CN104233278A - Fluorination-oxidation hydrophilic treatment method for metal and metalloid - Google Patents
Fluorination-oxidation hydrophilic treatment method for metal and metalloid Download PDFInfo
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- CN104233278A CN104233278A CN201410498674.9A CN201410498674A CN104233278A CN 104233278 A CN104233278 A CN 104233278A CN 201410498674 A CN201410498674 A CN 201410498674A CN 104233278 A CN104233278 A CN 104233278A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/04—Anodisation of aluminium or alloys based thereon
- C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
- C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
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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
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/32—Anodisation of semiconducting materials
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Abstract
The invention discloses a fluorination-oxidation hydrophilic treatment method for metal and metalloid. The method comprises the following steps: (1) cleanly polishing the surface of a metal or metalloid material, ultrasonically cleaning the metal or metalloid material in sequence by using acetone, ethanol and deionized water, removing pollutants, and drying the material; (2) calcining the material in the air atmosphere of 100-1,000 DEG C, so that a layer of oxidation film is formed on the surface of the material; (3) forming an oxyfluoride layer with a -F end group in an electro-migration or free diffusion mode under the conditions of constant temperature of 10-50 DEG C and lower fluoride ion concentration; (4) determining the fluoride content of a surface layer of the obtained material and the hydrophilic performance. A reagent and the material are cheap, simple and easily obtained, the operation method is quite simple, variables in the operation process are easy to control, the hydrophilic performance of a product subjected to fluorination-oxidation treatment is good, and the stability is higher. Through construction on hydrophilic interfaces of the metal, the metalloid and oxides, the method is widely applied to self-cleaning of the material, prevention of biological pollution, improvement of pool boiling heat transfer and the like.
Description
Technical field
The present invention relates to the fluorine oxidation hydrophilic treatment method of a kind of metal and metalloid.
Background technology
The achievement in research of hydrophilic interface material, at material automatically cleaning, strengthen boiling heat transfer efficiency, anti-biological pollution and biomedicine field have very important meaning.Constructing of hydrophilic interface, mainly sets about from surfaceness and surface chemical composition two aspect.Just control with regard to material surface microtexture, 2008, Wang Hui etc. were by anodic oxidation and be aided with liquid phase product, prepared super hydrophilic aluminium alloy interface (CN101665972); 2012, Wang Bo etc. utilized the method for chemical corrosion, went out microtexture in aluminium surface etch, thus obtained the excellent interface of hydrophilicity (CN102825260A); 2013, Jiang Yijian etc. in aluminium surface deposition one deck dendroid microstructure, thus obtained super hydrophilic interface (CN103668140A).On the other hand, Qin great Ke etc. carry out modification by utilizing number of chemical material to glass surface, obtain anti-fog performance super hydrophilic glass interface (CN103482883A) significantly.The research of hydrophilic interface and related process technologies are ripe day by day.
Fluorine is the extremely strong chemical element of a kind of electronegativity, and can react with most of material, this determines the universality of fluorine treatment technology to a certain extent; Meanwhile, due to this extremely strong electronegative existence, will greatly improve the polarity of material interface, thus the material that can have an electron deficiency H with water etc. forms stronger hydrogen bond action, greatly improves the hydrophilicity at interface.But, because fluorine element has extremely strong electronegativity, so most of fluorochemical is all ionic compound, very easily water-soluble, so just greatly limit the application of fluorination technology, the fluorine-containing layer how formed containing stable-F end group becomes the core of fluorinated hydrophilic technology, and this is the subject matter that this patent will solve, and is also main innovate point place.
