CN1445385A - Method for forming super hydrophilic film on metal board - Google Patents

Method for forming super hydrophilic film on metal board Download PDF

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Publication number
CN1445385A
CN1445385A CN 02104428 CN02104428A CN1445385A CN 1445385 A CN1445385 A CN 1445385A CN 02104428 CN02104428 CN 02104428 CN 02104428 A CN02104428 A CN 02104428A CN 1445385 A CN1445385 A CN 1445385A
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China
Prior art keywords
water
electrolysis
hydrophilic film
anode
super
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CN 02104428
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Chinese (zh)
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翟锦
江雷
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Institute of Chemistry CAS
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Institute of Chemistry CAS
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Priority to CN 02104428 priority Critical patent/CN1445385A/en
Publication of CN1445385A publication Critical patent/CN1445385A/en
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Abstract

A process for preparing ultra-hydrophilic film on the metal plate used in air conditioner or other antidewing metal plate includes such steps as cleaning high-purity (more than 70%) metal material, preparing electrolyte solution, and electrolyzing to form a film, where said metal material is used as anode and the graphit or Pt as cathode. Said the hydrophilic film with nano-structure (5-200 nm) has 5 deg of contact angle to water.

Description

On metal sheet, form the method for super-hydrophilic film
Technical field
The invention belongs to technical field of function materials, specially refer to the cooling top board in the cold drawing air-conditioning, the heating panel of radial pattern air-conditioning, and the method that forms super-hydrophilic film on the metal sheet of other antisweat.
Background technology
At present the refrigeration of air conditioning machinery mainly be by convection type Cryogenic air is forced to deliver to indoor, simultaneously with the refrigeration area of indoor warm air suction air conditioning machinery.This moment, exchange took place in indoor air, thereby reached the purpose that reduces room temperature.The shortcoming of this air-conditioning is that comfort is relatively poor.Be the Refrigeration Technique of improving the cooling top board of air-conditioning, be the cold drawing that 00249469,00218313 and 95233326 patents of being applied for are semiconductor refrigerating as number of patent application, but the material on cold drawing surface be generally common metallic substance and report more.In order to improve the level of comfort of air conditioning machinery, should adopt the radiating mode to reduce room temperature.But at present because the restriction of cold drawing metallic substance character, when using large-area cooling top board, when the humidity of air is bigger, and the temperature of cold drawing is lower, and at this moment water vapor just very easily forms condensation on metallic cold plate.Condensation not only can generate big water droplet, produces dripping phenomenon, but also can have influence on the conduction of heat, causes the refrigeration of air conditioning machinery and comfort level all not good enough.Therefore, develop prevent dewfall, can be used for that the metallic substance of cold drawing is very important in the air-conditioning.And ultra-hydrophilic surface (promptly to the contact angle of water less than 5 °) not only helps sprawling rapidly of water and do not form condensation, and helps the rapid evaporation of water.So construct one deck oxide nano structure in the metallic surface is one of best approach of preparation ultra-hydrophilic surface.
Summary of the invention
The purpose of this invention is to provide a kind of cooling top board, the heating panel of radial pattern air-conditioning in the cold drawing air-conditioning, and the method that forms super-hydrophilic film on the metal sheet of other antisweat.This film covers the surface of metal base, has super hydrophilic and super lipophilic super parents' characteristic, can be lower than 5 ° with the contact angle of water, with the contact angle of oil be 0 °, easily on metallic cold plate, form condensation to overcome water vapor, produce dripping phenomenon, improve the refrigeration and the comfort level of air conditioning machinery.
Principle of the present invention:
In order to obtain uniformly and film, can adopt the method for electrolytic oxidation at normal temperatures with certain nanostructure in metallic substrate surface.The oxidation of anode dissolution and anode itself during as anode, promptly takes place in metal in electrolyzer.Anode dissolution and anodised speed depend on current potential and electrode materials composition structure.When anodic polarization in the oxygen evolution potential scope, metallic surface will be covered by one deck hydrated metal oxide film, so regulating voltage and electric current can be regulated the membrane structure of metal oxide surface, thereby forms the film (seeing accompanying drawing) of nanostructure.Because the existence of surface nano-structure has increased surface energy, water and general liquid can drawouts on the surface of high energy, so make this surface embody super hydrophilic and super lipophilic character.
The method that forms super-hydrophilic film on metal sheet of the present invention is to form super-hydrophilic film by electrolytic method on metal sheet at normal temperatures, and this method steps is:
(1) purity that has that will select for use cleans up back standby at the metallic substance more than 70%.
(2) preparation electrolyte solution, concentration is controlled at 0.1-5M.Selected ionogen can be sulfuric acid, nitric acid, perchloric acid, hydrochloric acid, potassium hydroxide or sodium hydroxide etc.
(3) with metallic substance as anode, graphite or platinum carry out electrolysis as negative electrode, voltage is adjusted in the 1V-50V scope, current density during the control electrolysis is that 0.1A-5A and electrolysis time are 1 minute-60 minutes, through behind the certain hour, treat the metallic surface form layer of even, when having the nano structure membrane of obvious metalluster, electrolysis can stop.This film has super hydrophilic and super oleophilic properties, with the contact angle of water can be less than 5 °, with the contact angle of octadecane be 0 °.
(4) after being rinsed well, can use the metallic substance water after the electrolysis.
The particle diameter of the super hydrophilic nanostructure of described metal is between the 5-200nm.
Described thin-film material can be used for conditioner, cold blast engine, scatterer and other prevents on the metal device of water vapor dewfall.
Described metallic substance relates to Ti, Ni, Cu, Zn or the Al etc. in light metal element and the transition metal.
Method of the present invention does not have strict restriction to the shape and size of metallic substance, and method is simple, favorable repeatability, and exercisable voltage and time range are wide, can once formalize, and the prepared film that goes out is very even, and color is beautiful, has metalluster.The super-hydrophilic film that method of the present invention is prepared be close attachment on metal base, be metallic film material with nanostructure.
