CN109023319A - A method of preparing dendroid micro nano structure copper oxide super-hydrophobic coat - Google Patents

A method of preparing dendroid micro nano structure copper oxide super-hydrophobic coat Download PDF

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CN109023319A
CN109023319A CN201811086518.6A CN201811086518A CN109023319A CN 109023319 A CN109023319 A CN 109023319A CN 201811086518 A CN201811086518 A CN 201811086518A CN 109023319 A CN109023319 A CN 109023319A
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copper
copper oxide
sample
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aluminium
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CN109023319B (en
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于思荣
吕哲馨
尹晓丽
周雪
宋锴星
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China University of Petroleum East China
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/38—Coating with copper
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

The invention discloses the methods that one kind simply and rapidly prepares dendroid micro nano structure copper oxide super-hydrophobic coat.The copper oxide with dendroid micrometer structure has been prepared by chemistry displacement, directly thermal oxidation process first；Chemical displacement liquid can be copper chloride solution, be also possible to the mixed aqueous solution of copper sulphate and iron chloride (or sodium chloride)；The matrix sample handled well is immersed in chemical displacement liquid, forms the copper deposits of Non-smooth surface in specimen surface；It places it in Muffle furnace again, heat treatment certain time obtains the copper oxide of dendroid micro nano structure by copper deposits directly thermal oxidation at copper oxide；Finally, modifying through low energy, super-hydrophobic copper oxide coating is obtained.The static contact angle of deionized water and the copper oxide super-hydrophobic coat is greater than 150 °, and roll angle is less than 10 °.The equipment that copper oxide super-hydrophobic coat prepared by the present invention is not necessarily to complex and expensive, simple process, repeatability is strong, can be applied to the surfaces such as aluminium, magnesium, zinc, iron, is suitble to industrialized production.

Description

A method of preparing dendroid micro nano structure copper oxide super-hydrophobic coat
Technical field
The present invention relates to metal surface properties modification fields, and in particular to a kind of to prepare dendroid micro nano structure copper oxide The method of super-hydrophobic coat.By super hydrophobic surface intrinsic hydrophobic, anticorrosion, good antiscale property and self-cleaning function, improve aluminium The service life of material.
Background technique
Nearly three during the last ten years, special wellability film layer, and especially super-hydrophobic film layer has become domestic and international micro Nano material With the research hotspot in Surface Science field.The functions such as the intrinsic waterproof of super-hydrophobic coat, antifouling, anticorrosion, anti-frost, make original This corrosion-vulnerable, pollution and the material surface of destruction are effectively protected.Aluminium is widely used because of excellent performance In fields such as electric appliance, building, the vehicles, machine-building, national defense industry.But since the reactivity of element aluminum is higher, therefore Its surface is easy to happen dirt contamination, chemical attack.And aluminium material surface can effectively be promoted by preparing super-hydrophobic coat in aluminium material surface Fouling resistance, the performances such as anticorrosive, and realize its functionalized application.
According to existing surface wetting theory, for intrinsic hydrophilic material (such as aluminium, copper, zinc and magnesium), super-hydrophobic painting The basic preparation flow of layer: firstly, increasing the roughness of matrix surface；Secondly, being modified on the increased matrix surface of roughness Substance with low-surface-energy.Studies have shown that the substance for only modifying low-surface-energy can only at most incite somebody to action on the surface of relative smooth The Static Contact angle value of itself and water is improved to 119 °.Therefore, the key for manually preparing super hydrophobic material is that construction with micro- The rice even surface roughness of nanostructure, such as flower coronal structure, column structure, the hierarchical structure with multiple roughness Deng.
Currently, there are many methods for improving surface roughness, such as chemical etching method, laser ablation method, collosol and gel Method, vapour deposition process, electrochemical method etc..In recent years, transition-metals and their oxides ultra-fine grain catalysis, superconduction, sensing, The fields such as magnetic storage are widely used.Wherein, copper oxide is as narrow band gap (forbidden bandwidth EgFor 1.2Ev) p-type semiconductor material, Because of its unique physics and chemical characteristic, in solar battery, the catalysis of organic reaction, lithium battery, bio-sensing, air-sensitive, field The fields such as transmitting, photocatalysis degradation organic contaminant, magnetic storage device are widely used；It is well known that nano material has Different from the physical and chemical properties of body material, these physical and chemical performances depend greatly on the size and shape of material Looks, while the micro/nano structure unit of different-shape is also the basic module for constructing nano-device；Therefore, on associated materials It prepares copper oxide coarse structure and realizes that its functionalized application is a promising research.
