762.6,201310309217.6,201310311255.5,201410160316.7,201410604794.2
Patent application also discloses that some methods for preparing superoleophobic surface under water.From the point of view of comprehensive these methods, superoleophobic surface under water
Preparation be largely focused on glass or silicon substrate and build coarse structure using hydrophilic high molecular polymer, and in metal
The method that superoleophobic surface under water is prepared on matrix is less.
Li etc. sprays one layer of suspension containing ZnO nano granule using spraying process on stainless (steel) wire matrix, dries in the air under room temperature
After dry, the surface of acquisition is under water 155 degree to the contact angle of chloroform, and roll angle is 10 degree（J Li n, L Yan, W
Li, J Li, F Zha, Z Lei, Materials Letters, 2015, 153, 62.）.Nishimoto etc. is by titanium sheet
It is placed on the 0.3M NH containing 3vol% deionized waters4Anodic oxidation 20 minutes is carried out in F solution, is then calcined 1 hour, acquisition
Surface is more than 165 degree to the contact angle of hexadecane under water（S Nishimoto, Y Sawai, Y Kameshima, M
Miyake, Chemistry Letters, 2014, 43, 518.）.And the group is further carried out using acid etch to titanium sheet
Corrosion, the rough surface of acquisition is all higher than 150 degree to the contact angle of hexadecane, dodecane, heptane under water（S Nishimoto,
Y Sawai, Y Kameshima, M Miyake, Colloids and Surfaces A: Physicochemical and
Engineering Aspects, 2015, 464, 33.）.The obtained surface on metallic matrix of said method has good
Characteristic superoleophobic under water, but come with some shortcomings, such as the chemical reagent environmental pollution that uses, need specific apparatus, right
Operator are harmful and preparation time length etc..Therefore, a kind of process is simple, low cost, the side of environmentally safe are studied
Method, has important practical significance for superoleophobic surface under water is prepared on titanium alloy substrate.
The content of the invention
The technical problem to be solved is to provide a kind of process is simple, low cost, the titanium of environmentally safe and closes
The preparation method on auri body durability superoleophobic surface under water.The preparation method is carved by electrochemical etching on titanium alloy substrate
Lose micro/nano level coarse structure to obtain superoleophobic surface under water.
The technical solution used in the present invention is：A kind of preparation method on titanium alloy substrate durability superoleophobic surface under water,
Using following preparation steps：
（1）With the titanium alloy piece of No. 1500 abrasive paper for metallograph polishing 20mm × 30mm × 3mm（Ti-6Al-4V）, place into third
It is cleaned by ultrasonic 3min in ketone, dehydrated alcohol, deionized water successively and removes surface and oil contaminant；
（2）Titanium alloy piece is placed as anode, graphite cake as negative electrode, Parallel Symmetric, and spacing is 15mm, anode and negative electrode
Actually active size is 20mm × 20mm, and remainder is used for clamping and conduction, from the NaCl and 0.5mol/ of 0.5mol/L
The H of L2O2Mixed solution does electrolyte；It is connected with DC source by wire, titanium alloy piece connects positive pole, graphite cake connects negative pole,
Electrochemical etching is carried out to titanium alloy piece surface under constant current density, under room temperature, electrolyte is in all the time magnetic stirring, stirs
It is 700r/min to mix speed, and etching electric current density is fixed as 1A/cm2, the time is 10-30min；After the completion of etching, by titanium alloy
Piece is put in deionized water and is cleaned by ultrasonic, and taking-up just obtains titanium alloy substrate superoleophobic surface under water after drying up.
The invention has the beneficial effects as follows：Compared with existing the metallic matrix under water technology of preparing on superoleophobic surface, have
Advantages below：
（1）Using NaCl and H2O2It is neutral reagent, low cost, environmentally safe, and to the danger of operator
Little, the economical and efficient of evil；
（2）Operation is simple, processes the micro-nano coarse knot that just can be obtained needed for superoleophobic surface under water for 15 minutes
Structure, efficiency high；
（3）Obtained surface superoleophobic under water is to the contact angle of dichloromethane in water on titanium alloy substrate
158.9 degree, roll angle is less than 10 degree, and the surface has good durability under water and corrosion resistance characteristic, can be used for titanium alloy table
The oil-stain-preventing under water in face and anticorrosion；
（4）Under water superoleophobic surface not only still has after 12 weeks with ultraviolet light irradiation in atmosphere the titanium alloy substrate for obtaining
Have a good durability of superoleophobic property under water, and soak in 3.5 wt.% NaCl solutions after two months the surface in water
Still keep superoleophobic characteristic.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of obtained titanium alloy superoleophobic 5000 times of surface amplification under water.
Fig. 2 is the scanning electron microscope (SEM) photograph of obtained titanium alloy superoleophobic 20,000 times of surface amplification under water.
Fig. 3 is obtained titanium alloy hydrophilic schematic diagram in the air on superoleophobic surface under water.
Fig. 4 is the oleophobic schematic diagram under water on obtained titanium alloy superoleophobic surface under water.
Fig. 5 is the Taylor roughness schematic diagrams on obtained titanium alloy superoleophobic surface under water.
