CN102618913B - Method for preparing titanium or titanium alloy super-hydrophobic surface - Google Patents
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000010936 titanium Substances 0.000 title claims abstract description 51
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 50
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 34
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 18
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims abstract description 10
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 8
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 6
- XPBBUZJBQWWFFJ-UHFFFAOYSA-N fluorosilane Chemical compound [SiH3]F XPBBUZJBQWWFFJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- TWJNQYPJQDRXPH-UHFFFAOYSA-N 2-cyanobenzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1C#N TWJNQYPJQDRXPH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005639 Lauric acid Substances 0.000 claims abstract description 5
- 235000021360 Myristic acid Nutrition 0.000 claims abstract description 5
- TUNFSRHWOTWDNC-UHFFFAOYSA-N Myristic acid Natural products CCCCCCCCCCCCCC(O)=O TUNFSRHWOTWDNC-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000021314 Palmitic acid Nutrition 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011780 sodium chloride Substances 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005096 rolling process Methods 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 238000003486 chemical etching Methods 0.000 claims 1
- 239000002253 acid Substances 0.000 abstract description 6
- 230000007935 neutral effect Effects 0.000 abstract description 4
- 235000021355 Stearic acid Nutrition 0.000 abstract description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 abstract description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000008117 stearic acid Substances 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002848 electrochemical method Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000003513 alkali Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- DCXXMTOCNZCJGO-UHFFFAOYSA-N Glycerol trioctadecanoate Natural products CCCCCCCCCCCCCCCCCC(=O)OCC(OC(=O)CCCCCCCCCCCCCCCCC)COC(=O)CCCCCCCCCCCCCCCCC DCXXMTOCNZCJGO-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- KYIDJMYDIPHNJS-UHFFFAOYSA-N ethanol;octadecanoic acid Chemical compound CCO.CCCCCCCCCCCCCCCCCC(O)=O KYIDJMYDIPHNJS-UHFFFAOYSA-N 0.000 description 1
- 230000005661 hydrophobic surface Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002973 irritant agent Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- ing And Chemical Polishing (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
Abstract
本发明公开了一种制备钛或钛合金超疏水表面的方法，其特征是将作为阳极的钛或钛合金和阴极平行对称放置，并通过导线与直流电源相连，钛或钛合金接正极，阴极接负极，然后将其放入电解液中，接通电源开始电化学刻蚀；所采用的电解液为NaCl或NaBr水溶液；刻蚀完成后将钛或钛合金清洗，吹干；将得到的钛或钛合金表面用低表面能材料进行修饰，取出后烘干，即得到钛或钛合金超疏水表面；所采用的低表面能材料包括氟硅烷、硬脂酸、棕榈酸、月桂酸或肉豆蔻酸。本发明工艺简单，快速高效，可控性好，特别是中性电解液的使用使得该方法更加安全，环保，在航空、航天、舰船等领域有着广泛的应用前景。
The invention discloses a method for preparing a titanium or titanium alloy superhydrophobic surface, which is characterized in that the titanium or titanium alloy used as the anode and the cathode are placed in parallel and symmetrically, and are connected to a DC power supply through a wire, the titanium or titanium alloy is connected to the positive electrode, and the cathode Connect the negative electrode, then put it into the electrolyte, turn on the power and start electrochemical etching; the electrolyte used is NaCl or NaBr aqueous solution; after the etching is completed, the titanium or titanium alloy is cleaned and dried; the obtained titanium Or the surface of titanium alloy is modified with low surface energy materials, taken out and dried to obtain superhydrophobic surface of titanium or titanium alloy; the low surface energy materials used include fluorosilane, stearic acid, palmitic acid, lauric acid or myristic acid acid. The process of the invention is simple, fast and efficient, and has good controllability. In particular, the use of neutral electrolyte makes the method safer and more environmentally friendly, and has broad application prospects in the fields of aviation, aerospace, ships and the like.
Description
技术领域 technical field
本发明涉及金属表面处理，特别涉及到一种电化学制备钛或钛合金超疏水表面的工艺方法。The invention relates to metal surface treatment, in particular to a process method for electrochemically preparing super-hydrophobic surface of titanium or titanium alloy.