Chinese patent (Publication No. CN105505204A, publication date are on April 20th, 2016) discloses a kind of nano oxygen Change the preparation method of copper super hydrophobic coating.This method utilizes low-surface-energy material mercaptan (n octylmercaptan, Stearyl mercaptan) Or stearic acid is modified copper oxide nanometer particle surface, then modified copper oxide nanometer particle and silicon rubber difference is molten The coating of component a and component b is made in solution in isopropanol, after the ratio mixing of 0.5~1.5:1 of volume ratio of component a, b, system Obtained super hydrophobic coating.Requirement of the method to raw material is harsher, and improve the patent applies threshold.Chinese patent is (public The number of opening is CN104829143A, and publication date is August in 2015 12) disclose a kind of preparation of nano cupric oxide based superhydrophobic thin films Method.Firstly, being prepared for the nano cupric oxide of corolla shape crystal morphology using liquid-phase precipitation method, detailed process is in temperature 60- The mixed solution a that hexadecyl trimethylamine ammonium bromide and copper sulphate is made is stirred at 85 DEG C, then with certain density sodium hydroxide The pH value of mixed solution a is adjusted to 12 by solution, and stirs 8-12h, after the obtained black precipitate of vacuum filtration is being dried in vacuo 1-2h is dried in case at 60-90 DEG C, obtains copper oxide after grinding；Again by copper oxide disperses into deionized water, it is added organic Silicon defoaming agent is placed in vacuum oven and dries at 60-90 DEG C through spray gun even application on glass slide, and surface is made and applies There is the glass slide of nano cupric oxide；Finally, nano oxidized using being prepared after the modification of low-surface energy substance stearic acid ethanol solution Copper based superhydrophobic thin films.The invention mainly relies on pH value to regulate and control the amount of the substance of copper sulphate and sodium hydroxide in reaction system Proportion, the excessive too small variation for all causing reaction product of pH value, therefore, the invention control relevant experiment condition stringent.In State's patent (Publication No. CN104726875A, publication date are on June 24th, 2015) discloses a kind of super in steel surface preparation The method of hydrophobic oxidation copper film forms the copper plate of Non-smooth surface first in steel surface acid copper；Existed again by hydrothermal processes The copper facing layer surface forms one layer of oxidation copper film；The oxidation copper film of super hydrophobic functional is obtained finally by fluorination treatment.This method Plating and hydrothermal solution oxidation processes are all harsher to experiment parameter requirement, and hydrothermal solution oxidation processes are formed by copper oxide Film, heated liquid oxidation thin film-forming method are limited, and oxidation steel structure is more loose, and manufacturing cycle is longer, is unsuitable for being mass produced And practical application.Chinese patent (Publication No. CN107522161A, publication date are on December 29th, 2017) discloses a kind of micro- The controllable copper substrate superhydrophobic surface and preparation method thereof of nanostructure.Firstly, carrying out laser ablation, structure on red copper substrate surface Produce rectangular, triangle or strip groove micrometer structure array；Nano wire is grown on surface by way of thermal oxide again；Finally Standing one week or more time in air, the i.e. controllable copper substrate superhydrophobic surface of acquisition micro nano structure.In the laser of this method Etching process is high to the dependence of equipment, and power consumption is higher, is unsuitable for large-scale production and application.Chinese patent (Publication No. CN101476121A, publication date be on July 8th, 2009) disclose it is a kind of using low-voltage oxidation process prepared on copper surface it is super-hydrophobic The method of film.This method prepares one layer of Kocide SD film in the inorganic chemistry method of copper sheet