The modification that fluorine-containing chemical substance is used for hydrophilic interface is had it long ago.2007, Howarter etc., based on the oh group of glass surface, connected reagent by centre, and fluorine-containing tensio-active agent is keyed to glass surface, thus prepared the glass with good hydrophilic antifogging performance.But the fluorine reagent that this institute uses is hydrophobic perfluoro alkane, the realization of hydrophilicity mainly relies on the cis-trans isomerism of middle connection reagent under external stimulus.In this technique, that be directly connected with fluorine element is the weak metal of electronegativity or metalloid element (Ti, Al, Cu, Si etc.), thus electronic cloud can be made to be partial to fluorine atom by a relatively large margin, can with the material containing electron deficiency H (as water, alcohol etc.) form stronger hydrogen bond action, greatly strengthen the wetting property at interface, simultaneously in order to stablize the fluorochemical with-F end group, the mode that we are oxidized by fluorine, form the structure (the stability Albu of oxyfluoride reported in 2008) of-O-M-F, in this structure, because O element also has stronger electronegativity, so electronic cloud can be avoided excessively to be partial to fluorine atom and to form ionic compound,-F end group can be stabilized in again in the huge oxide network of system simultaneously, strengthen the stability of hydrophilic interface.Formation mechenism as shown in Figure 1.
Summary of the invention
The object of the invention is to by fluorine oxidation technology, fluorin radical is connected to metal and metalloid surface, thus greatly improves the hydrophilicity of material interface, reach super hydrophilic effect, for the application such as follow-up automatically cleaning are prepared.
To achieve these goals, the present invention adopts following technical scheme:
A fluorine oxidation hydrophilic treatment method for metal and metalloid, is characterized in that comprising the steps:
(1) pre-treatment of material: metal or metalloid material surface finish is clean, uses acetone, ethanol, deionized water ultrasonic cleaning successively, and the organic and mineral-type pollutent of removing glass surface, dries;
(2) oxide treatment of material interface: calcined in the air atmosphere of 100 DEG C-1000 DEG C by material, makes material surface form layer oxide film;
(3) fluoridation of material interface: under 10-50 DEG C of constant temperature and lower fluorinion concentration, utilize the mode of electromigration or free diffusing, make fluorion reach material interface and react with oxide compound, forming the stable oxyfluoride layer with-F end group;
(4) fluorine content measurement of resulting materials top layer and hydrophilicity measure: utilize the Oil repellent of EDS to material surface to measure, utilize high-speed camera to characterize the effect of impregnation of water droplet on interface.
In above-mentioned treatment process, adopt sand paper to polish in step (1), and carry out polishing with chemical rightenning cloth.
In above-mentioned treatment process, in step (1), the frequency of ultrasonic cleaning is 50-100KHZ, and oven temperature is 10-100 DEG C.
In above-mentioned treatment process, the time 2-10 hour of calcining in step (2), can guarantee form superficial oxidation layer and be unlikely to destroy matrix.
In above-mentioned treatment process, in step (3), homo(io)thermism is realized by constant temperature water bath, and reaction vessel is placed in water bath.
In above-mentioned treatment process, described in step (3), lower fluorinion concentration refers to below 20% quality, preferably below 10% quality, can guarantee partially fluorinated and form stable oxyfluoride.
In above-mentioned treatment process, described metal is common metal and the lanthanide series metals etc. such as Ti, Al, Cu, Pb, Fe, its essence is that the electronegativity of these elements itself is little, and fluorine element that can be large with electronegativity forms the chemical bond with very strong polarity, thus forms hydrophilic interface; Simultaneously because fluorine element almost can react with all substances, so this technology is all applicable to all metals that can react with fluorine, oxygen.
In above-mentioned treatment process, described metalloid is Si, Ge, As, Sb etc., mainly also less owing to the electronegativity of these elements own, the feature can reacted with fluorine, oxygen element again.Non-metallic element is not suitable for this fluorine oxide treatment mainly because its electronegativity is comparatively large, and the chemical bond polarity formed with fluorine element is inadequate, cannot form ultra-hydrophilic surface.
Compared with prior art, the present invention has following beneficial effect:
The fluorine oxidation hydrophilic treatment method of metal provided by the invention and metalloid, reagent and material are cheap and simple and easy to get, and working method is also very simple, and in operating process, variable easily controls, and the product hydrophilicity after fluorine oxide treatment is excellent, and stability is better.The present invention is by constructing in the hydrophilic interface of metal, metalloid and oxide compound thereof, and at material automatically cleaning, anti-biological pollution, strengthens the aspects such as pool Boiling Heat Transfer and have a wide range of applications.