背景技术 Background technique
钛及钛合金具有比强度高、耐热性好、耐腐蚀等优良特性，超疏水表面具有自清洁、减阻减摩、防结霜、抑制表面腐蚀等特点。因此，发明钛或钛合金超疏水表面制备方法，对航空、航天、舰船、兵器等工业发展有着极其重要的意义。Titanium and titanium alloys have excellent properties such as high specific strength, good heat resistance, and corrosion resistance. The superhydrophobic surface has the characteristics of self-cleaning, drag and friction reduction, frost prevention, and surface corrosion inhibition. Therefore, inventing a method for preparing superhydrophobic surfaces of titanium or titanium alloys is of great significance to the development of industries such as aviation, aerospace, ships, and weapons.
制备钛或钛合金超疏水表面一般需要两个步骤：一是对其表面进行粗糙化处理，构建微纳米粗糙结构；二是降低其表面能，通常利用低表面能物质硅烷、氟硅烷或硬脂酸等来修饰所获得的粗糙结构。Qu等通过在钛基底上制备导电聚苯胺纳米管薄膜制备超疏水表面(M.N.Qu，G.Y.Zhao，X.P.Cao，J.Y.Zhang，Langmuir 2008，24，4185)，Fujishima等利用印刷法在钛基底制备了超疏水表面(K.Nakata，S.Nishimoto，A.Kubo，D.Tryk，T.Ochiai，T.Murakami，A.Fujishima，Chem.Asian J.2009，4，984)，上述方法需要较多的步骤以及较长的加工时间。Lin等利用电化学法制备超疏水钛表面，以铂金为阴极，氢氟酸为电解液(Y.K.Lai，C.J.Lin，J.Y.Huang，H.F.Zhuang，L.Sun，T.Nguyen，Langmuir，2008，24，3867)，由于铂金是贵重金属，使得该方法成本较高，氢氟酸属于强酸，并具有较强的氧化性，会对环境造成污染。利用强酸或强碱制备超疏水钛表面的还有中国专利200810183386.9，Chen等(A.C.Chen，X.S.Peng，K.Koczkur，B.Miller，Chem.Commun.2004，1964)和Ivanova等(E.P.Ivanova，V.K.Truong，J.Y.Wang，C.C.Berndt，R.T.Jones，I.I.Yusuf，I.Peake，H.W.Schmidt，C.Fluke，D.Barnes，R.J.Crawford，Langmuir，2010，26，1973)，这些方法会在较大程度上对环境造成污染。The preparation of titanium or titanium alloy superhydrophobic surface generally requires two steps: one is to roughen the surface to construct a micro-nano rough structure; the other is to reduce its surface energy, usually by using low surface energy materials such as silane, fluorosilane or stearin acid etc. to modify the obtained rough structure. Qu et al prepared a superhydrophobic surface by preparing a conductive polyaniline nanotube film on a titanium substrate (M.N.Qu, G.Y.Zhao, X.P.Cao, J.Y.Zhang, Langmuir 2008, 24, 4185), Fujishima et al. prepared a superhydrophobic surface on a titanium substrate by printing Hydrophobic surfaces (K.Nakata, S.Nishimoto, A.Kubo, D.Tryk, T.Ochiai, T.Murakami, A.Fujishima, Chem.Asian J.2009, 4, 984), the above method requires more steps and longer processing times. Lin et al. used electrochemical methods to prepare superhydrophobic titanium surfaces, using platinum as the cathode and hydrofluoric acid as the electrolyte (Y.K.Lai, C.J.Lin, J.Y.Huang, H.F.Zhuang, L.Sun, T.Nguyen, Langmuir, 2008, 24, 3867), because platinum is a precious metal, the cost of this method is higher, and hydrofluoric acid is a strong acid, and has strong oxidizing properties, which will pollute the environment. There is also Chinese patent 200810183386.9 that utilizes strong acid or strong base to prepare superhydrophobic titanium surface, Chen et al. Truong, J.Y.Wang, C.C.Berndt, R.T.Jones, I.I.Yusuf, I.Peake, H.W.Schmidt, C.Fluke, D.Barnes, R.J.Crawford, Langmuir, 2010, 26, 1973), these methods will to a greater extent The environment is polluted.