Contact angle is carried out on the surface of this kind film measures (details is discussed with the following Examples) and water storage contrast experiment, find that this kind material has Superhydrophilic matter, with the contact angle of water be about 5 °.For area is 2.25cm 2The plain metal sheet and the tinsel after the super hydrophilic treatment, when carrying out the water storage contrast experiment, we find when volume be the water droplet of 0.3ml when tinsel is surperficial, water just begins to overflow.And volume be the water droplet of 1ml on the tinsel after the super hydrophilic treatment, just begin to overflow, promptly the storage capacity of super-hydrophilic film is about more than 3 times of plain metal base material.The prepared nano film material of the present invention can be used for the cooling top board in the air conditioning machinery, the heating panel of radial pattern air-conditioning, and the metallic substance of other antisweat.
The nano film material that the present invention is prepared is used for the cooling top board of air-conditioning, meets coldly when condensing on the cooling top board when water vapor, just can sprawl into moisture film rapidly, and not form water droplet, helps the rapid evaporation of water like this, prevents that dewfall from dripping.In addition, ultra-hydrophilic surface has increased the degree of sprawling of water, thereby compares with undressed metallic substance, and it can hold a large amount of relatively water.Utilize evaporation of water latent heat very big, these water that spread over the metallic surface can absorb the heat in the surrounding environment when evaporation, so can utilize radiation mode to freeze, thereby improve the level of comfort of air-conditioning greatly.The utilization of this film for the development of radial pattern air conditioning machinery provides favorable factor, can be quickened the upgrading of air conditioning machinery.
Method of the present invention has following characteristics:
1. the preparation method is easy at normal temperatures, easily goes favorable repeatability, exercisable voltage and time range broad.
2. the film of preparing is very even, and color is beautiful, has metalluster, and outward appearance is beautiful.
3. this preparation method is applicable to the finishing of multiple metallic substance, and shape, the size of material are not strict with.
Description of drawings
Fig. 1. the result of embodiments of the invention 1.Left side figure is the atomic force microscope photo of the aluminium oxide nano structure that forms behind the electrolysis aluminium, and its median size is 51nm; Right figure is the atomic force microscope photo of aluminium when not doing electrolysis.
Embodiment
Embodiment 1
At first, be that the aluminium water of 1mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.3M, is negative electrode with the platinum filament, is anode with the aluminium, carries out potentiostatic deposition, during voltage 20V, and current density 3-4 ampere, electrolysis 2-3 minute, after taking out the back water and rinsing well, the contact angle of surveying itself and water was 5.8 °.
Embodiment 2
At first, be that the aluminium water of 1mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.3M, is negative electrode with the platinum filament, is anode with the aluminium, carries out potentiostatic deposition, during voltage 10V, and 0.1 ampere of current density, electrolysis 5 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 3.7 °.
Embodiment 3
At first, be that the aluminium water of 1mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.3M, is negative electrode with the platinum filament, is anode with the aluminium, carries out potentiostatic deposition, during voltage 10V, and 0.1 ampere of current density, electrolysis 10 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 9.8 °.
Embodiment 4
At first, be that the aluminium water of 1mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.3M, is negative electrode with the platinum filament, is anode with the aluminium, carries out potentiostatic deposition, during voltage 15V, and 1 ampere of current density, electrolysis 5 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 8.8 °.
Embodiment 5
At first, be that the aluminium water of 1mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.1M, is negative electrode with the platinum filament, is anode with the aluminium, carries out potentiostatic deposition, during voltage 40V, and electrolysis 5 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 7 °.
Embodiment 6
At first, be that the titanium plate water of 1mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.5M, is negative electrode with the platinum filament, is anode with the titanium plate, carries out potentiostatic deposition, during voltage 15V, and electrolysis 5 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 6 °.Embodiment 7
At first, be that the aluminium water of 5mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.3M, is negative electrode with graphite, is anode with the aluminium, carries out potentiostatic deposition, and during voltage 40V, electrolysis 15-20 minute, after taking out the back water and rinsing well, the contact angle of surveying itself and water was 4 °.
Embodiment 8
At first, be that the metallic titanium plate water of 2mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.3M, is negative electrode with the platinum filament, is anode with the titanium material, carries out potentiostatic deposition, during voltage 40V, and electrolysis 5 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 7 °.
Embodiment 9
At first, be that the metallic titanium plate water of 3mm cleans up with selecting thickness for use, standby.Sodium hydroxide is mixed with the aqueous solution that concentration is 0.2M, is negative electrode with the platinum filament, is anode with the titanium material, carries out potentiostatic deposition, during voltage 15V, and electrolysis 5 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 5 °.
Embodiment 10
At first, be that the copper coin water of 1mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.2M, is negative electrode with graphite, is anode with the copper coin, carries out potentiostatic deposition, during voltage 30V, and electrolysis 10 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 6 °.
Embodiment 11
At first, be that the zine plate water of 5mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.1M, is negative electrode with the platinum filament, is anode with the zine plate, carries out potentiostatic deposition, during voltage 10V, and current density 0.5 amperes, electrolysis 10 minutes, after taking out the back water and rinsing well, the contact angle of surveying itself and water is 7 °.
Embodiment 12
At first, be that the nickel plate water of 3mm cleans up with selecting thickness for use, standby.The vitriol oil is mixed with the aqueous solution that concentration is 0.3M, is negative electrode with graphite, is anode with the nickel plate, carries out potentiostatic deposition, and during voltage 30V, electrolysis 15-20 minute, after taking out the back water and rinsing well, the contact angle of surveying itself and water was 6 °.

