CN107740083B - Preparation method of magnesium alloy surface super-hydrophobic fluorine conversion coating - Google Patents
Preparation method of magnesium alloy surface super-hydrophobic fluorine conversion coating Download PDFInfo
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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
- C23C22/05—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 using aqueous solutions
- C23C22/06—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 using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—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 using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
Abstract
The invention discloses a preparation method of a magnesium alloy surface super-hydrophobic fluorine conversion coating, which adoptsA method for preparing a micro/nano-structure super-hydrophobic fluorine conversion layer on the surface of a magnesium alloy by a liquid phase growth and hydrothermal treatment combined method. And forming the micro/nano-structure porous hydrophobic coating on the membrane layer through cleaning and polishing, preparation of a fluorine conversion layer and hydrophobic treatment. The contact angle of the coating in a bionic solution reaches 150 degrees, the contact area of a magnesium alloy sample and the solution can be reduced, the corrosion current density of the magnesium alloy can be reduced by 3 orders of magnitude, and the impedance modulus value is 12000 omega-cm2Increase to 1400000 omega cm2The increase is 100 times. The preparation method of the nano-structure hydrophobic coating is simple, the equipment is simple and easy to control, the cost is low, and the controllability is good.
Description
Technical Field
The invention belongs to the technical field of magnesium alloy surface modification and corrosion prevention, and particularly relates to a preparation method of a magnesium alloy surface super-hydrophobic fluorine conversion coating.
Background
Magnesium and magnesium alloy have excellent mechanical property, biocompatibility and degradability, and become a hot point for research of scholars at home and abroad as a novel degradable bone implantation material in the last decade. However, under physiological environment, the magnesium alloy implant degrades before the tissue is healed, and cannot meet the necessary mechanical and morphological requirements of the orthopedic implant device in the service period, and the excessively high magnesium ion concentration not only can induce severe inflammatory reaction of local tissues, but also can cause excessive protein secretion in bone morphology, activate osteoclasts and cause the phenomenon of bone dissolution. Therefore, the reduction of the corrosion rate of the magnesium alloy is a precondition for ensuring good application effect in the biomedical field.
The surface modification does not affect the strength of the magnesium alloy, but the degradation process can be controlled by adjusting the components and the structure of the modified surface, the mechanical property of the magnesium alloy in the service period is kept, and the method is an effective method for improving the corrosion performance of the magnesium alloy. Among various surface modification methods, the fluorine treatment can obviously improve the corrosion resistance of the magnesium alloy and delay the release of alloy elements, and a calcium fluoride film on the surface of the magnesium alloy is nontoxic to basic cells and is more favorable for the long-term growth of osteoblasts. However, the researches of the penmen find that when the magnesium alloy after the fluorine treatment is soaked in the Hank's bionic solution for 7 days, corrosion hole nuclei are formed on the surface; significant pitting occurred after soaking for 15 days. Generally, the bone implant device is maintained in vivo for 12 to 18 weeks and has sufficient strength because the conventional fluorine treatment adopts a liquid phase method, but the conventional fluorine treatment adopts a liquid phase methodFluorine conversion layer (MgF) prepared on magnesium alloy surface by liquid phase method2) In general, the thickness is limited and the hydrophilic coating allows the solution to penetrate through the pores of the membrane structure, which may cause the substrate to start etching before the fluorine conversion membrane layer is dissolved and etched. Thus, a single fluorine conversion layer has limited effectiveness in retarding corrosion of the substrate. Therefore, the single fluorine treatment cannot meet the mechanical and morphological requirements of the magnesium alloy as a bone implant material. How to keep certain mechanical property of the magnesium alloy material in the process of tissue healing, and the degradation process and the degradation speed of the magnesium alloy material can be controlled according to the age of a patient and the healing condition of a bone injury part, so that the magnesium alloy material is gradually degraded and absorbed or metabolized by a human body, which has been a difficult problem all the time.
