CN103966643B - A kind of preparation method of the titanium alloy super-hydrophobic surface of low roughness - Google Patents

A kind of preparation method of the titanium alloy super-hydrophobic surface of low roughness Download PDF

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CN103966643B
CN103966643B CN201410167916.6A CN201410167916A CN103966643B CN 103966643 B CN103966643 B CN 103966643B CN 201410167916 A CN201410167916 A CN 201410167916A CN 103966643 B CN103966643 B CN 103966643B
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titanium alloy
hydrophobic surface
super
put
low roughness
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CN201410167916.6A
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CN103966643A (en
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孙玉文
高玉泽
郭东明
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大连理工大学
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Abstract

The method of a kind of super hydrophobic surface preparing low roughness on titanium alloy of the present invention, the invention belongs to field of metal material surface treatment, relates to a kind of utilizing electrochemical anodic oxidation to prepare the process of titanium alloy super-hydrophobic surface in alkaline solution.The method is to be prepared the titanium alloy super-hydrophobic surface of low roughness by electrochemical anodic oxidation in alkaline solution, first polish titanium alloy with abrasive paper for metallograph, again the titanium alloy after polishing is respectively put into ultrasonic cleaning in acetone, ethanol, deionized water, to remove greasy dirt.Using the titanium alloy sheet as anode and the graphite cake as negative electrode, Parallel Symmetric is placed, and is connected with DC source by wire respectively, and titanium alloy connects positive pole, and graphite connects negative pole.Then carry out anodic oxidation, aoxidize and after terminating, titanium alloy is put into ultrasonic cleaning in deionized water.Present invention process is simple, economical and efficient, and controllability is good, and the super hydrophobic surface particularly prepared has low roughness.

Description

A kind of preparation method of the titanium alloy super-hydrophobic surface of low roughness

Technical field

The invention belongs to field of metal material surface treatment, utilize electrochemical anodic oxidation to prepare the process of titanium alloy super-hydrophobic surface in alkaline solution particularly to a kind of.

Background technology

Super hydrophobic surface refers to that the contact angle with water droplet is more than 150 °, the roll angle surface less than 10 °, has the characteristic such as automatically cleaning, anticorrosive, freezing, current drag reduction.Super hydrophobic surface is applied on metal material, can play antifouling, antirust, anti-freeze effect;It is applied to ships shell or inner-walls of duct, the frictional resistance between current can be effectively reduced.Titanium alloy have lightweight, intensity is high, the characteristic such as high temperature resistant, corrosion-resistant, has highly important application in the much industry such as aviation, chemical industry, transport, navigation.Therefore, superhydrophobic characteristic being combined with titanium alloy self character, preparing titanium alloy super-hydrophobic surface has meaning of crucial importance.

At present, on metallic matrix, super hydrophobic surface is main by the first micro-nano coarse structure of structured surface, then prepares with low-surface energy substance modification.For titanium or titanium alloy, generally being prepared surface roughness by chemical method or electrochemical method, low-surface-energy drops in conventional silicon fluoride, stearic acid, Palmic acid, lauric acid etc..Chemical method generally with acid corrosion titanium alloy or builds coarse structure by chemical plating, and then super hydrophobic surface is prepared in low-surface energy substance modification.The advantage of chemical method is to need not special instruments and equipment, and method is simple.But owing to chemical attack is relevant with crystal formation, being limited by lattice, and chemical plating is relevant to material surface activity, therefore the method is relatively tight to the restriction of material, and it is poor to react controllability.Electrochemical method prepares coarse structure generally by anode etching or anodic oxidation, and then super hydrophobic surface is prepared in low-surface energy substance modification.The advantage of electrochemical method be limited by material less, it is easy to producing nanoscale rough structure, and controllability is preferable.But uneven due to anode etching is easily caused surface roughness Ra relatively greatly, general roughness Ra is about 1~3 μm.Anodic oxidation is then generally carried out in acid solution or organic solvent, and needs the longer response time.Micro-nano coarse structure is built as China Patent No. CN 102618913A discloses a kind of anode etching that carries out titanium or titanium alloy in NaCl or NaBr solution, silicon fluoride prepares the method for super hydrophobic surface after modifying, the method efficiency is higher, but to be easily caused surface roughness bigger due to anode etching uneven;Zhang et al. is at F.Zhang, S.Chen, L.Dong, Y.Lei, T.Liu, Y.Yin, Appl.Surf.Sci.2011,257, in 2587, first pure titanium is put into and the ethylene glycol solution containing ammonium fluoride carries out anodic oxidation in 5 hours, then prepare super-hydrophobic titanium surface with low-surface energy substance modification, the method long processing time, inefficient;Lin et al. is at Y.K.Lai, C.J.Lin, J.Y.Huang, H.F.Zhuang, L.Sun, T.Nguyen, Langmuir.2008, in 24,3867, electrochemistry anodic oxidation is utilized to prepare super-hydrophobic titanium surface, using platinum as negative electrode, Fluohydric acid. is electrolyte, owing to platinum is precious metal so that the method is relatively costly.

