CN101665972A - Method for preparing ultra-hydrophilic surface of visible light type aluminum or aluminum alloy - Google Patents
Method for preparing ultra-hydrophilic surface of visible light type aluminum or aluminum alloy Download PDFInfo
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- CN101665972A CN101665972A CN200810120739A CN200810120739A CN101665972A CN 101665972 A CN101665972 A CN 101665972A CN 200810120739 A CN200810120739 A CN 200810120739A CN 200810120739 A CN200810120739 A CN 200810120739A CN 101665972 A CN101665972 A CN 101665972A
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Abstract
The invention provides a method for preparing the ultra-hydrophilic surface of visible light type aluminum or aluminum alloy. The method comprises the following steps of: 1, preparing an aqueous solution of hydrofluotitanic acid ammonium; 2, performing anode oxidation of aluminum or aluminum alloy so as to form a layer of porous oxide film on the surface of the aluminum or aluminum alloy; 3, performing liquid-phase sedimentation; and 4, performing thermal treatment. Compared with the prior art, the method has the advantages of simple preparation method, good repeatability, excellent hydrophilic property, an antifouling and self-cleaning effect under visible light, and wide application prospect.
Description
Technical field
The present invention relates to a kind of preparation method of metal ultra-hydrophilic surface, relate in particular to a kind of preparation method of titanium deoxid film ultra-hydrophilic surface under visible light who is applied to the aluminum or aluminum alloy surface.
Background technology
In nano semiconductor material, TiO
2Film is with its photocatalysis efficiency height, chemical stability height, safety non-toxic and advantage such as with low cost and receive much concern, moreover, and nano-TiO
2Film also has photic super hydrophilicity, generally be to define the Superhydrophilic titanium deoxid film like this, titanium dioxide is prepared into film on substrate, under normal conditions, with water droplet on the titanium deoxid film surface, there is bigger contact angle on the surface with water, and under the irradiation of UV-light, the contact angle of water is reduced to 0 °.
Further, discover nano-TiO
2The wetting ability of film has optical reciprocity, and this wetting ability state still can keep several hours to several days after stopping illumination, slowly returns to the preceding hydrophobic state of illumination then, again with after the UV-irradiation, can show as Superhydrophilic again.Can make the surface remain super hydrophily during employing UV-irradiation at intermittence.
TiO under the UV-irradiation
2The super hydrophilicity of film has broad application prospects at automobile rearview mirror, windshield glass, antimicrobial Superhydrophilic pottery, antifouling self-cleaning glass and aspects such as material of construction such as aluminium and alloy thereof, enjoys the concern of academia and business circles.The preparation method of titanium deoxid film has much in the prior art, and relative merits are respectively arranged, specifically " the nano-TiO that can be shown with reference to the 14th volume the 5th interim Cui Xiao jasmine etc. of " chemical progress "
2The preparation method of film ", can also be with reference to " preparation method of nano-titanium dioxide film and characterization technique " that November in 2005 the 19th of " material Leader ", honest and just little gorgeous grade was shown among the volume special edition V etc.
Yet, nano-TiO
2Film needs this requirement of UV-irradiation competence exertion effect that it is restricted on using.If film can use under visible light, do not need to adopt the intermittent type ultraviolet lighting to keep surperficial Superhydrophilic and then can improve film application in practice greatly.
In order to improve the utilization ratio of titanium deoxid film to visible light, many trials had been carried out, as application number be: (publication number: CN101069840A), this application adopts the reaction magnetocontrol sputtering coating system to prepare in 200710042334.5 Chinese invention patent application open " a kind of preparation method of carbon-doped nano titanium deoxid film of visible light activity "; And for example application number is that (publication number: CN101157521.A), this application is coated in TiO 2 sol by pulling machine on the conductive glass of carbon nanotube and finishes for the Chinese patent patent application open " nano titania coextruded film material of visible light activity and preparation method thereof " of 200710046178.X; The patent No. is for another example: the Chinese invention patent of 200410033800.X " having titanium deoxid film of high catalytic activity and preparation method thereof under visible light " (Granted publication number: CN1269992.C), this patent adds lithium salts and antimonic salt by sol-gel method in TiO 2 sol, make under the low-temperature heat treatment condition.
In sum, prior art does not also have specially at the document at the titanium deoxid film of aluminum or aluminum alloy surface preparation visible-light type, because of aluminum or aluminum alloy has advantages such as light weight, specific tenacity and specific rigidity are big, machining property is good, at mechanical component, the aircraft automobile parts, precision instrument and radio component parts, daily necessities and building decoration and field such as medical are widely used, and it is significant therefore to make up visible light Superhydrophilic surface on its surface.