The super-hydrophobic surface popular in recent years draws great attention worldwide due to unique surface properties of self-cleaning, corrosion prevention, super-hydrophobicity and the like, is one of research hotspots in the technical field of bionic nano materials, and researches find that the material surface has a uniform micro-nano-sized coarse structure and lower surface free energy which are two necessary conditions for realizing the super-hydrophobicity. Therefore, scientific researchers adopt various methods to construct the micro-nano rough structure, such as an etching method, a template method, a chemical vapor deposition method and the like; the super-hydrophobic surface is prepared by a sol-gel method, a chemical bath method, an electrostatic spraying method, a layer-by-layer adsorption method and the like, but the preparation method which can be applied to large-scale application production is less.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a simple and feasible preparation method of a magnesium alloy surface super-hydrophobic fluorine conversion coating by adopting a method combining liquid phase growth and hydrothermal treatment, and solve the problems that the corrosion resistance effect of the existing magnesium alloy as a bone implant material is poor and the existing magnesium alloy is not suitable for large-scale production.
In order to achieve the purpose, the invention adopts the following technical scheme that the preparation method of the magnesium alloy surface super-hydrophobic fluorine conversion coating comprises the following steps:
1) cleaning and polishing
Sequentially polishing the surface of a magnesium alloy sample to be treated by coarse-fine sand paper until the surface is smooth and traceless, sequentially cleaning the surface by distilled water and absolute ethyl alcohol, and airing the surface at room temperature; then putting the sample into an ultrasonic cleaning machine for cleaning, then putting the sample into polishing solution for soaking for 5-10 seconds, immediately taking the sample out, finally washing the surface of the sample with deionized water, and blow-drying the sample with a blower for later use;
2) preparation of micro/nano structure fluoride layer
Soaking the magnesium alloy sample polished in the step 1) in an HF aqueous solution for 5-7 days, taking out the sample, washing the sample with deionized water, and then adding saturated Ca (OH)2Soaking the sample in the solution for 24-48 hours, taking out the sample, and washing the sample with deionized water;
3) hydrophobizing treatment
Putting the sample treated in the step 2) into a reaction kettle filled with a stearic acid ethanol solution, performing hydrothermal treatment at 60-70 ℃, and airing at room temperature to obtain the magnesium alloy with the super-hydrophobic fluorine conversion coating on the surface of the product.
Further, the roughness of the sand paper is 200#, 400#, 600#, 800#, 1000# or 1200 #.
Further, the polishing solution is a mixed solution of hydrofluoric acid, nitric acid and water, wherein the volume ratio of the hydrofluoric acid to the nitric acid to the water is 0.5-2: 5-15: 83-94.5.
Furthermore, the concentration of the HF aqueous solution is 20-40%, and the soaking time of the sample in the HF aqueous solution is 7 days.
Further, the sample was saturated with Ca (OH)2The soaking time in the solution was 24 hours.
Further, the concentration of the stearic acid ethanol solution is 0.025-0.125 mol/L, and the hydrothermal treatment time is 3-12 hours.
Further, the concentration of the stearic acid ethanol solution is 0.05 mol/L.
Further, the inner cup material of the reaction kettle is polytetrafluoroethylene.
Compared with the prior art, the invention has the following beneficial effects:
1. the magnesium alloy with the super-hydrophobic fluorine conversion coating on the surface prepared by the method has the advantages that the uniformity of the fluorine conversion layer on the surface of the magnesium alloy and the hydrophobic film layer of the fluorine conversion layer is better. The prepared fluorine conversion layer has a micro/nano pore structure, the stearic acid hydrophobic membrane layer is prepared by adopting a liquid phase growth and hydrothermal treatment combined method, the surface of the membrane layer has hydrophobic performance, the stearic acid solution can permeate into the micro/nano structure fluorine conversion membrane layer by controlling the concentration of the stearic acid solution, the interior of the membrane layer structure with the gap also has hydrophobic performance, and the substrate is tightly sealed. Therefore, a compact super-hydrophobic layer is obtained on the surface of the magnesium metal, the contact between magnesium and the surrounding corrosive water environment is avoided, the corrosion medium is isolated from permeating into the film layer, the corrosion medium is not contacted with the film layer within a period of time, the time for the film layer to start to corrode is slowed down, the time for the film layer to start to perform ion exchange with the environment medium is slowed down, the corrosion tendency of the magnesium alloy is reduced, and the corrosion of the magnesium alloy is greatly delayed. Meanwhile, the requirements of mechanical property and morphology of the magnesium alloy as a biological material are met. Compared with the prior art, the corrosion speed of the fluorine conversion layer subjected to hydrophobization treatment is reduced by nearly ten times, and the corrosion of the magnesium alloy is greatly delayed.