电化学刻蚀法是一种简单，高效，可控性好的传统技术。使用电化学法构造超疏水表面的粗糙结构具有操作简单方便、加工时间短等优点。此外，与上述制备钛或钛合金超疏水表面的方法相比，本发明使用中性电解液，避免强酸强碱溶液的使用，使得加工过程更加环保，操作人员更加安全。目前，采用中性电解液的电化学法制备钛或钛合金超疏水表面的方法尚无文献报道。Electrochemical etching is a simple, efficient, and well-controllable traditional technology. The use of electrochemical methods to construct rough structures on superhydrophobic surfaces has the advantages of simple and convenient operation and short processing time. In addition, compared with the above-mentioned methods for preparing superhydrophobic surfaces of titanium or titanium alloys, the present invention uses a neutral electrolyte and avoids the use of strong acid and strong alkali solutions, making the processing process more environmentally friendly and operators safer. At present, there is no literature report on the preparation of titanium or titanium alloy superhydrophobic surface by electrochemical method with neutral electrolyte.
发明内容 Contents of the invention
本发明所要解决的技术问题是提供一种安全、环保、加工过程简单且加工效率高的方法来制备钛或钛合金超疏水表面。为了解决上述技术问题，本发明提供构建钛或钛合金超疏水表面的工艺方法，包括如下步骤：The technical problem to be solved by the present invention is to provide a method for preparing superhydrophobic surfaces of titanium or titanium alloys with safety, environmental protection, simple processing process and high processing efficiency. In order to solve the above technical problems, the present invention provides a process for constructing a titanium or titanium alloy superhydrophobic surface, comprising the steps of:
(1)将金属钛或钛合金清洗除油；(1) Clean and degrease metal titanium or titanium alloy;
(2)将钛或钛合金和阴极平行对称放置，并通过导线与直流电源相连，钛或钛合金接正极，阴极接负极，然后将其放入盛有电解液的容器中，接通电源开始电化学刻蚀；所采用的电解液为NaCl或NaBr水溶液；刻蚀完成后将钛或钛合金清洗，吹干；(2) Place the titanium or titanium alloy and the cathode in parallel and symmetrically, and connect them to the DC power supply through wires. The titanium or titanium alloy is connected to the positive pole, and the cathode is connected to the negative pole. Electrochemical etching; the electrolyte used is NaCl or NaBr aqueous solution; after the etching is completed, the titanium or titanium alloy is cleaned and dried;
(3)将步骤(2)得到的钛或钛合金表面用低表面能材料进行修饰，取出后烘干，即得到钛或钛合金超疏水表面；所采用的低表面能材料包括氟硅烷、硬脂酸、棕榈酸、月桂酸或肉豆蔻酸。(3) modify the surface of the titanium or titanium alloy obtained in step (2) with a low surface energy material, take it out and dry it to obtain a superhydrophobic surface of titanium or titanium alloy; the low surface energy material used includes fluorosilane, hard fatty acid, palmitic acid, lauric acid or myristic acid.
本发明与现有的钛或钛合金超疏水表面制备技术相比具有以下优点：Compared with the existing titanium or titanium alloy superhydrophobic surface preparation technology, the present invention has the following advantages:
(1)本发明无需复杂的加工装置和操作步骤，且极易大面积制备。(1) The present invention does not require complex processing devices and operating steps, and is extremely easy to prepare in large areas.
(2)本发明采用中性电解液，无需强酸、强碱，反应过程中无刺激性气体产生，对操作人员和环境的危害小。(2) The present invention adopts neutral electrolyte, does not need strong acid and strong alkali, produces no irritating gas during the reaction process, and has little harm to operators and the environment.
(3)本发明的加工效率高，只需几分钟的时间就可得到超疏水表面所需的二元微纳米粗糙结构。(3) The processing efficiency of the present invention is high, and the binary micro-nano rough structure required by the super-hydrophobic surface can be obtained in only a few minutes.
