CN102303006B - Method for preparing metal carboxylate super-hydrophobic coating layer on metal surface - Google Patents
Method for preparing metal carboxylate super-hydrophobic coating layer on metal surface Download PDFInfo
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- CN102303006B CN102303006B CN2011102142766A CN201110214276A CN102303006B CN 102303006 B CN102303006 B CN 102303006B CN 2011102142766 A CN2011102142766 A CN 2011102142766A CN 201110214276 A CN201110214276 A CN 201110214276A CN 102303006 B CN102303006 B CN 102303006B
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Abstract
The invention relates to a method for preparing a metal carboxylate super-hydrophobic coating layer on a metal surface. The method is characterized in rapid reaction, no needing immersion and only needing to coat a reaction solution onto a metal plate surface. Used raw materials are common and have low prices so that the cost of preparing the super-hydrophobic coating layer is greatly reduced; in addition, the method provided by the invention can be applied to the super-hydrophobic coating layer preparation on multiple varieties of metal surfaces, the application range of the super-hydrophobic coating layer is widened, and the scale production is ensured to be more market values.
Description
Technical field
The present invention relates to a kind of metal carboxylate super-hydrophobic coating layer on metal surface preparation method, the invention belongs to functional material, metal surface modification and protection field.
Background technology
The surface of solids all has certain surface energy, and surface can directly affect solid this wellability of the wellability of liquid is characterized by passing through Young ' s equation.(structure, composition homogeneous) contact angle has specific value on the desirable surface of solids, and is determined by surface tension, meets Young ' s equation
cosθ＝(γ
sg-γ
sl)/γ
lg
γ
Sg, γ
Sl, γ
LgBe respectively the interfacial tension between solid and gas, solid-liquid, gas-liquid.
All coarse injustice or component differ the actual surface of solids to a certain extent.So contact angle and Young ' the s equation result of calculation measured have larger difference.Wenzel and Cassie etc. have disclosed respectively in eighties of last century the forties, and the infiltrating impact of heterogencity effects on surface of real surface, revised Young ' s equation.
The Wenzel discovery, surface of solids coarse structure causes the actual contact of solid-liquid to be greater than apparent contact area, draws equation,
cosθ′＝r(γ
sg-γ
sl)/γ
lg r≥1
R is roughness.If when θ<90 °, θ '<θ, namely the hydrophily on surface strengthens with the increase of surface roughness; If θ>90 °, θ '>θ, namely the hydrophobicity on surface strengthens with the increase of surface roughness.
Cassie etc. have studied the infiltrating impact of inhomogeneity effects on surface formed, and obtain equation
cosθ′＝α
1cosθ
1+α
2cosθ
2
α i is the weight fraction that forms each component of surface, α 1+ α 2=1.That is, non-homogeneous components surface, wellability be each component infiltrating add and.
The ground surface energy effect of super hydrophobic surface, have boundless application prospect in industrial production and daily life.The resistance of the discoveries such as Barrat when the coarse super hydrophobic surface of microfluid inner-walls of duct coating can reduce microfluid by passage; Communication quality variation or interruption that super-hydrophobic surface coating also can avoid accumulated snow to cause for satellite earth antenna.Has important military strategy meaning; Super hydrophobic surface has self-cleaning property, is applied to exterior wall, the glass curtain wall of high-rise, and the dust on it can be saved in a large number manually along with the rainwater automated cleaning, and safety and environmental protection; After in metal surface, building super-hydrophobic coat, can prevent that metal and airborne moisture from reacting, namely prevent getting rusty, like this, can save great deal of steel every year.Significant to national product.
Wang Shutao, Feng Lin, Jiang Lei etc. have invented a kind of " the solution submergence prepares the method for super-hydrophobic coat ".This method is carried out chemical synthesis by copper coin being immersed in the tetradecylic acid ethanolic solution.After submergence 3 days, take out copper coin, clean and dry, obtain super-hydrophobic coat.Its contact angle is that 162 ° of roll angles are less than 2 °.