2. In the preparation process of the magnesium alloy surface super-hydrophobic fluorine conversion coating, the raw materials are cheap and easy to obtain, the equipment is simple and easy to control, and the preparation method has the advantages of simple operation, low cost and good controllability. Wherein stearic acid is used as a main raw material, the stearic acid is an organic fatty acid, and is used as an excipient in the pharmaceutical industry and used as a matrix of milk, ointment and suppository. Stabilizers, emulsifiers, dispersants, viscosity modifiers for chewing gum and food quality improvers important in the food industry. The biological compatibility is good, and the decomposition product in the human body is harmless to the human body, thus being an ideal medical material.
3. The invention designs a chemical liquid phase method for preparing a micron-scale and nanometer-scale sheet fluorine conversion crystal layer on the surface of a magnesium alloy, then adopts a hydrothermal treatment method to prepare a stearic acid film on the surface of the micron/nanometer-structure fluorine conversion layer to form an ultra-hydrophobic film layer with a contact angle of 150 degrees in a bionic solution, reduces the contact area of a magnesium alloy sample and the solution, can reduce the corrosion current density of the magnesium alloy by 3 orders of magnitude, and can coat the magnesium alloy with the ultra-hydrophobic film layerThe layer impedance modulus value is from 12000 omega cm2Increase to 1400000 omega cm2The increase is 100 times. Therefore, the corrosion of the magnesium alloy is greatly delayed.
Drawings
FIG. 1 is an SEM image of a coating of AZ31 magnesium alloy;
(a) the surface of the AZ31 magnesium alloy is a fluorine conversion coating (b) the surface of the AZ31 magnesium alloy is a stearic acid treated fluorine conversion coating;
FIG. 2 is a graph of the measurement of the hydrophobic property of AZ31 magnesium alloy coatings;
(a) the surface of the AZ31 magnesium alloy is not treated, (b) the surface of the AZ31 magnesium alloy is a fluorine conversion coating, (c) the surface of the AZ31 magnesium alloy is a stearic acid treated fluorine conversion coating;
FIG. 3 is a Tafel plot of magnesium alloy AZ31 without treatment, with a fluorine conversion coating and a stearic acid treated fluorine conversion coating;
FIG. 4 is a Nyqusit plot of magnesium alloy AZ31 without treatment, with a fluorine conversion layer and a stearic acid treated fluorine conversion coating;
FIG. 5 is a Bode-Frequents plot of magnesium alloy AZ31 without treatment, with a fluorine conversion layer and a stearic acid treated fluorine conversion coating.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and the accompanying drawings. In the following examples, magnesium alloy AZ31 was used as a research object, and the preparation method is also applicable to other medical magnesium alloys.
Preparation method of magnesium alloy surface super-hydrophobic fluorine conversion coating
Example 1
1) Cleaning and polishing
The magnesium alloy AZ31 was cut into 15mm by 1.5mm by 2mm specimens with a small hole of 1 mm diameter at the corner, which could be tied with a thin wire for hanging during the experiment. The samples were sequentially sanded with SiC sandpaper (sandpaper roughness 200#, 400#, 600#, 800#, 1000#, respectively) until the surface was smooth and no scratch was visible. Cleaning in an ultrasonic cleaner, and adding polishing solution (HF: HNO in volume ratio)3：H2O=1：10：89)And immediately taking out after soaking for 5-10 seconds, washing the surface with deionized water, and blow-drying with a blower for later use.