Summary of the invention

The present invention is for overcoming the deficiencies in the prior art, a kind of method having invented titanium alloy super-hydrophobic surface being prepared low roughness by anodic oxidation, the method is first to construct micron-sized pore space structure on titanium alloy surface by electrochemical anodic oxidation in alkaline electrolyte, and recycling low-surface energy substance is modified and prepared super hydrophobic surface.This invention is simple, economical and efficient.

The technical solution used in the present invention is the preparation method of the titanium alloy super-hydrophobic surface of a kind of low roughness, it is characterized in that, preparation method prepares the titanium alloy super-hydrophobic surface of low roughness by electrochemical anodic oxidation in alkaline solution, specifically comprising the following steps that of method

1) titanium alloy sheet 3 and graphite cake 7 being all cut into 20mm × 30mm, but actual working (finishing) area is 20mm × 20mm, remainder is used as clamping and conduction;First with #1500 abrasive paper for metallograph polish titanium alloy, then will polishing after titanium alloy be respectively put into ultrasonic cleaning 3min in acetone, ethanol, deionized water, to remove greasy dirt;

2) using the titanium alloy sheet 3 as anode and the graphite cake 7 as negative electrode, Parallel Symmetric is placed, and is connected with DC source 1 by wire respectively, and titanium alloy connects positive pole, and graphite connects negative pole;Then negative electrode and anode are put into jointly by NaOH and H2O2In the alkaline electrolyte 4 of composition, carrying out anodic oxidation 30~60min by 10~15V constant voltages, titanium alloy is put into ultrasonic cleaning in deionized water after terminating, is dried up stand-by by oxidation;

3) oxidized titanium alloy is put into immersion 2h in the silicon fluoride ethanol solution that mass fraction is 1% configured;Put into baking 20min in 120 DEG C of baking ovens after taking-up, be cooled to room temperature, obtain the titanium alloy super-hydrophobic surface with low roughness.

The invention has the beneficial effects as follows employing NaOH and H2O2It is general chemistry reagent, and the micro-rough structure only needing just can obtain required for super hydrophobic surface for 30 minutes;The super hydrophobic surface of preparation has the hydrophobic performance that low roughness is become reconciled, and roughness Ra is only 0.669 μm, and the contact angle to water droplet is 158.5 °, and roll angle is 5.3 °.Process is simple, it is not necessary to complicated processing instrument and operating procedure, and prepared by suitable large area, economical and efficient.

Accompanying drawing explanation

Fig. 1 is processing unit (plant) schematic diagram.Wherein: 1-DC source, 2-grip device, 3-titanium alloy sheet, 4-electrolyte, 5-magnetic stirring apparatus, 6-stirring rotator, 7-graphite cake, 8-container.

Fig. 2 is the prepared titanium alloy super-hydrophobic surface schematic diagram to water droplet wettability.θ and β is respectively titanium alloy super-hydrophobic surface to the contact angle of water droplet and roll angle, the super-hydrophobic titanium alloy sheet of 1-water droplet, 2-

Fig. 3 is the scanning electron microscope (SEM) photograph that the titanium alloy super-hydrophobic surface that embodiment 1 prepares amplifies 5000 times.

Detailed description of the invention

Being embodied as of the present invention is described in detail below in conjunction with technical scheme and accompanying drawing.As shown in Figure 1, titanium alloy sheet 3 is parallel with graphite cake 7 just to placement, and is fixed on grip device 2 for processing unit (plant) needed for this embodiment.Titanium alloy sheet 3 and graphite cake 7 are connected on positive pole and the negative pole of DC source 1 by wire respectively.The effect of magnetic stirring apparatus 5 is to make the electrolyte in reaction more uniform.Titanium alloy super-hydrophobic surface is to the wettability of water droplet as shown in Figure 2,5 μ L water droplets 1 are dropped on the super-hydrophobic titanium alloy sheet 2 of horizontal positioned at random, water droplet is similar to spherical, θ is this super hydrophobic surface contact angle to water droplet, when rolling angle beta for making water droplet start to roll, the minimum angles of the required inclination of super-hydrophobic titanium alloy sheet 2 plate.