surface routine, then uses Low-voltage oxidation process carries out oxygenolysis processing to the Kocide SD film on copper sheet surface, and obtained upper layer is a micron flower-like structure, under Layer is the copper oxide based superhydrophobic thin films of the double-deck micro nano structure of nanowire structure.The invention is suitable only for preparing oxygen on copper surface Change copper based superhydrophobic thin films, and, preparation process requirement to experiment parameter stringent to the ratio requirement of potassium hydroxide and potassium peroxydisulfate Relatively high, this is mass produced it restricted.(Publication No. CN104357827A, publication date are 2 months 2015 to Chinese patent 18 days) disclose a kind of preparation method of super-hydrophobic corrosion-resistant copper substrate superhydrophobic surface.Firstly, by after cleaning treatment copper sheet with Certain density ammonia spirit is put into the stainless steel cauldron with polytetrafluoroethyllining lining, and reaction temperature is 60-120 DEG C, Constant temperature time is 3-24h, is cleaned after taking-up with deionized water, is dried with nitrogen；The copper sheet is immersed in different branch sulfuric acid again In ethanol solution, impregnate 6-24h after, obtain surface with nanometer rods, nano whiskers, nano-sheet, petal-like structures it is super thin Water copper sheet.But a series of oxidation steel structure, entire confined reaction are mainly prepared in the invention by way of hydrothermal growth Container can generate high temperature and pressure and a large amount of byproducts of reaction and volatile gas during the reaction, therefore right in actual production The airtightness of container, security requirement are relatively high, are unsuitable for being mass produced.Chinese patent (Publication No. CN101864571A, Publication date is on October 20th, 2010) disclose a kind of method for preparing copper substrate superhydrophobic surface.Firstly, by copper-based surfaces in nitre In acid solution etching a moment take out, then uniformly spray acetic acid, at room temperature, 50% or more relative humidity, dry in the shade 24 hours after, Acetic acid is sprayed again, forms the superficial layer throughout green spot；Then the baking oven baking that above-mentioned surface is put into 300 ± 50 DEG C is taken Out, it cools down in air；Finally, by sample in 40- in the ethanol solution of certain density positive stearylmercaptan or lauryl mercaptan 60 DEG C of water-baths are impregnated, and super hydrophobic surface is made.The invention mainly by high temperature decompose verdigris in the way of in copper sheet surface system Different structure copper oxide, so the combination of the copper oxide and copper sheet on surface is weaker, and its of verdigris preparation process pair early period Environmental condition requires relatively high, unsuitable large-scale production and practical application.
The present invention has been prepared by the simple procedure of chemistry displacement, directly thermal oxidation with dendroid micro nano structure Copper oxide can prepare super-hydrophobic coat on aluminium matrix in conjunction with low energy modification.Preparation method in the present invention, work Skill process is simple, at low cost, the copper oxide stable structure of preparation；And the super-hydrophobic coat of low energy modification preparation is combined to have Good automatically cleaning and thermal stability etc..In addition, this method may be applied not only on aluminium material surface, magnesium, zinc, iron can also be applied to On equal metal material surfaces, it is suitble to industrialized production.
Summary of the invention
It is an object of the invention to research and develop a kind of simple, quick preparation dendroid micro nano structure copper oxide super-hydrophobic coat Method, using this method aluminium alloy matrix surface preparation have super-hydrophobicity copper oxide coating, to enable aluminum alloy to table Face has super-hydrophobic, anticorrosion, good antiscale property and self-cleaning function, improves the service life of aluminium alloy.