Specific embodiment
Embodiment 1
（1）Pretreating process：Titanium alloy piece (20mm × 30mm × 3mm) is polished with No. 1500 abrasive paper for metallograph, Ran Houyi
Secondary being put in acetone, dehydrated alcohol, deionized water is cleaned by ultrasonic 3min；
（2）Electrochemical etching：Using the titanium alloy piece of pretreatment as anode, there is graphite of the same area with titanium alloy piece
Plate is used as negative electrode, wherein actually active size（Etch areas）For 20mm × 20mm, remainder is for clamping and conduction, and two is electric
Pole Parallel Symmetric is placed, and anode is connected by wire with DC power anode, and negative electrode is connected with negative pole, by two electrodes be put into by
0.5mol/L NaCl and 0.5mol/L H2O2In the mixing neutral electrolyte of composition, switch on power and proceed by electrochemical etching,
Etching constant current density is in 1A/cm2, etch period is 15min, and electrolyte is in all the time magnetic stirring in etching process
（Mixing speed is 700r/min）, processing temperature is room temperature, after the completion of electrochemical etching, titanium alloy piece is put in deionized water
It is cleaned by ultrasonic, superoleophobic surface under water is obtained by drying up after taking-up.
Using above-mentioned technical scheme, the electron scanning micrograph on the titanium alloy of acquisition superoleophobic surface under water is for example attached
Shown in Fig. 1 and 2, there is a large amount of irregular pits and cavity structure in surface, and size is 1-3 μm, on micron scale construction also
There are concave surface and raised structures, size is between 100-500nm.The surface roughness Ra is 17.101 μm.Accompanying drawing 3 is in air
Middle water drippage static contact angle picture on a surface, water droplet contact angle thereon is 0 degree.Accompanying drawing 4 is the oil droplet in water
The static contact angle picture for falling on a surface, to the contact angle of dichloromethane is 158.9 degree in water, and roll angle is 6.4 degree.
Accompanying drawing 5 is the roughness schematic diagram on the superoleophobic surface under water of titanium alloy obtained in embodiment 1.
Claims (1)
1. the preparation method on a kind of titanium alloy substrate durability superoleophobic surface under water, it is characterised in that：Walked using following preparation
Suddenly：
（1）Polished with No. 1500 abrasive paper for metallograph the titanium alloy piece of 20mm × 30mm × 3mm, place into acetone, dehydrated alcohol, go from
It is cleaned by ultrasonic 3min in sub- water successively and removes surface and oil contaminant；
（2）Titanium alloy piece is placed as anode, graphite cake as negative electrode, Parallel Symmetric, and spacing is 15mm, anode and negative electrode reality
Effective dimensions is 20mm × 20mm, remainder is used for clamping and conduction, from the NaCl and 0.5mol/L of 0.5mol/L
H2O2Mixed solution does electrolyte；It is connected with DC source by wire, titanium alloy piece connects positive pole, graphite cake connects negative pole, constant
Electrochemical etching is carried out to titanium alloy piece surface under electric current density, under room temperature, electrolyte is in all the time magnetic stirring, stirring speed
Spend for 700r/min, etching electric current density is fixed as 1A/cm2, the time is 10-30min；After the completion of etching, titanium alloy piece is put
Enter in deionized water and be cleaned by ultrasonic, taking-up just obtains titanium alloy substrate superoleophobic surface under water after drying up.
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| CN106271419A (en) * | 2016-08-26 | 2017-01-04 | 长春理工大学 | The most superoleophobic titanium alloy and the preparation method of aluminum alloy surface |
| CN110102450B (en) * | 2019-05-17 | 2021-08-31 | 哈尔滨工业大学 | Nano metal oxide array with underwater super-oleophobic and oleophilic reversible conversion functions and preparation method thereof |
| CN114752990A (en) * | 2022-03-26 | 2022-07-15 | 四川轻化工大学 | Metal-based nest type micro-structure super-hydrophobic surface and preparation method and application thereof |
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| JPH06306620A (en) * | 1993-04-21 | 1994-11-01 | Nkk Corp | Plating pretreatment of titanium material and method for plating titanium material |
| CN101748461B (en) * | 2008-12-02 | 2011-10-19 | 中国科学院兰州化学物理研究所 | Super-hydrophobic and super-oleophobic surface preparation technology |
| CN102021628A (en) * | 2009-09-11 | 2011-04-20 | 中国科学院兰州化学物理研究所 | Method for preparing metal titanium or titanium alloy super-oleophobic surface |
| CN103100239B (en) * | 2013-01-04 | 2016-03-09 | 中国科学院苏州纳米技术与纳米仿生研究所 | Tool super hydrophilic/the separation nethike embrane of super oleophobic property, its preparation method and application under water |
| CN103849916B (en) * | 2014-03-03 | 2016-04-13 | 宝鸡三盛稀有金属科技有限公司 | A kind of micro-arc oxidation prepares method and the microarc oxidation solution of titanium alloy surface best bright finish ceramic wearing coat |
| CN103949167B (en) * | 2014-04-21 | 2016-06-08 | 北京航空航天大学 | A kind of preparation method with automatically cleaning and the micro-nano oil-water separation film of superoleophobic character under water |
| CN103966643B (en) * | 2014-04-24 | 2016-08-24 | 大连理工大学 | A kind of preparation method of the titanium alloy super-hydrophobic surface of low roughness |
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