CN101942663B - Compound method for preparing magnesium alloy having superhydrophobic surface - Google Patents
Compound method for preparing magnesium alloy having superhydrophobic surface Download PDFInfo
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- CN101942663B CN101942663B CN2010105208987A CN201010520898A CN101942663B CN 101942663 B CN101942663 B CN 101942663B CN 2010105208987 A CN2010105208987 A CN 2010105208987A CN 201010520898 A CN201010520898 A CN 201010520898A CN 101942663 B CN101942663 B CN 101942663B
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Abstract
The invention relates to a compound method for preparing a superhydrophobic surface of magnesium alloy, which comprises the following steps: carrying out chemical etching on the surface of the magnesium alloy with sulfuric acid to construct a primary minute structure, and then simultaneously constructing a secondary structure and carrying out low-surface energy modification on the surface of the magnesium alloy by an anodic oxidation process to obtain the magnesium alloy surface which enables water drops not to adhere easily and has fine superhydrophobicity. The technical method of the invention has the following advantages: 1) the contact angle between the prepared magnesium alloy surface and water is up to 160 degrees, and the surface has low adhesion and excellent superhydrophobicity; 2) the superhydrophobic surface is prepared by combining chemical etching and electrochemical processes, thereby achieving better hydrophobicity and stability; 3) the construction of the secondary structure and the low-surface energy modification are simultaneously carried out by using the anodic oxidation process, thereby further optimizing the minute structure and ensuring prefarably bonding force between film and substrate; and 4) the invention has the characteristics of simple preparation process and required equipment, high preparation process efficiency, easy operation, high controllability, low combined cost and easy industrialized application.
Description
Technical field
The present invention relates to a kind of method for preparing super-hydrophobic surface of magnesiumalloy,, and adopt reaction reagent with low cost, obtain super-hydrophobic Mg alloy surface through the Combined Processing of chemical method and electrochemical process.
Background technology
Magnesiumalloy is described as " the green engineering material of 21 century ", has that light specific gravity, specific tenacity and specific rigidity are high, a damping and amortization and machinability is good, thermal conductivity is good, electromagnetic shielding ability and capability of resistance to radiation are strong, is easy to the advantage of a series of uniquenesses such as reclaiming.Aspects such as energy-saving and environmental protection, automobile lightweight had vital role; Having extremely important using value and wide application prospect at automobile, electronics, electrical equipment, traffic, space flight, aviation and national defense and military industrial circle, is the 3rd metalloid structured material that after iron and steel and duraluminum, grows up.But magnesiumalloy is because the influence of factor such as self chemically reactive is high, extremely sensitive to impurity element, the corrosion potential in typical media is very low, the sull MgO that in air, forms comparatively loosens; Corrosion resisting property is poor; Can not play a protective role to magnesium matrix, therefore restrict the performance and the resources advantage of its performance structured material all the time.
The material that the surface has a super-hydrophobicity has extremely wide application prospect at waterproof, self-cleaning, aspect such as anti-corrosion.In recent years; Growing along with nano material preparation technology and structural analysis characterization techniques; The material that design and preparation have a superhydrophobic characteristic has all been obtained breakthrough progress from theory into action, and the research of this respect also becomes one of forward position and focus of ambits such as Materials science, biology, bionics.Research with super-hydrophobicity is inspiration, after Mg alloy surface makes up microtexture, modifies the low surface energy material again, can obtain superhydrophobic characteristic, thereby makes its hydrophobic with super hydrophobic material, special performance such as self-cleaning, anti-corrosion.This provides a new thinking for the corrosion prevention that solves magnesiumalloy, has important significance for theories and great application prospect.