(4)本发明得到的钛或钛合金超疏水表面具有较好的超疏水性能，对水的接触角大于150°，滚动角小于5°。(4) The titanium or titanium alloy superhydrophobic surface obtained by the present invention has good superhydrophobic performance, the contact angle to water is greater than 150°, and the rolling angle is less than 5°.
附图说明 Description of drawings
图1为实施例1的加工装置示意图。Fig. 1 is the schematic diagram of the processing device of embodiment 1.
图2为实施例1获得的钛超疏水表面的扫描电镜图。Fig. 2 is the scanning electron micrograph of the superhydrophobic surface of titanium obtained in Example 1.
图3为实施例1获得的钛超疏水表面的扫描电镜图。3 is a scanning electron microscope image of the titanium superhydrophobic surface obtained in Example 1.
图4为实施例1获得的钛超疏水表面的扫描电镜图。FIG. 4 is a scanning electron micrograph of the titanium superhydrophobic surface obtained in Example 1.
图5为实施例1获得的钛超疏水表面的疏水示意图。5 is a schematic diagram of the hydrophobicity of the titanium superhydrophobic surface obtained in Example 1.
具体实施方式 Detailed ways
以下结合技术方案和附图详细叙述本发明的具体实施例。Specific embodiments of the present invention will be described in detail below in conjunction with technical solutions and accompanying drawings.
实施例1Example 1
(1)将钛板和阴极铜板切割成20mm×30mm，实际加工面积为20mm×20mm，其余部分用于装夹和导电。加工前，对钛板和阴极铜板依次使用无水乙醇和去离子水超声波清洗，吹干。(1) Cut the titanium plate and cathode copper plate into 20mm×30mm, the actual processing area is 20mm×20mm, and the rest is used for clamping and conducting. Before processing, the titanium plate and the cathode copper plate are ultrasonically cleaned with absolute ethanol and deionized water in sequence, and dried.
(2)将钛板和阴极铜板平行对称固定，两板间距为10mm，两板通过导线与直流电源相连，钛板接电源正极，阴极铜板接电源负极；将两板放入盛有0.2mol/L NaCl水溶液中；接通直流电源，开始加工，电流密度为1A/cm2。加工时溶液温度为室温(约25℃)，加工时间为3min。(2) Fix the titanium plate and cathode copper plate symmetrically in parallel, the distance between the two plates is 10mm, the two plates are connected to the DC power supply through wires, the titanium plate is connected to the positive pole of the power supply, and the cathode copper plate is connected to the negative pole of the power supply; put the two plates into a container containing 0.2mol/ L NaCl aqueous solution; turn on the DC power supply, start processing, and the current density is 1A/cm 2 . During processing, the solution temperature is room temperature (about 25° C.), and the processing time is 3 minutes.
(3)加工完成后将钛板用去离子水冲洗，吹干，最后将其放入配制好的质量分数为1％的氟硅烷乙醇溶液中，在室温下浸泡2h后取出，放入烘箱中，在80℃下烘15min，取出后在空气中冷却到室温，即可得到超疏水表面。水滴在钛或钛合金超疏水表面上的接触角为153°，滚动角为2°。如果使用硬脂酸、棕榈酸、月桂酸或肉豆蔻酸等来降低表面能时，接触角都会超过150°。(3) After the processing is completed, rinse the titanium plate with deionized water, dry it, and finally put it into the prepared fluorosilane ethanol solution with a mass fraction of 1%, soak it at room temperature for 2 hours, take it out, and put it in an oven , bake at 80°C for 15 minutes, take it out and cool it to room temperature in the air to obtain a superhydrophobic surface. The contact angle of a water droplet on a titanium or titanium alloy superhydrophobic surface is 153°, and the rolling angle is 2°. If stearic acid, palmitic acid, lauric acid or myristic acid are used to reduce the surface energy, the contact angle will exceed 150°.
实施例2Example 2
(1)将钛板和阴极铜板切割成20mm×30mm，实际加工面积为20mm×20mm，其余部分用于装夹和导电。加工前，对钛板和阴极铜板依次使用无水乙醇和去离子水超声波清洗，吹干。(1) Cut the titanium plate and cathode copper plate into 20mm×30mm, the actual processing area is 20mm×20mm, and the rest is used for clamping and conducting. Before processing, the titanium plate and the cathode copper plate are ultrasonically cleaned with absolute ethanol and deionized water in sequence, and dried.