To achieve the above object, concrete technology flow process of the invention is as follows:
1, the pre-treatment of aluminium substrate: the aluminium that will be processed with metallographic waterproof abrasive paper (being polishing to 2000# step by step by 300#) Sample polishes smooth, and the sample polished is sequentially placed into acetone, carries out ultrasonic cleaning 5-15min in dehydrated alcohol, To remove the grease and pollutant of specimen surface；Then cleaned aluminium substrate sample is successively subjected to surface alkali cleaning except oxidation Film and pickling processes: alkali cleaning oxide film dissolving is the alkaline water that the aluminium sample that will be polished smooth is put into the sodium hydroxide containing 3%-10% In washing lotion after room temperature processing 1-2min, washes of absolute alcohol is used；Pickling processes are to use the aluminium sample after alkali cleaning oxide film dissolving After the pickling solution of the nitric acid containing 20%-30% rinses, with washes of absolute alcohol, drying for standby；
2, chemistry displacement reactive deposition layers of copper: the CuCl of 30-150g/L is configured2·2H2O aqueous solution, or configuration contain 20- The CuSO of 120g/L4·5H2The FeCl of O and 2.5-40g/L3·6H2The mixed aqueous solution of O (or NaCl of 5-60g/L) composition, The aluminium sample cleaned up in step 1 is immersed in above-mentioned configured mixed solution and carries out chemistry displacement reaction, reaction Time is 0.5-5min；The sample after reaction is immersed in suitable clear water (1-2L) again, time 10-20min, removal surface is residual The reaction solution stayed；Then sample is put into drying box and is dried at 50-150 DEG C；
3, the aluminium sample that surface in step 2 is covered with copper deposits thermal oxidation: is put into tube furnace (or Muffle Furnace) it is heat-treated, atmosphere is air, and 2-6 DEG C of heating rate/min, heat treatment temperature is 300-600 DEG C, soaking time For 1-5h, is taken out after heat treatment, be air-cooled to room temperature；
4, low energy is modified: sample obtained in step 3 is put into katakinetomere (the hard acid acid, palm fibre of 0.005-0.05mol/L Palmitic acid acid, lauric acid, perfluoro caprylic acid) 1-5h is impregnated in ethanol solution, it is put into culture dish after taking-up, is then placed in drying box In dried at 50-120 DEG C, can be obtained surface have dendroid microscopic appearance copper oxide super-hydrophobic coat.
Deionized water is dripped on copper oxide super hydrophobic surface obtained above and carries out contact angle determination, contact angle is all larger than 150 °, roll angle is less than 10 °.In addition, the super hydrophobic surface is placed 9 months or more in air is still able to maintain its super-hydrophobicity, After taking out after impregnating 1 month in water, contact angle is still greater than 150 °, and roll angle is less than 10 °.
Compared with prior art, the beneficial effects of the present invention are:
It (1) is that direct in-situ generates on the copper coating with micro nano structure in a manner of directly thermal oxidation in the present invention Copper oxide coating with micro nano structure, it is simple and easy to do.
(2) preparation method in the present invention, production cost is low, and high production efficiency is easy to realize industrial production.
(3) treatment process that the present invention uses does not have particular/special requirement to the shape and size of sample, increases of the invention Application, and other metal material surfaces such as extend to magnesium, zinc, iron.
Detailed description of the invention
Fig. 1 is the SEM figure of copper oxide super hydrophobic surface；
Fig. 2 is contact angle and roll angle of the deionized water drop in copper oxide super-hydrophobic coat；
Fig. 3 is the relational graph that copper oxide super hydrophobic surface continues soaking time and contact angle, roll angle in water；
Fig. 4 is the relational graph of copper oxide super hydrophobic surface soaking time and contact angle, roll angle at 200 DEG C；
Fig. 5 is the self-cleaning performance schematic diagram of copper oxide super hydrophobic surface.
Specific embodiment
It elaborates with reference to the accompanying drawing to the present invention:
It is an object of the invention to develop one kind simply and rapidly to prepare copper oxide super-hydrophobic coat in aluminium material surface, according to By super hydrophobic surface intrinsic hydrophobic, anticorrosion, good antiscale property and self-cleaning function, improve the service life of aluminium.
In order to achieve the above objectives, the present invention is using fine aluminium and 6061 aluminium alloys as research object, in aluminium and aluminum alloy surface system For copper oxide super-hydrophobic coat.