Existing super-hydrophobic metallic surface preparation method is a lot of both at home and abroad; Mostly be on metals such as steel, iron, aluminium, copper, zinc, to prepare; All can obtain the super hydrophobic surface of excellent performance; But still have certain problem, like complex process, need specific installation and starting material, length consuming time, have and pollute and shortcomings such as comprehensive cost height.And magnesiumalloy self unique chemical activity makes the method for preparing super-hydrophobic surface that on other metals, is suitable for can not be suitable for its surface equally.Preparing method's limitation causes to the correlative study of magnesium alloy super-hydrophobic surface comparatively rare, still is the difficult point of metal current substrate superhydrophobic surface preparation field.Kang Zhi newly waits in " preparation method of metallic surface super-hydrophobic organic nano film " (patent No. CN200810220287.3), to mention and adopts acetate that Mg alloy surface is carried out the chemical etching processing; The structure microtexture adopts the method for organic film plating to carry out the low surface energy modification at the Mg alloy surface through etching processing again.The building method of coarse structure is simple and easy to do, but the organic film plating electrolytic solution that uses contains triazine organic compound organic salt, borons acid sodium and Sodium Nitrite, complicated component, the complicated difficult control of modification process.This study group has also adopted the method for differential arc oxidation to construct microtexture at Mg alloy surface; Low surface energy is modified the same organic film plating that adopts; Prepared well behaved magnesium alloy super-hydrophobic surface; But still have the difficult control of complicated process of preparation, need specific installation, and the problem such as suitability for industrialized production that is not suitable for high costs.Wang Yanhua etc. have proposed a kind of comparatively simple and convenient preparation method in " a kind of preparation method of metallic magnesium surface ultra-hydrophobic water film " (patent No. CN201010102884.3); Adopting sulfuric acid that Mg alloy surface is carried out chemical etching earlier handles; Utilize ydrogen peroxide 50 that the magnesiumalloy of handling through chemical etching is carried out oxide treatment again; Thereby construct surface fine structure, the magnesiumalloy substrate that will pass through above-mentioned processing at last places stearic ethanolic soln to soak to carry out in 1～3 hour low surface energy to modify.Though equipment is not had particular requirement, preparation technology is comparatively easy, still be divided into multistep and accomplish whole process of preparation, and long poor controllability consuming time.
Therefore seek a kind of truly simple and easy to do, with low cost, and the method for can obtained performance good super-hydrophobic Mg alloy surface, be still the emphasis of present research.
Summary of the invention
The invention provides a kind of compound preparation method,, and adopt reaction reagent with low cost, obtain super-hydrophobic Mg alloy surface through the Combined Processing of chemical method and electrochemical process with magnesiumalloy of super hydrophobic surface.
The present invention adopts following technical scheme:
A kind of compound preparation method with magnesiumalloy of super hydrophobic surface, said method comprises the following steps:
(1) adopting mass and size concentration is that the aqueous sulfuric acid of 5g/L～20g/L carries out chemical etching to Mg alloy surface and handles, and etching temperature is 20 ℃～30 ℃, and etching time is 5min～10min,
(2) adopt myristic acid solution as electrolytic solution, use anonizing, Mg alloy surface is carried out simultaneously the modification of the structure and the low surface energy of secondary structure; Described myristic acid solution is that myristic acid, glycerine are dissolved in the ethanol, and myristic acid concentration is 2wt%～6wt%, and glycerol concentration is 0.6wt%～1.6wt%; Alcohol concn is 92.4wt%～97.4wt%, and described anodic oxidation is: be negative electrode with nickel, the magnesiumalloy of handling through above-mentioned chemical etching is an anode; Place myristic acid electrolytic solution, electrolysis temperature is 20 ℃～30 ℃, and voltage is 3V～10V; Electrolysis time is 0.5 hour～2 hours
(3) after the anodize, take out magnesiumalloy, be placed in the cabinet-type electric furnace through washed with de-ionized water, 50 ℃-90 ℃ following solidification treatment 0.5-1.5 hour.
Technological method provided by the invention has following advantage:
The present invention adopts the low tractable sulphuric acid soln etching processing Mg alloy surface that pollutes; Make up the one-level coarse structure; Carry out the modification of the structure and the low surface energy of secondary coarse structure through anodic oxidation simultaneously at Mg alloy surface then, obtained the super-hydrophobic Mg alloy surface of ideal.The electrolytic solution that uses is pollution-free, composition is single and cheap.This method device simple, easy to operate, preparation technology is simple and easy to do, and significantly reduces preparation cost, is easy to industrial applications.
1. the magnesium alloy materials of handling through the present invention has good ultra-hydrophobicity, and contact angle can be up to 160 °, and stick very little.
2. the super hydrophobic surface that the method that adopts chemical etching to combine with anodic oxidation prepares, hydrophobic performance are more excellent and stability is better.
3. not only make the structure of secondary structure and the modification of low surface energy carry out simultaneously through anodised method, the microtexture of having gone forward side by side one-step optimization, and film-substrate cohesion is better.