Li Mei, Xu Jianhai, Lu Qinghua etc. have invented " by wet chemistry, preparing the method for super-hydrophobic coat on nickel sheet surface ".This method need to be immersed in the nickel sheet of pickling alkali cleaning 3-5 days in the monoalkyl-phosphonic acid ethanolic solution of 0.01mol/L.Take out to clean and dry afterwards and namely obtain super-hydrophobic coat.
At present, super-hydrophobic coat also is not widely used in daily life.This is because prior art needs tediously long technique mostly, and complex process is with high costs, needs special installation and expensive all factors that are unfavorable for large-scale production such as material.Therefore, invent a kind of equipment simple, cheap, the technology for preparing rapidly prepares super-hydrophobic coat and just seems particularly important.In prior art, consuming time tediously long,
Summary of the invention
The technical problem solved
For fear of the deficiencies in the prior art part, the present invention proposes a kind of metal carboxylate super-hydrophobic coating layer on metal surface preparation method, and a kind of the preparation rapidly, cost is lower, simple and convenient, is suitable for the industrial method for preparing the metal surface superhydrophobic coating.
Technical scheme
A kind of metal carboxylate super-hydrophobic coating layer on metal surface preparation method is characterized in that step is as follows:
Step 1 preparation reaction solution: slaine and aliphatic acid and ethanol are made to the ethanolic solution of 0.01mol/L to 10mol/L, described slaine is CuCl
2Or FeCl
3, described aliphatic acid is CH
3(CH
2)
12COOH, slaine mole ratio aliphatic acid molal quantity equals 1 than metal ion chemical valence, M[CuCl
2]: M[CH
3(CH
2)
12COOH]=1: 2, M[FeCl
3]: M[CH
3(CH
2)
12COOH]=1: 3;
Step 2 pair metallic plate carries out surface treatment: adopt abrasive paper for metallograph 80 orders～1000 order polishing metallic plates to remove surface oxide layer, then with distilled water, clean and dry; Metallic plate is dipped in to ultrasonic cleaning 5min～35min in ethyl acetate solution, removes surface and oil contaminant, then with distilled water, clean and dry;
Step 3: the solution that adopts the mode of smearing that step 1 is prepared is applied to the metal sheet surface that step 2 is handled well;
Step 4: the metallic plate that will scribble solution is immersed in deionized water and cleans, and at room temperature dries after taking-up, obtains the metal carboxylate super-hydrophobic coat.
The described mode of smearing is spray gun spraying or applies with absorbent cotton.
Beneficial effect
A kind of metal carboxylate super-hydrophobic coating layer on metal surface preparation method that the present invention proposes, be swift in response, without submergence, as long as reaction solution is coated to metal sheet surface.The raw material that this method adopts is common and cheap, greatly reduces the cost for preparing super-hydrophobic coat.In addition, this method can prepare super-hydrophobic coat on the various metals surface, has widened the range of application of super-hydrophobic coat, makes large-scale production have more market value.
The accompanying drawing explanation
The metal carboxylate super-hydrophobic coat scanning electron microscope (SEM) photograph that Fig. 1: embodiment 1 obtains;
The metal carboxylate super-hydrophobic coat hydrophobic effect figure that Fig. 2: embodiment 1 obtains;
The metal carboxylate super-hydrophobic coat coating composition EDS spectrum that Fig. 3: embodiment 1 obtains.
The specific embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Example 1:
(1) the fine copper plate is carried out to surface treatment.With 600 order abrasive paper for metallograph, polish to remove surface oxide layer, with distilled water, clean and dry afterwards.
(2) the fine copper plate is dipped in to ultrasonic cleaning 10min in 99% ethyl acetate solution, removes surface and oil contaminant, with distilled water, clean and dry afterwards.
(3) use 1.7gCuCl
22H
2O and 100mL mass fraction are the solution of 99.7% ethanolic solution preparation 0.1mol/L.The solution prepared is coated on the fine copper plate of handling well.
The fine copper plate that (4) will apply solution is immersed in water and cleaned several minutes, takes out dry 2h under room temperature and namely obtains super-hydrophobic coat.Contact angle is about 170 ° of roll angles and is less than 2 °.