(2)将钛板和阴极铜板平行对称固定，两板间距为10mm，两板通过导线与直流电源相连，钛板接电源正极，阴极铜板接电源负极；将两板放入盛有0.2mol/L NaBr水溶液中；接通直流电源，开始加工，电流密度为0.5A/cm2。加工时溶液温度为室温(约25℃)，加工时间为15min。(2) Fix the titanium plate and cathode copper plate symmetrically in parallel, the distance between the two plates is 10mm, the two plates are connected to the DC power supply through wires, the titanium plate is connected to the positive pole of the power supply, and the cathode copper plate is connected to the negative pole of the power supply; put the two plates into a container containing 0.2mol/ L NaBr aqueous solution; turn on the DC power supply, start processing, and the current density is 0.5A/cm 2 . During processing, the solution temperature is room temperature (about 25° C.), and the processing time is 15 minutes.
(3)加工完成后将钛板用去离子水冲洗，吹干，最后将其放入配制好的质量分数为1％的硬脂酸乙醇溶液中，在室温下浸泡2h后取出，放入烘箱中，在80℃下烘15min，取出后在空气中冷却到室温，即可得到超疏水表面。水滴在钛或钛合金超疏水表面上的接触角为161°，滚动角为2°。如果使用氟硅烷、棕榈酸、月桂酸或肉豆蔻酸等来降低表面能时，接触角都会超过150°。(3) After the processing is completed, rinse the titanium plate with deionized water, dry it, and finally put it into the prepared stearic acid ethanol solution with a mass fraction of 1%, take it out after soaking at room temperature for 2 hours, and put it into an oven Bake at 80°C for 15 minutes, take it out and cool to room temperature in the air to obtain a superhydrophobic surface. The contact angle of water droplets on the superhydrophobic surface of titanium or titanium alloy is 161°, and the rolling angle is 2°. If fluorosilane, palmitic acid, lauric acid or myristic acid are used to reduce the surface energy, the contact angle will exceed 150°.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210103931.5A CN102618913B (en) | 2012-04-10 | 2012-04-10 | Method for preparing titanium or titanium alloy super-hydrophobic surface |
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| CN104152921B (en) * | 2014-09-02 | 2016-11-16 | 南昌航空大学 | A method for improving blood compatibility of medical titanium alloy |
| CN104532337A (en) * | 2015-01-09 | 2015-04-22 | 中国矿业大学 | Electro erosion method for rapidly preparing iron base super-hydrophobic surface in large area |
| CN106637316B (en) * | 2016-12-07 | 2018-12-21 | 广东工业大学 | A method of preparing super hydrophobic surface in titanium substrate |
| CN106968010A (en) * | 2017-04-20 | 2017-07-21 | 沈阳航空航天大学 | A kind of preparation method of almag super hydrophobic surface |
| CN110144613A (en) * | 2019-07-04 | 2019-08-20 | 烟台大学 | A kind of preparation method of Zr-based amorphous alloy superhydrophobic surface |
| CN110552042A (en) * | 2019-08-27 | 2019-12-10 | 重庆大学 | preparation method of super-wetting coating on inner surface of U-shaped titanium pipe |
| CN110721888A (en) * | 2019-10-23 | 2020-01-24 | 中国科学院宁波材料技术与工程研究所 | Lubricating grease filled porous structure antifouling surface, and preparation method and application thereof |
| DE102021111147A1 (en) * | 2021-04-29 | 2022-11-03 | Christian-Albrechts-Universität zu Kiel, Körperschaft des öffentlichen Rechts | COMPOSITE STRUCTURE OF TITANIUM AND/OR A TITANIUM ALLOY AND/OR NITI AND A POLYMER AND ELECTROCHEMICAL ETCHING MANUFACTURING METHOD THEREOF |
| CN114752990A (en) * | 2022-03-26 | 2022-07-15 | 四川轻化工大学 | Metal-based nest type micro-structure super-hydrophobic surface and preparation method and application thereof |
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