CN106637316A - Method for preparing super-hydrophobic surface on titanium substrate - Google Patents
Method for preparing super-hydrophobic surface on titanium substrate Download PDFInfo
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- CN106637316A CN106637316A CN201611117595.4A CN201611117595A CN106637316A CN 106637316 A CN106637316 A CN 106637316A CN 201611117595 A CN201611117595 A CN 201611117595A CN 106637316 A CN106637316 A CN 106637316A
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- titanium substrate
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/08—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain an anti-friction or anti-adhesive surface
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Abstract
The invention provides a method for preparing a super-hydrophobic surface on a titanium substrate. The method comprises the steps of S1, electrochemically depositing a gold-tin alloy film on the surface of the titanium substrate; S2, putting the titanium substrate, on the surface of which the gold-tin alloy film is deposited, into a concentrated nitric acid solution for carrying out dealloying treatment; S3, self-assembling a perfluorinated mercaptan film on the surface of the titanium substrate which is subjected to the dealloying treatment to obtain the super-hydrophobic surface. According to the method, a graded uneven surface is formed by building a nano-porous fractal heterogeneous metal surface on the surface of the titanium substrate, and the perfluorinated mercaptan film is self-assembled on the porous metal surface by utilizing the interaction of metal-sulfur atoms so as to reduce the surface energy, so that the super-hydrophobic surface is formed on the titanium substrate.
Description
Technical field
The invention belongs to super hydrophobic material technical field, is related to a kind of method on the constructing super-drainage surface in titanium substrate.
Background technology
Titanium and its alloy due to intensity it is high, corrosion resistance is strong, the excellent feature of bio-compatibility and be widely used in ship
The fields such as oceangoing ship, aviation and biologic medical.Because super hydrophobic surface has extreme wettability so that its all kinds of productions with
The prospect of being widely applied is respectively provided with sphere of life.For example, super hydrophobic surface being applied into naval vessel shell can play reduction resistance
Power, the adhesion of suppression biomass and anticorrosive effect；Aircraft surface is applied to, the effect of anti-ice can be reached, for biology
Medical material surface, then can improve its biocompatibility.It is to learn how effectively in titanium substrate surface construction super hydrophobic surface
The problem that art is paid close attention to jointly with industrial circle.The preparation method of current existing titanium-based super hydrophobic surface, such as laser ablation method, heat
Oxidizing process, anodizing, sand-blast, solution etches method etc., are respectively provided with high cost, instrument requirements are special or process is complicated etc.
Shortcoming, it is difficult to realize industrialized production, thus also there is a certain distance from practical application.
The content of the invention
Based on this, the technical problem to be solved be a kind of process is simple is provided, it is with low cost in titanium-based
The method that super hydrophobic surface is prepared on bottom.
The invention provides a kind of method that super hydrophobic surface is prepared in titanium substrate, including：
S1) electrochemical deposition gold-tin alloy film in titanium substrate；
S2) titanium substrate that surface is coated with gold-tin alloy film is carried out into alloy treatment in concentrated nitric acid solution；
S3) in the titanium substrate surface self-organization perfluorinated thiols film through going alloy treatment.
Preferably, step S1) in depositing current density be 0.5～0.8mA cm-2, depositing temperature be 40～55 DEG C,
Sedimentation time is 600s～2000s；Step S2) in red fuming nitric acid (RFNA) concentration be 70wt.%, the reaction time be 3～7 days；Institute
State step S3) in perfluorinated thiols be that, with the one kind in perfluor nomercaptans more than 8 carbon atoms, the concentration of thiol solution is
2～5mmol L-1, self assembly temperature is 25～40 DEG C, and the self assembly time is 12～24h.
The invention provides a kind of method on the constructing super-drainage surface in titanium substrate, including：S1) the electrification in titanium substrate
Learn gold-tin alloy film；S2) titanium substrate that surface is coated with gold-tin alloy film is carried out in concentrated nitric acid solution to close
Gold is processed；S3) in the titanium substrate surface self-organization perfluorinated thiols film through going alloy treatment.Compared with prior art, this
It is bright that the increase of nano porous metal structure is formed in titanium-based basal surface with alloy process is removed by combined with electrochemical deposit alloy film
Surface roughness, then reduces surface energy in nano porous metal surface self-organization perfluorinated thiols film, so as to obtain with super
The titanium substrate of hydrophobic surface.The super hydrophobic surface preparation process only needs to use conventional DC power supply and using solution corrosion and certainly
Assembling process, it is to avoid the instrument of costliness using precision, it is not required that complicated technical process, is highly suitable in metallic substrates
Upper constructing super-drainage surface.