4. preparation technology and required equipment are simple, easy handling, efficient height, and comprehensive cost is cheap, is easy to industrial applications.Simultaneously, the reagent that electrolytic solution adopts is only elementary composition by C, H, three kinds of O, environmentally safe.
Description of drawings:
After Fig. 1 aqueous sulfuric acid carries out the chemical etching processing to Mg alloy surface, the one-level coarse structure figure of surface construction.
Fig. 2 is myristic acid concentration 3wt%, and after etching-anodize of glycerol concentration 0.9wt%, the sem photograph of Mg alloy surface microtexture and water droplet are in the state graph on this surface.
Fig. 3 is myristic acid concentration 3wt%, and water droplet is at the adhesion figure of Mg alloy surface after etching-anodize of glycerol concentration 0.9wt%.
Fig. 4 is myristic acid concentration 6wt%, and after etching-anodize of glycerol concentration 1.4wt%, the sem photograph of Mg alloy surface microtexture and water droplet are in the state graph on this surface.
Fig. 5 is myristic acid concentration 6wt%, and water droplet is at the adhesion figure of Mg alloy surface after etching-anodize of glycerol concentration 1.4wt%.
Embodiment
Embodiment 1
Utilize concentration to handle for the aqueous sulfuric acid of 7g/L carries out chemical etching to the AZ31 Mg alloy surface, etching temperature is 20 ℃, and etching time is 10min, with at its surface construction one-level coarse structure [shown in Figure 1].To the used for magnesium alloy washed with de-ionized water after the sulfuric acid etching, remove remaining sulfuric acid, take out dry for standby then;
Preparation myristic acid electrolytic solution: myristic acid, glycerine are dissolved in the ethanol, and myristic acid concentration is 3wt%, and glycerol concentration is 0.9wt%, and alcohol concn is 96.1wt%.
With nickel is negative electrode, and the magnesiumalloy of handling through above-mentioned chemical etching is an anode, places myristic acid electrolytic solution, and electrolysis temperature is 20 ℃, and voltage is 3V, and electrolysis time is 1 hour.After the anodize, take out magnesiumalloy, be placed in the cabinet-type electric furnace,, take out the back air cooling 90 ℃ of following solidification treatment 0.5 hour through washed with de-ionized water.
Sample is after over etching-anodize, and surface tissue is as shown in Figure 2, and lower left corner illustration is for amplifying pattern.Through detecting, the contact angle of sample and water is 160 ° (being 50 °) before the processing, accordingly water droplet at the state of sample surfaces shown in the illustration of Fig. 2 upper right corner.The adhesion situation is as shown in Figure 3.
Embodiment 2
Utilize concentration to handle for the aqueous sulfuric acid of 15g/L carries out chemical etching to the AZ31 Mg alloy surface, etching temperature is 20 ℃, and etching time is 5min, with at its surface construction one-level coarse structure.To the used for magnesium alloy washed with de-ionized water after the sulfuric acid etching, remove remaining sulfuric acid, take out oven dry then;
Preparation myristic acid electrolytic solution: myristic acid, glycerine are dissolved in the ethanol, and myristic acid concentration is 6wt%, and glycerol concentration is 1.4wt%, and alcohol concn is 92.6wt%.
With nickel is negative electrode, and the magnesiumalloy of handling through above-mentioned chemical etching is an anode, places myristic acid electrolytic solution, and electrolysis temperature is 20 ℃, and voltage is 7V, and electrolysis time is 0.5 hour.After the anodize, take out magnesiumalloy, be placed in the cabinet-type electric furnace through washed with de-ionized water, 90 ℃ of following solidification treatment 0.5 hour, air cooling was taken out in the back.
Sample is after over etching-anodize, and the contact angle of sample and water is 161 ° (being 50 °) before the processing, and corresponding water droplet is as shown in Figure 4 at the state of sample surfaces.The adhesion situation is as shown in Figure 5.