2) Preparation of micro/nano structure fluoride layer
Putting the magnesium alloy sample polished in the step 1) into a solvent bottle filled with 40% hydrofluoric acid solution, sealing a preservative film, winding the preservative film by using a transparent adhesive tape, and soaking for 7 days. And taking out the sample, washing the sample with deionized water, then putting the sample into a saturated calcium hydroxide solution, soaking the sample for 24 hours at room temperature, taking out the sample, and washing the sample with deionized water.
3) Hydrophobizing treatment
Weighing stearic acid, dissolving the stearic acid in absolute ethyl alcohol, stirring the stearic acid solution by using a magnetic heating stirrer to ensure that the concentration of the obtained stearic acid ethanol solution is 0.05M, pouring a proper amount of the solution into a polytetrafluoroethylene reaction kettle, putting the sample treated in the step 2) into the polytetrafluoroethylene reaction kettle filled with the stearic acid ethanol solution, covering the reaction kettle with a cover, carrying out hydrothermal treatment for 8 hours at the temperature of between 60 and 70 ℃, and airing the reaction kettle at room temperature to obtain the magnesium alloy with the superhydrophobic fluorine conversion coating on the surface of the product.
Comparative example 1
The magnesium alloy AZ31 was not subjected to any treatment.
Comparative example 2
The magnesium alloy AZ31 was treated with a micro/nano-structured fluorine conversion coating and not hydrophobized, and the procedure was the same as in example 1.
Secondly, detecting the microstructure and the contact angle of the hydrophobic fluorinated film layer of the micro-nano structure
Example 2
The morphology of the magnesium alloy coatings prepared in example 1 and comparative example 2 was observed using a sigma IGMA HDTM field emission Scanning Electron Microscope (SEM) (fig. 1).
As can be seen from FIG. 1, the single fluorine conversion coating (comparative example 2) formed a micron-sized and nanometer-sized flaky fluorine conversion crystal layer (see FIG. 1 a) on the surface of the magnesium alloy under SEM, but there were many gaps between the crystals. After further performing hydrophobic treatment on the fluorine conversion surface (example 1), a stearic acid film with super-hydrophobic property is formed on the fluorine conversion surface (as shown in fig. 1 b), and the stearic acid film permeates into the fluorine conversion film with the micro-nano structure to fill a plurality of gaps between crystals, so as to effectively prevent the solution from permeating into the gaps of the film structure to corrode the substrate.
The contact angle of the sample surface is measured by a Drop Meter A-100P interfacial tension measuring instrument, if the contact angle is less than 90 degrees, the solid surface is hydrophilic, namely the liquid is easier to wet the solid, the smaller the angle is, the better the wettability is, and if the contact angle is more than 90 degrees, the solid surface is hydrophobic, namely the liquid is not easy to wet the solid, and the liquid is easy to move on the surface. If the contact angle is >150 °, the solid surface is superhydrophobic. As shown in fig. 2.
The contact angle of the membrane layer of the fluorine conversion layer (comparative example 2) was measured to be 30-50 ° (see fig. 2 b). The contact angle of the film layer of the stearic acid treated fluorine conversion layer (example 1) was 153 ° (see fig. 2 c). Therefore, the invention has good hydrophobicity.
Thirdly, carrying out electrochemical performance test on the hydrophobic fluorinated membrane layer with the micro-nano structure
Example 3
Using E G&The G model 273 electrochemical workstation tests the electrochemical corrosion performance. The measurement adopts a three-electrode system: the reference electrode is a Saturated Calomel Electrode (SCE), the auxiliary electrode is a platinum electrode, and the working electrode is the sample to be tested. Hank's bionic solution (composition: NaCl:8 g/l, KCl:0.4 g/l, CaCl) with corrosion medium p H being 7.42:0.14 g/l，NaHCO3:0.35 g/l，C6H6O6:1.0 g/l，MgCl2·6H2O:0.1 g/l， MgSO4·7H2O:0.06 g/l，KH2PO4:0.06 g/l， Na2HPO4·12H2O is 0.06 g/l). The results are shown in FIG. 3.