Description of the drawings
Fig. 1 is the stereoscan photograph on the gold-tin alloy/titanium surface obtained in the embodiment of the present invention 1；
Fig. 2 is the stereoscan photograph on the nano-porous gold/titanium surface obtained in the embodiment of the present invention 1；
Fig. 3 is the nano-porous gold/titanium surface water droplet contact angle test chart obtained in the embodiment of the present invention 1.
Specific embodiment
The invention provides a kind of method that super hydrophobic surface is prepared in titanium substrate, including：S1) the electrification in titanium substrate
Learn gold-tin alloy film；S2) titanium substrate that surface is coated with gold-tin alloy film is carried out in concentrated nitric acid solution to close
Gold is processed；S3) in the titanium substrate surface self-organization perfluorinated thiols film through going alloy treatment.
Wherein, the present invention is not particularly limited to the source of all raw materials, is commercially available or self-control.
In the present invention, the gold-tin alloy film carries out electrochemical deposition using gold-tin alloy plating solution, and preferred electricity is heavy
Accumulating technological parameter is：Current density be 0.5～0.8mA cm-2, depositing temperature be 40～55 DEG C, sedimentation time be 600s～
2000s；Described to go alloy process to carry out in concentrated nitric acid solution, optimum condition is：The concentration of red fuming nitric acid (RFNA) is 70wt.%, is reacted
Time is 3～7 days；The optimum condition of the perfluorinated thiols film self assembling process is：Perfluorinated thiols are with 8 carbon atoms
One kind in perfluor nomercaptan above, the concentration of thiol solution is 2～5mmol L-1, self assembly temperature is 25～40 DEG C, from
Built-up time is 12～24h.
Combined with electrochemical sedimentation of the present invention, alloyage and self-assembling technique are removed, three-dimensional manometer is constructed in titanium substrate many
On the basis of the gold structure of hole, further surface energy is further reduced by the modification of self assembly perfluorinated thiols film, effectively existed
Super hydrophobic surface is formed in titanium substrate, the method is highly suitable to be applied for preparing super hydrophobic surface in conducting metal substrate.
It is clearly and completely described below in conjunction with the technical scheme of the embodiment of the present invention, it is clear that described enforcement
Example is only a part of embodiment of the invention, rather than the embodiment of whole.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model of present invention protection
Enclose.
Embodiment 1
1.1 take 100 milliliters of gold-tin alloy plating solutions, and with titanium substrate as negative pole, platinum plating titanium net is positive pole, in two electrode systems
In carry out electrochemical deposition, electrode face product is 1cm2, and deposition current is 0.0005A；Depositing temperature is 50 DEG C, sedimentation time
For 2000s, electro-deposition takes out titanium substrate after terminating, and deionized water is rinsed repeatedly, is dried up with nitrogen, you can must be covered to surface
The titanium substrate of Gai Jin-tin alloy film.
1.2 take the red fuming nitric acid (RFNA) that 100 milliliters of concentration is 70%, by gold-tin alloy obtained in 1.1/titanium material immersion red fuming nitric acid (RFNA)
In solution, take out after soaking 5 days at room temperature, rinsed repeatedly with a large amount of deionized waters, dried up with nitrogen, you can must cover to surface
It is stamped the titanium substrate of nanoporous gold thin film.
1.3 1H for taking 20mL 5mM, the ethanol solution of 1H, 2H, 2H- perfluoro decyl mercaptan, by nanoporous obtained in 1.2
In gold/titanium material immersion thiol solution, take out after soaking 12 hours at 25 DEG C, rinsed repeatedly with a large amount of absolute ethyl alcohols, use nitrogen
Air-blowing is done, you can super hydrophobic surface is obtained in titanium substrate.
Gold-tin alloy/titanium the material obtained in 1.1 is analyzed using SEM, obtains its scanning electricity
Mirror photo, as shown in Figure 1.As can be seen from Figure 1 the surface of gold-tin alloy film is in ridge shape.
Nano-porous gold/titanium the material obtained in 1.2 is analyzed using SEM, obtains its scanning electricity
Mirror photo, as shown in Figure 2.Find out as can be seen from Figure 2, nanoporous gold thin film is presented three-dimensional porous fractal structure.
To the modification 1H obtained in 1.3, the nano-porous gold/titanium material of 1H, 2H, 2H- perfluoro decyl mercaptan self-assembled film
Contact angle test is carried out, still image of the 5 μ L water droplets in the material surface is obtained, as shown in Figure 3.From figure 3, it can be seen that water droplet
It is spherical in shape in the material surface, understand that contact angle is 160 ° by measurement, show to define super hydrophobic surface in titanium substrate.