Accompanying drawing explanation
Fig. 1 is that metal and metalloid interface fluorine are oxidized hydrophilic Analysis on Mechanism figure;
Fig. 2 is the static contact angle change before and after Ti, Al and glass fluorine oxide treatment;
Fig. 3 is: (a) pure titanium sheet; 0.1wt% NH is being contained again after titanium sheet after (b) oxide treatment and oxide treatment
4in the ethylene glycol electrolytic solution of F, 1wt% water, 25 DEG C, under the voltage of 40V, anodic oxidation (c) 0.5h respectively; (d) 1h; (e) 1.5h; SEM figure after (f) 2h and contact angle (5ul water droplet);
Fig. 4 is 5ul water droplet at titanium sheet interfacial contact angle and the Oil repellent changing trend diagram with the fluorine treatment time.
Embodiment
Embodiment 1:
The pre-treatment of the first step material: Ti material surface is polished clean with sand paper and chemical rightenning cloth respectively, use analytical pure acetone, ethanol, deionized water at 80KHZ ultrasonic cleaning 30min successively, remove the organic and mineral-type pollutent of glass surface respectively, with baking oven 50 DEG C of oven dry.
The oxide treatment of second step material interface: Ti material is calcined 4h in the air atmosphere of 450 DEG C, makes material surface form layer oxide film.
The fluoridation of the 3rd step material interface: the sample of oxide treatment, at 25 DEG C of constant temperatures and containing 0.1wt% NH
4in the ethylene glycol electrolytic solution of F, 1wt% water, under the voltage of 40V, react 2h, make fluorion reach material interface and react with oxide compound, form the stable oxyfluoride layer with-F end group.
4th step video camera takes the static effects of 5ul deionized water on interface, to determine the size of static contact angle.
Gained workpiece, surface contact angle is 10 °, and wetting property is tending towards super hydrophily, increases surfaceness on this basis, will strengthen the hydrophilicity at interface further.(as Fig. 2)
To be illustrated in figure 3 after the titanium sheet after (a) pure titanium sheet, (b) oxide treatment and oxide treatment again containing in the ethylene glycol electrolytic solution of 0.1wt% NH4F, 1wt% water, 25 DEG C, under the voltage of 40V, anodic oxidation (c) 0.5h respectively; (d) 1h; (e) 1.5h; SEM figure after (f) 2h and the static contact angle of 5ul water droplet at interface, little from the change of figure known interfacial microstructure, and contact angle is on a declining curve; Known to the further composition analysis in interface, interface Oil repellent increases with the prolongation in fluorine treatment time, and this is the immediate cause that interface static contact angle diminishes.(as Fig. 4)
Embodiment 2:
The pre-treatment of the first step material: Al material surface is polished clean with sand paper and chemical rightenning cloth respectively, use analytical pure acetone, ethanol, deionized water at 80KHZ ultrasonic cleaning 30min successively, remove the organic and mineral-type pollutent of glass surface respectively, with baking oven 50 DEG C of oven dry.
The fluorine oxide treatment of second step material interface: at 25 DEG C of constant temperatures and containing 3wt% HF, in the ethylene glycol electrolytic solution of 8wt% water, 1h is reacted under the voltage of 40V, first because oxonium ion and interface interaction form zone of oxidation, make fluorion reach material interface and react with oxide compound again, form the stable oxyfluoride layer with-F end group.
3rd step video camera takes the static effects of 5ul deionized water on interface, to determine the size of static contact angle.
Gained workpiece, surface contact angle is 4 °, and wetting property is super hydrophily, excellent performance, and stability is excellent.(as Fig. 2)
Embodiment 3:
The pre-treatment of the first step material: use analytical pure acetone, ethanol, deionized water at 80KHZ ultrasonic cleaning 30min successively sheet glass (common slide glass), removes the organic and mineral-type pollutent of glass surface, respectively with baking oven 50 DEG C of oven dry.