Specific embodiment one:
(1) choosing the fine aluminium that size is 20 × 40 × 2mm is substrate sample, and substrate sample is polished light with metallographic waterproof abrasive paper It is sliding, and the sample polished is sequentially placed into acetone, ultrasonic cleaning 5min in dehydrated alcohol, to remove the oil of specimen surface Rouge and pollutant；
(2) above-mentioned cleaned fine aluminium sample is submerged initially in the alkaline water lotion containing 3% sodium hydroxide at (room temperature) After managing 2min, sample washes of absolute alcohol；It is dry with washes of absolute alcohol after being rinsed again with the pickling solution of 20% nitric acid, it is real The oxide film dissolving and activation processing of existing surface of pure aluminum；
(3) the above-mentioned fine aluminium sample handled well is immersed in the CuCl containing 50g/L2·2H2In O aqueous solution, when chemistry is replaced Between be 4.5min, then by after reaction surface immerse 1L clear water in, time 20min removes remaining reaction solution, then will examination Sample is put into drying box dries at 80 DEG C, obtains to surface and is covered with the fine aluminium of the copper deposits of dendroid micro nano structure pattern Sample；
(4) sample that step (3) obtains is put into Muffle furnace and is heat-treated, heating rate is 3 DEG C/min, heat treatment Temperature is 300 DEG C, and soaking time 2h takes out after heat treatment, is air-cooled to room temperature；
(5) sample that step poly- (4) obtains is put into the stearic acid ethanol solution that concentration is 0.01mol/L and is impregnated 2h is put into culture dish after taking-up, is put into drying box and is dried at 60 DEG C, and surface can be obtained with dendroid micro-nano structure Copper oxide super-hydrophobic coat (as shown in Figure 1)；3 μ L deionized water drops are about in the contact angle of the copper oxide super hydrophobic surface 159.64 °, roll angle is about 4.5 ° (as shown in Figure 2).
(6) the copper oxide super hydrophobic surface being prepared is fully immersed in a period of time (5 days, 10 days, 15 in clear water It, 20 days, 25 days, 30 days), measure 3 μ L deionized water drops in the contact angle of the super hydrophobic surface, roll angle and soaking time Relationship (as shown in Figure 3).After the super hydrophobic surface is completely soaked 30 days in clear water, water contact angle value is about 159.41 °, Roll angle is about 4.6 °, it was demonstrated that the super hydrophobic surface can be kept in contact angle, roll angle stability for a long time in clear water.
(7) the copper oxide super hydrophobic surface being prepared is placed on 200 DEG C of heating furnace inside holding (3 is small for a period of time When, 6 hours, 9 hours, 12 hours), measure 3 μ L deionized water drops in the contact angle of the super hydrophobic surface, roll angle and immersion The relationship (as shown in Figure 4) of time.For the super hydrophobic surface after heat preservation 12 hours, water contact angle value is about 159.60 °, is rolled Angle is about 4.8 °, it was demonstrated that the super hydrophobic surface can be kept in contact angle at 200 DEG C or less for a long time, roll angle is stablized.
(8) by the floating bead powder of a certain amount of granularity (100-150 μm) uniform one layer of shakedown on the super hydrophobic surface, and This super hydrophobic surface is tilted about 8 °, then drips the deionized water drop of 10 μ L in the surface, deionized water drop in the height of about 5cm It is easy to the floating bead powder that surface covers taking away (as shown in Figure 5), it was demonstrated that the super hydrophobic surface has good self-cleaning property Energy.
Specific embodiment two:
(1) choosing 6061 aluminium alloys that size is 20 × 40 × 2mm is substrate sample, with metallographic waterproof abrasive paper by substrate sample It polishes smooth, and the sample polished is sequentially placed into acetone, ultrasonic cleaning 10min in dehydrated alcohol, to remove sample The grease and pollutant on surface；
(2) above-mentioned 6061 cleaned aluminum alloy specimens are submerged initially in the alkaline water lotion containing 10% sodium hydroxide After (room temperature) handles 1min, sample washes of absolute alcohol；It is clear with dehydrated alcohol after being rinsed again with the pickling solution of 30% nitric acid It washes, it is dry, realize the oxide film dissolving and activation processing of 6061 aluminum alloy surfaces；
(3) above-mentioned 6061 aluminum alloy specimens handled well are immersed in the CuSO containing 25g/L4·5H2O's and 5g/L FeCl3·6H2In O aqueous solution, chemical time swap be 4min, then by after reaction surface immerse 1L clear water in, the time 15min removes remaining reaction solution；Then sample is put into drying box and is dried at 100 DEG C, obtain surface with dendroid The copper coating of microscopic appearance；
(4) 6061 aluminum alloy specimens that the surface that step (3) obtains is covered with copper deposits are put into Muffle furnace and are carried out Heat treatment, heating rate are 3 DEG C/min, and heat treatment temperature is 400 DEG C, and soaking time 4h takes out after heat treatment, air-cooled To room temperature；
(5) sample that step poly- (4) obtains is put into the palmitinic acid ethanol solution that concentration is 0.02mol/L and is impregnated 2h is put into culture dish after taking-up, is put into drying box and is dried at 60 DEG C, super hydrophobic surface can be obtained.Deionized water drop It is about 158.76 ° in the contact angle of the copper oxide super hydrophobic surface, roll angle is about 5.2 °.