As can be seen in fig. 3, the magnesium alloy samples of the stearic acid-treated fluorine conversion layer had an increased self-corrosion potential, a reduced self-corrosion current density, and an increased breakdull potential in the Hank's solution as compared to the single fluorine conversion coating. And the smaller the corrosion current density, the better the corrosion resistance of the sample.
Example 4
The products of example 1, comparative examples 1 and 2 described above were subjected to impedance spectroscopy. Electrochemical impedance testing Using an IM6e impedance Meter, test frequency Range 105Hz~10-2Hz。
The Nyquist plot of the AC impedance is composed of a high-frequency region and a low-frequency region, and R can be determined by extending the high-frequency end to the intersection point of the semicircle and the abscissa axissThe value of (solution ohmic resistance); extending to the intersection point of the semicircle and the abscissa axis at the low frequency end to obtain Rs+RpA value of (d); the distance between the two intersection points is the polarization resistance R of the corrosion metal electrode to be detectedp。
As can be seen from fig. 4, compared with the untreated magnesium alloy, the arc of the ac impedance is significantly increased after the treatment of the fluorine conversion layer and the hydrophobic fluorine conversion layer, wherein the capacitive arc radius of the hydrophobic fluorine conversion layer is increased more, which indicates that the ac impedance of the superhydrophobic fluorine conversion layer is greater than that of the single fluorine conversion layer, and the corrosion resistance of the obtained sample is the best.
As can be seen from FIG. 5, the impedance mode values of the magnesium alloy treated by the fluorine conversion layer and the hydrophobic fluorine conversion layer are both significantly increased compared with the untreated magnesium alloy, and the impedance mode value of the magnesium alloy treated by the hydrophobic fluorine conversion layer is 12000 omega cm2Increase to 1400000 omega cm2Approximately 3.5 times that of a single fluorine conversion layer. The super-hydrophobic fluorine conversion layer can play a role in protecting a substrate for a long time.
The data measured in the above examples can be obtained as shown in table 1:
TABLE 1
| Sample (I) | Contact angle | Self-corrosion potential/V | Self-corrosion current density/A/cm2 | Coating impedance modulus/omega cm2 |
| Comparative example 1 | 66° | -1.464 | 1.409×10-5 | 12063 |
| Comparative example 2 | 50° | -1.402 | 4.91×10-7 | 451622 |
| Example 1 | 159° | -1.369 | 2.07×10-8 | 1485349 |
As can be seen from Table 1, the stearic acid film is prepared on the surface of the fluorine conversion layer with the micro/nano structure to form the super-hydrophobic film layer with the contact angle of more than 150 degrees in the bionic solution, the change of the corrosion current density is the largest, and the corrosion current density is 2.07 multiplied by 10-8A/m2. The film layer can reduce the corrosion current density of the magnesium alloy by 3 orders of magnitude. The lower the corrosion current density, the better the corrosion resistance of the sample, i.e. the slower the corrosion rate. The resistance of the resistance film layer is increased, and the resistance modulus of the coating is from 12000 omega cm2Increase to 1400000 omega cm2The corrosion resistance of the film layer is enhanced.
Finally, the above embodiments are only for illustrating the technical solutions of the present invention and not for limiting, although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all of them should be covered in the claims of the present invention.