The fluoridation of second step material interface: because glass is originally as oxide compound, so oxidation step can omit, be statically placed in by sheet glass in the aqueous solution containing 2wt% HF and react 140min, homo(io)thermism is 25 DEG C, by diffusion, fluorion is made to be bonded in glass surface.
3rd step video camera takes the static effects of 3ul deionized water on interface, to determine the size of static contact angle.
Gained workpiece, surface contact angle is 5.5 °, and wetting property is super hydrophily, excellent performance, stability excellent (as Fig. 2).
Claims (9)
1. a fluorine oxidation hydrophilic treatment method for metal and metalloid, is characterized in that comprising the steps:
(1) pre-treatment of material: metal or metalloid material surface finish is clean, uses acetone, ethanol, deionized water ultrasonic cleaning successively, and the organic and mineral-type pollutent of removing glass surface, dries;
(2) oxide treatment of material interface: calcined in the air atmosphere of 100 DEG C-1000 DEG C by material, makes material surface form layer oxide film;
(3) fluoridation of material interface: under 10-50 DEG C of constant temperature and lower fluorinion concentration, utilize the mode of electromigration or free diffusing, make fluorion reach material interface and react with oxide compound, forming the stable oxyfluoride layer with-F end group;
(4) fluorine content measurement of resulting materials top layer and hydrophilicity measure: utilize the Oil repellent of EDS to material surface to measure, utilize high-speed camera to characterize the effect of impregnation of water droplet on interface.
2. treatment process as claimed in claim 1, is characterized in that adopting sand paper to polish in step (1), and carries out polishing with chemical rightenning cloth.
3. treatment process as claimed in claim 1, it is characterized in that the frequency of ultrasonic cleaning in step (1) is 50-100KHZ, oven temperature is 10-100 DEG C.
4. treatment process as claimed in claim 1, is characterized in that the time of calcining in step (2) is 2-10 hour.
5. treatment process as claimed in claim 1, it is characterized in that in step (3), homo(io)thermism is realized by constant temperature water bath, reaction vessel is placed in water bath.
6. treatment process as claimed in claim 1, is characterized in that described in step (3), lower fluorinion concentration refers to below 20% quality.
7. treatment process as claimed in claim 6, is characterized in that described in step (3), lower fluorinion concentration refers to below 10% quality.
8. treatment process as claimed in claim 1, is characterized in that described metal is Ti, Al, Cu, Pb, Fe or lanthanide series metal.
9. treatment process as claimed in claim 1, is characterized in that described metalloid is Si, Ge, As or Sb.
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| CN201410498674.9A CN104233278B (en) | 2014-09-26 | 2014-09-26 | A kind of fluorine oxidation hydrophilic treatment method of metal and metalloid |
| PCT/CN2015/075292 WO2016045339A1 (en) | 2014-09-26 | 2015-03-27 | Method for oxyfluoridation hydrophilic treatment of metals and metalloids |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016045339A1 (en) * | 2014-09-26 | 2016-03-31 | 中山大学 | Method for oxyfluoridation hydrophilic treatment of metals and metalloids |
| CN111349921A (en) * | 2018-12-21 | 2020-06-30 | 罗伯特·博世有限公司 | Hydrophobic surface treatment method for metal material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693859A (en) * | 2013-12-11 | 2014-04-02 | 中山大学 | Fog preventing treatment method for glass |
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| 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 |
| CN104233278B (en) * | 2014-09-26 | 2016-08-17 | 中山大学 | A kind of fluorine oxidation hydrophilic treatment method of metal and metalloid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103693859A (en) * | 2013-12-11 | 2014-04-02 | 中山大学 | Fog preventing treatment method for glass |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016045339A1 (en) * | 2014-09-26 | 2016-03-31 | 中山大学 | Method for oxyfluoridation hydrophilic treatment of metals and metalloids |
| CN111349921A (en) * | 2018-12-21 | 2020-06-30 | 罗伯特·博世有限公司 | Hydrophobic surface treatment method for metal material |
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| WO2016045339A1 (en) | 2016-03-31 |
| CN104233278B (en) | 2016-08-17 |
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