Summary of the invention
Technical problem to be solved by this invention is the preparation method that a kind of visible-light type aluminum or aluminum alloy ultra-hydrophilic surface is provided at the above-mentioned state of the art.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: the preparation method of visible-light type aluminum or aluminum alloy ultra-hydrophilic surface comprises the steps:
1. dispose the ammonium titanium fluoride aqueous solution;
2. aluminum or aluminum alloy anodic oxidation makes its surface generate one deck porous oxide film;
3. liquid deposition is immersed the ammonium titanium fluoride aqueous solution of step in 1. with the aluminum or aluminum alloy after the anodic oxidation, after for some time is placed in the dehydration back, takes out aluminum or aluminum alloy, promptly forms TiO at microcosmic porous alumina surface after the drying
2Following chemical reaction, take place in nano particle:
[Ti
(6-n)(HO)
n]
2-Promptly form TiO after the dehydration at microcosmic porous alumina surface
2Nano particle;
4. thermal treatment will deposit TiO
2The aluminum or aluminum alloy of nano particle is put into heat treatment furnace and is carried out pyroprocessing, then cooling.
The ammonium titanium fluoride concentration of aqueous solution of step described in 1. is preferably 0.05～0.2mol/L.
The aluminum or aluminum alloy anodic oxidation of step described in 2. is preferably as follows: adopt acidic aqueous solution as electrolytic solution, current density is 0.5～5A/dm
2, oxidizing temperature is 0～30 ℃, and oxidization time is 0.5～3 hour, and further, it is one of following that described electrolytic solution is preferably: the H of 30～100g/L
3PO
4The H of the aqueous solution, 100～250g/L
2SO
4The C of the aqueous solution and 30～80g/L
2H
2O
4The aqueous solution is further optimized, and the 2. described aluminum or aluminum alloy anodic oxidation of step is as follows: with 50g/LC
2O
2O
4The aqueous solution is electrolytic solution, and current density is 1.5A/dm
2, oxidizing temperature is 10～15 ℃, oxidization time is 40 minutes.
As preferably, the liquid deposition temperature of step described in 3. is controlled at 50～100 ℃, and the time is 0.5～3 hour.
As preferably, step 4. described in the thermal treatment heat-up rate be 50 ℃/h, thermal treatment temp is 420～650 ℃.
As preferably, the ammonium titanium fluoride concentration of aqueous solution of step described in 1. is 0.5～1.5mol/L, and the liquid deposition temperature of step described in 3. is controlled at 60～80 ℃, depositing time 1.5 hours, 650 ℃ of thermal treatment temps.
Compared with prior art, the invention has the advantages that: simple, the good reproducibility of method preparation, the hydrophilic film on the aluminum or aluminum alloy surface that makes is under visible light, its water droplet promptly is tiled in the surface after dripping several seconds, contact angle approaches 0 °, therefore the hydrophilicity excellence has antifouling self-cleaning effect under visible light, and application prospect is extensive.
Description of drawings
Fig. 1 is the field emission scanning electron microscope figure of the water-wetted surface of embodiment 1 gained.
Fig. 2 is the water-wetted surface and the water contact angle state graph of embodiment 1 gained.
Fig. 3 is the field emission scanning electron microscope figure of the water-wetted surface of embodiment 2 gained.
Fig. 4 is the water-wetted surface and the water contact angle state graph of embodiment 2 gained.
Fig. 5 is the field emission scanning electron microscope figure of the water-wetted surface of embodiment 3 gained.
Fig. 6 is the water-wetted surface and the water contact angle state graph of embodiment 3 gained.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1: the aluminum or aluminum alloy sample of surperficial degrease is carried out anodic oxidation in the phosphoric acid electrolyte of 50g/L, oxygenation parameters is 2A/dm
2, 10 ℃, 2 hours.Immerse 0.05mol/L then, soak in 60 ℃ the ammonium titanium fluoride aqueous solution and put 1 hour, put into heat treatment furnace after the seasoning at 450 ℃ of thermal treatments 2 hours, furnace cooling.As can be seen from Figure 1, the vesicular structure of alumina surface still keeps, and has all deposited tiny nano particle in hole wall and the hole.As shown in Figure 2, the contact angle of surveying itself and water is 12 °.
Embodiment 2: the aluminum or aluminum alloy sample of surperficial degrease is carried out anodic oxidation in the oxalic acid electrolytic solution of 70g/L, oxygenation parameters is 1.5A/dm
2, 15 ℃, 1 hour.Immerse 0.1mol/L then, soak in 80 ℃ the ammonium titanium fluoride aqueous solution and put 1 hour, put into heat treatment furnace after the seasoning at 650 ℃ of thermal treatments 2 hours, furnace cooling.As can be seen from Figure 3, the regular porous structure of aluminum oxide disappears, surface arrangement the macrobead that is of a size of 150～300nm, the small-particle of each 20～30nm that distributing above the macrobead, as shown in Figure 4, water droplet almost completely tiles on this surface, presents fabulous super hydrophily, and the contact angle of surveying itself and water is near 0 °.