Embodiment 2
2.1 take 100 milliliters of gold-tin alloy plating solutions, and with titanium substrate as negative pole, platinum plating titanium net is positive pole, in two electrode systems
In carry out electrochemical deposition, electrode face product is 1cm2, depositing current density is 0.0005A；Depositing temperature is 40 DEG C, deposition
Time is 1000s, and electro-deposition takes out titanium substrate after terminating, and deionized water is rinsed repeatedly, is dried up with nitrogen, you can obtain table
Face covers the titanium substrate of gold-tin alloy film.
2.2 take the red fuming nitric acid (RFNA) that 100 milliliters of concentration is 70%, by gold-tin alloy obtained in 2.1/titanium material immersion red fuming nitric acid (RFNA)
In solution, take out after soaking 5 days at room temperature, rinsed repeatedly with a large amount of deionized waters, dried up with nitrogen, you can must cover to surface
It is stamped the titanium substrate of nanoporous gold thin film.
2.3 1H for taking 20mL 5mM, the ethanol solution of 1H, 2H, 2H- perfluoro decyl mercaptan, by nanoporous obtained in 2.2
In gold/titanium material immersion thiol solution, take out after soaking 12 hours at 25 DEG C, rinsed repeatedly with a large amount of absolute ethyl alcohols, use nitrogen
Air-blowing is done, you can super hydrophobic surface is obtained in titanium substrate.
Embodiment 3
3.1 take 100 milliliters of gold-tin alloy plating solutions, and with titanium substrate as negative pole, platinum plating titanium net is positive pole, in two electrode systems
In carry out electrochemical deposition, electrode face product is 1cm2, depositing current density is 0.0006A；Depositing temperature is 45 DEG C, deposition
Time is 1500s, and electro-deposition takes out titanium substrate after terminating, and deionized water is rinsed repeatedly, is dried up with nitrogen, you can obtain table
Face covers the titanium substrate of gold-tin alloy film.
3.2 take the red fuming nitric acid (RFNA) that 100 milliliters of concentration is 70%, by gold-tin alloy obtained in 3.1/titanium material immersion red fuming nitric acid (RFNA)
In solution, take out after soaking 5 days at room temperature, rinsed repeatedly with a large amount of deionized waters, dried up with nitrogen, you can must cover to surface
It is stamped the titanium substrate of nanoporous gold thin film.
3.3 1H for taking 20mL 5mM, the ethanol solution of 1H, 2H, 2H- perfluoro decyl mercaptan, by nanoporous obtained in 2.2
In gold/titanium material immersion thiol solution, take out after soaking 12 hours at 25 DEG C, rinsed repeatedly with a large amount of absolute ethyl alcohols, use nitrogen
Air-blowing is done, you can super hydrophobic surface is obtained in titanium substrate.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
Claims (6)
1. a kind of method that super hydrophobic surface is prepared in titanium substrate, it is characterised in that include：
S1) in titanium substrate surface electrochemistry gold-tin alloy film；
S2) titanium substrate that surface covers gold-tin alloy film is carried out into alloy treatment in concentrated nitric acid solution；
S3) in the titanium substrate surface self-organization perfluorinated thiols film through going alloy process to process.
2. method according to claim 1, it is characterised in that the gold-tin alloy film passes through electrochemical deposition legal system
It is standby.
3. method according to claim 2, it is characterised in that the current density of electrochemical deposition is 0.5～0.8mA cm-
2, depositing temperature is 40～55 DEG C, and sedimentation time is 600s～2000s.
4. preparation method according to claim 3, it is characterised in that the concentration of red fuming nitric acid (RFNA) is 70wt.%, goes the alloy time
For 3～7 days.
5. preparation method according to claim 4, base is characterised by, the perfluorinated thiols be with 8 carbon atoms with
On perfluor nomercaptan in one kind, the concentration of thiol solution is 2～5mmol L-1, self assembly temperature is 25～40 DEG C, from group
ETL estimated time of loading is 12～24h.
6. the super hydrophobic surface in a kind of titanium substrate, it is characterised in that be prepared by method by described in any one of claim 1-5
Obtain.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107447235A (en) * | 2017-06-20 | 2017-12-08 | 广东工业大学 | A kind of ordered porous nickel composite materials of nano-porous gold@and its preparation method and application |
| CN110468415A (en) * | 2019-08-19 | 2019-11-19 | 山东大学 | A kind of metal super-hydrophobic surface preparation method and applications |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107447235A (en) * | 2017-06-20 | 2017-12-08 | 广东工业大学 | A kind of ordered porous nickel composite materials of nano-porous gold@and its preparation method and application |
| CN110468415A (en) * | 2019-08-19 | 2019-11-19 | 山东大学 | A kind of metal super-hydrophobic surface preparation method and applications |
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| CN106637316B (en) | 2018-12-21 |
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