Embodiment 1

1) titanium alloy (Ti-6Al-4V) plate and graphite cake being all cut into 20mm × 30mm, but actual working (finishing) area is 20mm × 20mm, remainder is used as clamping and conduction.Before processing, first with 1500# sand papering titanium alloy sheet, ultrasonic cleaning 3min in acetone, ethanol, deionized water, goes to degrease the most successively.

2) titanium alloy sheet being spaced 15mm with graphite cake is parallel just to placement, connected with DC source by two plates with wire, titanium alloy sheet connects positive pole, and graphite cake connects negative pole.Two plates are put into the H of NaOH and 0.15mol/L filling 1.5mol/L simultaneously2O2In mixed solution, opening magnetic stirring apparatus (1000r/min), connect DC source, voltage is fixed on 10V.Oxidization time is 30min, adds solution temperature in man-hour and is about room temperature (25 DEG C).

3), after machining, first titanium alloy sheet is put into ultrasonic cleaning 3min in deionized water, dries up.Exemplar is put into immersion 2h in the silicon fluoride ethanol solution that mass fraction is 1% configured again, finally exemplar is put in baking oven, at 120 DEG C, dry 20min.Take out exemplar and be cooled to room temperature, available titanium alloy super-hydrophobic surface.

As shown in Figure 3, surface is the pore space structure of random distribution to the electron scanning micrograph on titanium alloy super-hydrophobic surface, and pore size is 5~10 μm.This super hydrophobic surface roughness Ra is only 0.669 μm, and as shown in accompanying drawing 2, can record this super hydrophobic surface to the contact angle of water droplet is 158.5 °, and roll angle is 5.3 °.

Embodiment 2

By operation and the step of embodiment 1, change oxidization time into 60min.Obtained titanium alloy super-hydrophobic surface microscopic appearance is without significant change, and for pore space structure, pore size is also 5~10 μm.This super hydrophobic surface roughness Ra is 0.822 μm, and the contact angle to water droplet is 158.8 °, and roll angle is 5.1 °.

Embodiment 3

By operation and the step of embodiment 1, change constant voltage into 15V.Obtained titanium alloy super-hydrophobic surface is still the pore space structure of random distribution, and hole size is 5~10 μm.This super hydrophobic surface roughness Ra is 0.785 μm, and the contact angle to water droplet is 157.8 °, and roll angle is 5.6 °.

Claims (1)

1. a preparation method for the titanium alloy super-hydrophobic surface of low roughness, is characterized in that, preparation Method is to be prepared the titanium alloy of low roughness by electrochemical anodic oxidation in alkaline solution Super hydrophobic surface, specifically comprising the following steps that of method
1) titanium alloy sheet (3) and graphite cake (7) are all cut into 20mm × 30mm, but actual Working (finishing) area is 20mm × 20mm, and remainder is used as clamping and conduction;First with #1500 gold Phase sand papering titanium alloy, then will polishing after titanium alloy be respectively put into acetone, ethanol, go from Ultrasonic cleaning 3min in sub-water, to remove greasy dirt;
2) using the titanium alloy sheet (3) as anode and the graphite cake (7) as negative electrode, parallel Symmetrically placed, and be connected with DC source (1) by wire respectively, titanium alloy connects positive pole, Graphite connects negative pole;Then negative electrode and anode are put into jointly by NaOH and H2O2The alkalescence of composition In electrolyte (4), carry out anodic oxidation 30~60min, oxygen by 10~15V constant voltages Change, after terminating, titanium alloy is put into ultrasonic cleaning in deionized water, dry up stand-by;
3) oxidized titanium alloy is put into the silicon fluoride ethanol that mass fraction is 1% configured Solution soaks 2h;Put into baking 20min in 120 DEG C of baking ovens after taking-up, be cooled to room temperature, Obtain the titanium alloy super-hydrophobic surface with low roughness.
CN201410167916.6A 2014-04-24 2014-04-24 A kind of preparation method of the titanium alloy super-hydrophobic surface of low roughness CN103966643B (en)

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CN106802095A (en) * 2017-01-20 2017-06-06 中国石油大学(华东) A kind of microchannel cooling
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