Embodiment 3: the aluminum or aluminum alloy sample of surperficial degrease is carried out anodic oxidation in the sulfuric acid electrolyte of 150g/L, oxygenation parameters is 2.5A/dm
2, 20 ℃, 1 hour.Immerse 0.15mol/L then, soak in 70 ℃ the ammonium titanium fluoride aqueous solution and put 2 hours, put into heat treatment furnace after the seasoning at 600 ℃ of thermal treatments 2 hours, furnace cooling.Show that as Fig. 5 deposited particles reaches the hole wall gathering and grows up in the hole of aluminum oxide, formation is of a size of the macrobead of 100～300nm, around reaching, each oarse-grained surface depositing the small-particle that is of a size of 20～30nm, as shown in Figure 6, water droplet is at this surface spreading, present super preferably hydrophily, the contact angle of surveying itself and water is 4～6 °.
Claims (9)
1, a kind of preparation method of visible-light type aluminum or aluminum alloy ultra-hydrophilic surface comprises the steps:
1. dispose the ammonium titanium fluoride aqueous solution;
2. aluminum or aluminum alloy anodic oxidation makes its surface generate one deck porous oxide film;
3. liquid deposition is immersed the ammonium titanium fluoride aqueous solution of step in 1. with the aluminum or aluminum alloy after the anodic oxidation, place for some time after, take out aluminum or aluminum alloy, promptly form TiO after the drying at microcosmic porous alumina surface
2Nano particle;
4. thermal treatment will deposit TiO
2The aluminum or aluminum alloy of nano particle is put into heat treatment furnace and is carried out pyroprocessing, then cooling.
2, preparation method according to claim 1 is characterized in that the ammonium titanium fluoride concentration of aqueous solution described in step 1. is 0.05～0.2mol/L.
3, preparation method according to claim 1 is characterized in that the aluminum or aluminum alloy anodic oxidation described in step 2., and is as follows: adopt acidic aqueous solution as electrolytic solution, current density is 0.5～5A/dm
2, oxidizing temperature is 0～30 ℃, oxidization time is 0.5～3 hour.
4, preparation method according to claim 3 is characterized in that described electrolytic solution is one of following: the H of 30～100g/L
3PO
4The H of the aqueous solution, 100～250g/L
2SO
4The C of the aqueous solution and 30～80g/L
2H
2O
4The aqueous solution.
5, preparation method according to claim 4 is characterized in that the 2. described aluminum or aluminum alloy anodic oxidation of step, and condition is as follows: with 50g/LC
2O
2O
4The aqueous solution is electrolytic solution, and current density is 1.5A/dm
2, oxidizing temperature is 10～15 ℃, oxidization time is for being 40 minutes.
6, preparation method according to claim 1 is characterized in that the liquid deposition temperature described in step 3. is controlled at 50～100 ℃, and the time is 0.5～3 hour.
7, preparation method according to claim 6 is characterized in that the liquid deposition temperature described in step 3. is controlled at 60～80 ℃, depositing time 1.5 hours.
8, preparation method according to claim 1 is characterized in that heat-up rate is 50 ℃/h in the thermal treatment described in step 4., and thermal treatment temp is 420～650 ℃.
9, preparation method according to claim 8 is characterized in that 4. 650 ℃ of thermal treatment temps in the thermal treatment of step.
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| Application Number | Priority Date | Filing Date | Title |
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| CN200810120739A CN101665972A (en) | 2008-09-03 | 2008-09-03 | Method for preparing ultra-hydrophilic surface of visible light type aluminum or aluminum alloy |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102825260A (en) * | 2012-06-28 | 2012-12-19 | 北京工业大学 | Method for preparing super-hydrophilic infiltrating surface on aluminum surface |
| CN103114330A (en) * | 2013-02-20 | 2013-05-22 | 北京工业大学 | Method for attaching titanium dioxide one-dimensional array on porous aluminium mesh used for sewage treatment |
| CN110573660A (en) * | 2017-04-13 | 2019-12-13 | 惠普发展公司，有限责任合伙企业 | Treating alloy substrates having oxide layers |
-
2008
- 2008-09-03 CN CN200810120739A patent/CN101665972A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102825260A (en) * | 2012-06-28 | 2012-12-19 | 北京工业大学 | Method for preparing super-hydrophilic infiltrating surface on aluminum surface |
| CN103114330A (en) * | 2013-02-20 | 2013-05-22 | 北京工业大学 | Method for attaching titanium dioxide one-dimensional array on porous aluminium mesh used for sewage treatment |
| CN103114330B (en) * | 2013-02-20 | 2015-11-18 | 北京工业大学 | A kind of method of sewage disposal porous aluminum net appendix titanium dioxide one-dimensional array |
| CN110573660A (en) * | 2017-04-13 | 2019-12-13 | 惠普发展公司，有限责任合伙企业 | Treating alloy substrates having oxide layers |
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