Claims (8)
1. A preparation method of a magnesium alloy surface super-hydrophobic fluorine conversion coating is characterized by comprising the following steps:
1) cleaning and polishing
Sequentially polishing the surface of a magnesium alloy sample to be treated by coarse-fine sand paper until the surface is smooth and traceless, sequentially cleaning the surface by distilled water and absolute ethyl alcohol, and airing the surface at room temperature; then putting the sample into an ultrasonic cleaning machine for cleaning, then putting the sample into polishing solution for soaking for 5-10 seconds, immediately taking the sample out, finally washing the surface of the sample with deionized water, and blow-drying the sample with a blower for later use;
2) micro/nano-structured fluorine conversion layer preparation
Soaking the magnesium alloy sample polished in the step 1) in an HF aqueous solution for 5-7 days, taking out the sample, washing the sample with deionized water, and then adding saturated Ca (OH)2Soaking in the solution for 24-48 hours, taking out the sample, and washing the sample clean with deionized water, namely preparing a micron-scale and nanometer-scale flaky fluorine conversion crystal layer on the surface of the magnesium alloy; the concentration of the HF aqueous solution is 20-40%;
3) hydrophobizing treatment
Putting the sample treated in the step 2) into a reaction kettle filled with a stearic acid ethanol solution, performing hydrothermal treatment at 60-70 ℃, and airing at room temperature to obtain the magnesium alloy with the super-hydrophobic fluorine conversion coating on the surface of the product.
2. The method for preparing the magnesium alloy surface super-hydrophobic fluorine conversion coating according to claim 1, wherein the roughness of the sand paper is 200#, 400#, 600#, 800#, 1000# or 1200 #.
3. The preparation method of the magnesium alloy surface super-hydrophobic fluorine conversion coating according to claim 1, wherein the polishing solution is a mixed solution of hydrofluoric acid, nitric acid and water in a volume ratio of 0.5-2: 5-15: 83-94.5.
4. The method for preparing the magnesium alloy surface super-hydrophobic fluorine conversion coating according to claim 1, wherein the soaking time of the sample in the HF aqueous solution is 7 days.
5. The method for preparing the magnesium alloy surface super-hydrophobic fluorine conversion coating according to claim 1, wherein the sample is saturated with Ca (OH)2The soaking time in the solution was 24 hours.
6. The preparation method of the magnesium alloy surface super-hydrophobic fluorine conversion coating according to claim 1, wherein the concentration of the stearic acid ethanol solution is 0.025-0.125 mol/L, and the hydrothermal treatment time is 3-12 hours.
7. The preparation method of the magnesium alloy surface super-hydrophobic fluorine conversion coating according to claim 6, wherein the concentration of the ethanol solution of stearic acid is 0.05 mol/L.
8. The preparation method of the magnesium alloy surface super-hydrophobic fluorine conversion coating according to claim 1, wherein the inner cup material of the reaction kettle is polytetrafluoroethylene.
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| CN109267054B (en) * | 2018-08-22 | 2020-12-01 | 山东第一医科大学(山东省医学科学院) | Method for improving corrosion resistance of magnesium alloy by using ultrasonic fluorination coating method |
| CN110592569B (en) * | 2019-09-23 | 2021-02-05 | 河海大学 | Method for constructing super-hydrophobic corrosion-resistant conversion coating on surface of magnesium-lithium alloy and magnesium-lithium alloy with super-hydrophobic corrosion resistance |
| CN110724946A (en) * | 2019-10-31 | 2020-01-24 | 广东省人民医院(广东省医学科学院) | Impure-phase-free Mg-Al LDH coating on surface of magnesium alloy and preparation method and application thereof |
| CN112247097B (en) * | 2020-10-22 | 2022-03-18 | 重庆建谊祥科技有限公司 | Semi-solid die-casting and double-fluorination combined manufacturing method for magnesium alloy building template |
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| CN102423755A (en) * | 2011-10-20 | 2012-04-25 | 西北师范大学 | Method for constructing nanotube-like super-hydrophobic structure on surface of zinc sheet |
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| CN105401153A (en) * | 2015-08-26 | 2016-03-16 | 上海电力学院 | Corrosion-resistant pure copper superhydrophobic surface preparation method |
| CN105413994A (en) * | 2015-12-15 | 2016-03-23 | 大连理工大学 | Preparation method for super-hydrophobic surface with bionic micro-nano composite structure |
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| CN102423755A (en) * | 2011-10-20 | 2012-04-25 | 西北师范大学 | Method for constructing nanotube-like super-hydrophobic structure on surface of zinc sheet |
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| CN104561999A (en) * | 2014-12-19 | 2015-04-29 | 北京科技大学 | Method for preparing superhydrophobic film on magnesium alloy surface |
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