Claims (3)

1. method that forms super-hydrophilic film on metal sheet is characterized in that: form super-hydrophilic film by electrolytic method on metal sheet at normal temperatures, steps of the method are:
(1) purity that has that will select for use cleans up back standby at the metallic substance more than 70%;
(2) preparation electrolyte solution, concentration is controlled at 0.1-5M;
(3) with metallic substance as anode, graphite or platinum carry out electrolysis as negative electrode, treat metal material surface form layer of even, when having the nano structure membrane of obvious metalluster, electrolysis can stop, described nanometer particle size is between the 5-200nm;
Described ionogen is sulfuric acid, nitric acid, perchloric acid, hydrochloric acid, potassium hydroxide or sodium hydroxide.
2. the method for claim 1, it is characterized in that: described step (3) voltage is adjusted in the 1V-50V scope, and current density is 0.1A-5A, and electrolysis time is 1 minute-60 minutes.
3. the method for claim 1, it is characterized in that: described metal is Ti, Ni, Cu, Zn or Al.
CN 02104428 2002-03-14 2002-03-14 Method for forming super hydrophilic film on metal board Pending CN1445385A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7651863B2 (en) 2005-07-14 2010-01-26 3M Innovative Properties Company Surface-enhanced spectroscopic method, flexible structured substrate, and method of making the same
US7906057B2 (en) 2005-07-14 2011-03-15 3M Innovative Properties Company Nanostructured article and method of making the same
CN101556126B (en) * 2008-04-09 2011-08-17 中国科学院化学研究所 Film with high heat conduction efficiency and antifouling capability and preparation method thereof
CN102517576A (en) * 2011-12-22 2012-06-27 北京工业大学 Preparation method of simple long-acting super-hydrophilic molybdenum surface
CN108204702A (en) * 2016-12-20 2018-06-26 松下电器产业株式会社 Dew removing structure and the cold and hot equipment for having dew removing structure

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7651863B2 (en) 2005-07-14 2010-01-26 3M Innovative Properties Company Surface-enhanced spectroscopic method, flexible structured substrate, and method of making the same
US7888129B2 (en) 2005-07-14 2011-02-15 3M Innovative Properties Company Surface-enhanced spectroscopic method, flexible structured substrate, and method of making the same
US7906057B2 (en) 2005-07-14 2011-03-15 3M Innovative Properties Company Nanostructured article and method of making the same
CN101556126B (en) * 2008-04-09 2011-08-17 中国科学院化学研究所 Film with high heat conduction efficiency and antifouling capability and preparation method thereof
CN102517576A (en) * 2011-12-22 2012-06-27 北京工业大学 Preparation method of simple long-acting super-hydrophilic molybdenum surface
CN108204702A (en) * 2016-12-20 2018-06-26 松下电器产业株式会社 Dew removing structure and the cold and hot equipment for having dew removing structure

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