Example 2:
(1) iron plate is carried out to surface treatment.With 240 order abrasive paper for metallograph, polish to remove surface oxide layer, with distilled water, clean and dry afterwards.
(2) metallic plate is dipped in to ultrasonic cleaning 20min in 99% ethyl acetate solution, removes surface and oil contaminant, with distilled water, clean and dry afterwards.
(3) use 5.5g FeCl
36H
2O and 100mL mass fraction are the solution of 99.7% ethanol preparation 0.2mol/L.
The solution prepared is coated on the iron plate of handling well.
The iron plate that (4) will apply the mistake of solution is immersed in water and cleaned several minutes, takes out dry 2h under room temperature and namely obtains super-hydrophobic coat.Contact angle is about 165 ° of roll angles and is less than 2 °.
Claims (1)
1. metal carboxylate super-hydrophobic coating layer on metal surface preparation method is characterized in that step is as follows:
Step 1 preparation reaction solution: slaine and aliphatic acid and ethanol are made to the ethanolic solution of 0.01mol/L to 10mol/L, described slaine is CuCl
2Or FeCl
3, described aliphatic acid is CH
3(CH
2)
12COOH, slaine mole ratio aliphatic acid molal quantity equals 1 than metal ion chemical valence, M[CuCl
2]: M[CH
3(CH
2)
12COOH]=1: 2, M[FeCl
3]: M[CH
3(CH
2)
12COOH]=1: 3;
Step 2 pair metallic plate carries out surface treatment: adopt abrasive paper for metallograph 80 orders～1000 order polishing metallic plates to remove surface oxide layer, then with distilled water, clean and dry; Metallic plate is dipped in to ultrasonic cleaning 5min～35min in ethyl acetate solution, removes surface and oil contaminant, then with distilled water, clean and dry;
Step 3: the solution that adopts the mode of smearing that step 1 is prepared is applied to the metal sheet surface that step 2 is handled well;
Step 4: the metallic plate that will scribble solution is immersed in deionized water and cleans, and at room temperature dries after taking-up, obtains the metal carboxylate super-hydrophobic coat.
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| CN2011102142766A CN102303006B (en) | 2011-07-28 | 2011-07-28 | Method for preparing metal carboxylate super-hydrophobic coating layer on metal surface |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011102142766A CN102303006B (en) | 2011-07-28 | 2011-07-28 | Method for preparing metal carboxylate super-hydrophobic coating layer on metal surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102303006A CN102303006A (en) | 2012-01-04 |
| CN102303006B true CN102303006B (en) | 2013-11-27 |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352499A (en) * | 2011-09-08 | 2012-02-15 | 西北工业大学 | Method for preparing metal carboxylate super-hydrophobic coating on surface of metal |
| CN109518175B (en) * | 2018-11-29 | 2022-04-01 | 鲁东大学 | Super-hydrophobic metal surface coating and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440510A (en) * | 2007-11-21 | 2009-05-27 | 国家纳米科学中心 | Preparation of super-hydrophobic surface for metal anti-corrosive and self-cleaning effects |
| CN102041534A (en) * | 2010-10-14 | 2011-05-04 | 西北工业大学 | Method for simultaneously preparing two types of super-hydrophobic films by utilizing copper chloride |
-
2011
- 2011-07-28 CN CN2011102142766A patent/CN102303006B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101440510A (en) * | 2007-11-21 | 2009-05-27 | 国家纳米科学中心 | Preparation of super-hydrophobic surface for metal anti-corrosive and self-cleaning effects |
| CN102041534A (en) * | 2010-10-14 | 2011-05-04 | 西北工业大学 | Method for simultaneously preparing two types of super-hydrophobic films by utilizing copper chloride |
Non-Patent Citations (2)
| Title |
|---|
| One-step solution-immersion process for the fabrication of stable bionic superhydrophobic surfaces;Shutao Wang et al.;《Advanced Materials》;20061231;第18卷(第6期);第767-770页 * |
| Shutao Wang et al..One-step solution-immersion process for the fabrication of stable bionic superhydrophobic surfaces.《Advanced Materials》.2006,第18卷(第6期),第767-770页. |
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Granted publication date: 20131127 Termination date: 20160728 |