Specific embodiment three:
(1) choosing 6061 aluminium alloys that size is 20 × 40 × 2mm is substrate sample, with metallographic waterproof abrasive paper by substrate sample It polishes smooth, and the sample polished is sequentially placed into acetone, ultrasonic cleaning 20min in dehydrated alcohol, to remove sample The grease and pollutant on surface；
(2) above-mentioned 6061 cleaned aluminum alloy specimens are submerged initially in (room in the alkaline water lotion containing 8% sodium hydroxide Temperature) processing 1.3min after, sample washes of absolute alcohol；After being rinsed again with the pickling solution of 25% nitric acid, with washes of absolute alcohol, It is dry, realize the oxide film dissolving and activation processing of 6061 aluminum alloy surfaces；
(3) above-mentioned 6061 aluminum alloy specimens handled well are immersed in the CuSO containing 25g/L4·5H2The NaCl of O and 10g/L In aqueous solution, chemical time swap is 4min, then by the clear water of the surface immersion 1.5L after reaction, time 20min is removed residual The reaction solution stayed；Then sample is put into drying box and is dried at 80 DEG C, obtain the copper that surface has dendroid microscopic appearance Coating；
(4) 6061 aluminum alloy specimens that the surface that step (3) obtains is covered with copper deposits are put into Muffle furnace and are carried out Heat treatment, heating rate are 4 DEG C/min, and heat treatment temperature is 500 DEG C, and soaking time 3h takes out after heat treatment, air-cooled To room temperature；
(5) sample that step poly- (4) obtains is put into the lauric acid ethanol solution that concentration is 0.04mol/L and is impregnated 2h is put into culture dish after taking-up, is put into drying box and is dried at 60 DEG C, super hydrophobic surface can be obtained.Deionized water drop It is about 158.97 ° in the contact angle of the copper oxide super hydrophobic surface, roll angle is 4.8 °.
Specific embodiment four:
(1) choosing 6061 aluminium alloys that size is 20 × 40 × 2mm is substrate sample, with metallographic waterproof abrasive paper by substrate sample It polishes smooth, and the sample polished is sequentially placed into acetone, ultrasonic cleaning 15min in dehydrated alcohol, to remove sample The grease and pollutant on surface；
(2) above-mentioned 6061 cleaned aluminum alloy specimens are submerged initially in (room in the alkaline water lotion containing 6% sodium hydroxide Temperature) processing 1.5min after, sample washes of absolute alcohol；After being rinsed again with the pickling solution of 30% nitric acid, with washes of absolute alcohol, It is dry, realize the oxide film dissolving and activation processing of 6061 aluminum alloy surfaces；
(3) above-mentioned 6061 aluminum alloy specimens handled well are immersed in the CuSO containing 50g/L4·5H2The NaCl of O and 30g/L In aqueous solution, chemical time swap is 3.5min, then by the clear water of the surface immersion 2L after reaction, time 20min is removed residual The reaction solution stayed；Then sample is put into drying box and is dried at 80 DEG C, obtain the copper that surface has dendroid microscopic appearance Coating；
(4) 6061 aluminum alloy specimens that the surface that step (3) obtains is covered with copper deposits are put into Muffle furnace and are carried out Heat treatment, heating rate are 5 DEG C/min, and heat treatment temperature is 500 DEG C, and soaking time 2h takes out after heat treatment, air-cooled To room temperature；
(5) sample that step poly- (4) obtains is put into the perfluoro caprylic acid ethanol solution that concentration is 0.05mol/L and is impregnated 3h is put into culture dish after taking-up, is put into drying box and is dried at 60 DEG C, super hydrophobic surface can be obtained.Deionized water drop It is about 159.31 ° in the contact angle of the copper oxide super hydrophobic surface, roll angle is 4.6 °.