Embodiment 3
A kind of compound preparation method with magnesiumalloy of super hydrophobic surface, said method comprises the following steps:
(1) adopting mass and size concentration is that the aqueous sulfuric acid of 5g/L～20g/L carries out chemical etching to Mg alloy surface and handles; Etching temperature is 20 ℃～30 ℃, and etching time is 5min～10min, in the present embodiment; The mass and size concentration of aqueous sulfuric acid is 5g/L or 20g/L; Etching temperature is 20 ℃ or 30 ℃, and etching time is 5min or 10min
(2) adopt myristic acid solution as electrolytic solution, use anonizing, Mg alloy surface is carried out simultaneously the modification of the structure and the low surface energy of secondary structure; Described myristic acid solution is that myristic acid, glycerine are dissolved in the ethanol, and myristic acid concentration is 2wt%～6wt%, and glycerol concentration is 0.6wt%～1.6wt%; Alcohol concn is 92.4wt%～97.4wt%, and described anodic oxidation is: be negative electrode with nickel, the magnesiumalloy of handling through above-mentioned chemical etching is an anode; Place myristic acid electrolytic solution, electrolysis temperature is 20 ℃～30 ℃, and voltage is 3V～10V; Electrolysis time is 0.5 hour～2 hours, and in the present embodiment, the myristic acid concentration in the myristic acid solution is 2wt% or 6wt%; Glycerol concentration is 0.6wt% or 1.6wt%, and alcohol concn is 92.4wt% or 97.4wt%, and electrolysis temperature is 20 ℃ or 30 ℃; Voltage is 3V or 10V, and electrolysis time is 0.5 hour or 2 hours
(3) after the anodize, take out magnesiumalloy, be placed in the cabinet-type electric furnace through washed with de-ionized water, 50 ℃-90 ℃ following solidification treatment 0.5-1.5 hour, in the present embodiment, magnesiumalloy was 50 ℃ or 90 ℃ of following solidification treatment 0.5 or 1.5 hours, air cooling is taken out in the back.
Claims (1)
1. the compound preparation method with magnesiumalloy of super hydrophobic surface is characterized in that said method comprises the following steps:
(1) adopting mass and size concentration is that the aqueous sulfuric acid of 5g/L ~ 20g/L carries out chemical etching to Mg alloy surface and handles, and etching temperature is 20 ℃ ~ 30 ℃, and etching time is 5min ~ 10min,
(2) adopt myristic acid solution as electrolytic solution, use anonizing, Mg alloy surface is carried out simultaneously the modification of the structure and the low surface energy of secondary structure; Described myristic acid solution is that myristic acid, glycerine are dissolved in the ethanol, and myristic acid concentration is 2wt% ~ 6wt%, and glycerol concentration is 0.6wt% ~ 1.6wt%, and alcohol concn is 92.4wt% ~ 97.4wt%; Described anodic oxidation is: be negative electrode with nickel, the magnesiumalloy of handling through above-mentioned chemical etching is an anode, places myristic acid electrolytic solution, and electrolysis temperature is 20 ℃ ~ 30 ℃, and voltage is 3V ~ 10V, and electrolysis time is 0.5 h ~ 2 hours,
(3) after the anodize, take out magnesiumalloy, be placed in the cabinet-type electric furnace through washed with de-ionized water, 50 ℃-90 ℃ following solidification treatment 0.5-1.5 hour, take out the back air cooling.
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| CN102286768B (en) * | 2011-09-07 | 2013-02-27 | 大连理工大学 | Process method for preparing superhydrophobic magnesium alloy surfaces |
| CN102643967B (en) * | 2012-05-01 | 2014-10-29 | 中国石油大学(华东) | Preparation method of steel bionic multiscale dewatering function surface |
| CN103952732B (en) * | 2014-04-11 | 2017-04-19 | 华南理工大学 | Metal super-hydrophobic surface and preparation method thereof |
| CN104005066A (en) * | 2014-05-16 | 2014-08-27 | 华南理工大学 | Magnesium alloy surface super hydrophobic membrane layer and preparation method and application thereof |
| CN105039953B (en) * | 2015-05-28 | 2017-12-05 | 陕西师范大学 | The method on protein self assembly constructing super-drainage surface |
| CN106801239B (en) * | 2017-01-18 | 2019-02-01 | 东南大学 | A kind of preparation method of super-hydrophobic magnesium alloy coating |
| CN109112599A (en) * | 2018-08-22 | 2019-01-01 | 大连理工大学 | A kind of preparation method obtaining sliding porous surface on aluminum substrate |
| CN115142107A (en) * | 2022-06-10 | 2022-10-04 | 中国科学院金属研究所 | Preparation method of environment-friendly conductive protective film on surface of magnesium alloy |
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| CN101469438A (en) * | 2007-12-25 | 2009-07-01 | 中国科学院兰州化学物理研究所 | Preparation of self-lubricating and hydrophobic structure integrated differential arc oxidation coating on magnesium alloy surface |
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