Claims (1)

1. a kind of method for preparing dendroid micro nano structure copper oxide super-hydrophobic coat, it is characterised in that the micro-nano copper oxide Super-hydrophobic coat preparation method the following steps are included:
(1) pre-treatment of aluminium substrate: the aluminium sample that will be processed with metallographic waterproof abrasive paper (being polishing to 2000# step by step by 300#) It polishes smooth, and the sample polished is sequentially placed into acetone, carries out ultrasonic cleaning 5-15min in dehydrated alcohol, with removal The grease and pollutant of specimen surface；Then cleaned aluminium substrate sample is successively subjected to surface alkali cleaning oxide film dissolving and acid Wash processing: alkali cleaning oxide film dissolving is that the aluminium sample that will be polished smooth is put into the alkaline water lotion of the sodium hydroxide containing 3%-10% After room temperature handles 1-2min, washes of absolute alcohol is used；Pickling processes are by the aluminium sample 20%- after alkali cleaning oxide film dissolving After the pickling solution of 30% nitric acid rinses, with washes of absolute alcohol, drying for standby；
(2) chemistry displacement reactive deposition layers of copper: the CuCl of 30-150g/L is configured2·2H2O aqueous solution, or configuration contain 20-120g/L CuSO4·5H2The FeCl of O and 2.5-40g/L3·6H2The mixed aqueous solution of O (or NaCl of 5-60g/L) composition, by step (1) the aluminium sample cleaned up in, which is immersed in above-mentioned configured mixed solution, carries out chemistry displacement reaction, reaction time For 0.5-5min；The sample after reaction is immersed in suitable clear water (1-2L) again, time 10-20min removes remaining reaction Liquid；Then sample is put into drying box and is dried at 50-150 DEG C；
(3) the aluminium sample that surface is covered with copper deposits in step (2) thermal oxidation: is put into tube furnace (or Muffle furnace) In be heat-treated, atmosphere is air, 2-6 DEG C of heating rate/min, and heat treatment temperature is 300-600 DEG C, soaking time For 1-5h, is taken out after heat treatment, be air-cooled to room temperature；
(4) low energy modify: by sample obtained in step (3) be put into 0.005-0.05mol/L katakinetomere (hard acid acid, Palmitinic acid, lauric acid, perfluoro caprylic acid) 1-5h is impregnated in ethanol solution, it is put into culture dish after taking-up, is then placed in drying It is dried at 50-120 DEG C in case, the copper oxide super-hydrophobic surface coating with dendroid microscopic appearance can be obtained.
CN201811086518.6A 2018-09-18 2018-09-18 Method for preparing copper oxide super-hydrophobic coating with dendritic micro-nano structure Expired - Fee Related CN109023319B (en)

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CN111167686A (en) * 2019-08-22 2020-05-19 中国船舶重工集团公司第七二五研究所 Long-acting anticorrosive coating on copper alloy surface and preparation method thereof
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CN110791785A (en) * 2019-11-06 2020-02-14 山东科技大学 Electrodeposition layer-lyophobic-super-slippery triple film with composite anticorrosion function and preparation method and application thereof
CN111647909A (en) * 2020-07-01 2020-09-11 中国科学技术大学 Dendritic copper electrode with hydrophobic surface and preparation method and application thereof
CN111926299A (en) * 2020-08-05 2020-11-13 北京信息科技大学 Multi-level Cu film with surface interface regulation and control function and preparation method thereof
CN111926299B (en) * 2020-08-05 2022-07-26 北京信息科技大学 Multi-level Cu film with surface interface regulation and control function and preparation method thereof
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