CN106086835A - A kind of aluminum and the preparation method of superhydrophobic surface of aluminum alloy - Google Patents

A kind of aluminum and the preparation method of superhydrophobic surface of aluminum alloy Download PDF

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CN106086835A
CN106086835A CN201610596941.5A CN201610596941A CN106086835A CN 106086835 A CN106086835 A CN 106086835A CN 201610596941 A CN201610596941 A CN 201610596941A CN 106086835 A CN106086835 A CN 106086835A
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aluminum
mixed solution
preparation
aluminum alloy
dehydrated alcohol
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CN106086835B (en
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朱艳
王力
黎振华
贺胤
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Kunming University of Science and Technology
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Kunming University of Science and Technology
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    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/31Coating with metals
    • C23C18/38Coating with copper
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1635Composition of the substrate
    • C23C18/1637Composition of the substrate metallic substrate
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23CCOATING 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
    • C23C18/00Chemical 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
    • C23C18/16Chemical 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
    • C23C18/1601Process or apparatus
    • C23C18/1633Process of electroless plating
    • C23C18/1646Characteristics of the product obtained

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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)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Abstract

The invention discloses the preparation method of a kind of aluminum and superhydrophobic surface of aluminum alloy, belong to field of metal surface treatment.The method of the invention is the super hydrophobic surface that the preparation technology by a step chemical deposition and modification goes out low-surface-energy dendritic crystalline micro-nano compound structure at aluminum or aluminum alloy surface structure; with the common method of fractional steps (such as chemical deposition or chemical etching etc.; modify again) compare; used by the method, the time is short; preparation efficiency is high, and pollution-free, conditioning apparatus is simple; with low cost, beneficially large-scale production.

Description

A kind of aluminum and the preparation method of superhydrophobic surface of aluminum alloy
Technical field
The present invention relates to the preparation method of a kind of aluminum and superhydrophobic surface of aluminum alloy, belong to field of metal surface treatment.
Background technology
It is little that aluminum and alloy thereof have density, and intensity is high, and the features such as electrical and thermal conductivity is good, it is at building, traffic, aviation, machine The fields such as tool manufacture and household electrical appliances have a wide range of applications.Such as: the fin of the indoor evaporator of air-conditioning and outdoor condenser with And catheter segment is alumina-base material, high-voltage power transmission cable is aluminum stranded conductor, and the blade of a part of aero-engine is aluminium alloy.This The most easily there is condensed water or icing, frosting in the aluminum or aluminum alloy that a little occasions use, and the lighter causes indoor power failure, air-conditioning leakage Water, freezing and heat inefficacy etc., severe one can cause transmission line of electricity to fall bar, the accident such as tower and air crash of falling.Research shows super-hydrophobic table Face processes the deicing properties that not only can improve aluminum or aluminum alloy, the most also makes it have anti-fouling and self-cleaning, anticorrosion, fall resistance etc. Function.
Super hydrophobic surface is that water contact angle is more than 150 ° and the roll angle surface less than 10 °.Super hydrophobic surface is thought in research Structure must be fulfilled for two conditions: surface must have micro-nano coarse structure and this material has extremely low surface free energy. For metal especially alumina-base material, its surface activity is high, surface can be big, the most first needs by method chemically or physically Rough surfaceization is made to modify to obtain superhydrophobic characteristic to existing coarse structure by low-surface energy substance again.Patent CN101007304 discloses and utilizes two-step method first aluminum and aluminium alloy to be placed in containing nitric acid and slaine (mantoquita or nickel salt) solution After middle corrosion 0.5-20 min, then can obtain, through silane immersion modification (12-14 h), the super-hydrophobic table that maximum contact angle is 165 ° Face, but this chemical attack adds that to soak the whole preparation time of method modified long, and preparation efficiency is relatively low, in mixed liquor Nitric acid there is stronger corrosivity.Patent CN104911599A discloses one and utilizes laser ablation to increase temperature oxidation (100- 250 DEG C, 2-8 h) method prepare superhydrophobic surface of aluminum alloy, but this method, be only applicable to regular aluminum alloy plate materials, Appointed condition and cost used by Tong Shi are high, and preparation time is long, is unfavorable for scale.For simplifying the preparation work of super hydrophobic surface Skill, the course synchronization enabling aluminum alloy to rough surface and low-surface-energy is carried out, and patent CN2012101423432 discloses aluminum and closes The method of gold super hydrophobic surface one step immersion treatment will be dipped in the mixed solution dissolved with hydrochloric acid, stearic acid and ethanol by aluminium alloy (temperature 30-70 DEG C, soak time 5-25 min), takes out and is placed on cabinet-type electric furnace solidification (temperature 50-90 DEG C, time 30-90 Min) obtain super hydrophobic surface, although preparation technology is simplified, but this step soaks the preparation work obtaining super hydrophobic surface Skill condition is relatively high, and overall manufacturing cycle is longer.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of aluminum and superhydrophobic surface of aluminum alloy, specifically include following step Rapid:
(1) preparation of mixed solution: by CuCl2It is dissolved in the mixed solvent of water and dehydrated alcohol and obtains mixed solution A, mix molten CuCl in liquid A2Concentration be 0.2-0.25 mol/L, then n-dodecyl mereaptan is dropwise added dropwise in mixed solution A and fully Being mixed to get mixed solution B, the addition of n-dodecyl mereaptan is the 0.8 ~ 1.2% of mixed solution A volume.
(2) pre-treatment: remove greasy dirt and the oxide layer on aluminum or aluminum alloy surface.
(3) one step rapid chemicals depositions with modify: the aluminum or aluminum alloy of pre-treatment is placed in mixed solution B after 5-10s Take out, take out after being dipped in dehydrated alcohol and quickly dry up.
Preferably, in mixed solvent of the present invention, the volume ratio of deionized water and dehydrated alcohol is 1:2.
Preferably, step of the present invention (2) use sand paper remove surface of low-carbon steel oxide layer and greasy dirt, and at acetone Dry up with ultrasonic cleaning in ethanol.
The technical method that the present invention provides has the advantage that
(1) present invention employs with low cost, the copper chloride of nontoxic pollution-free, n-dodecyl mereaptan, ethanol and the mixed solution of water, By a step rapid chemical deposition and the preparation technology modified, make the structure of aluminum or aluminum alloy surface micro-nano coarse structure and low The chemical modification of surface energy is carried out simultaneously, so greatly simplifies the preparation technology of aluminum substrate superhydrophobic surface, this preparation process The shortest have only to 5 seconds;In general, the time used by this preparation technology is short, and preparation efficiency is high, nontoxic pollution-free, and condition sets Standby simple, with low cost, beneficially large-scale production.
(2) the method for the invention can varying in size, different aluminum or aluminum alloy surface prepare have antifouling The super hydrophobic surface of the excellent properties such as self-cleaning and drag reduction, and by process optimization can prepare with water contact angle be 156 °, When roll angle is 2 °, super-hydrophobic aluminum or aluminum alloy, its anti-fouling and self-cleaning and resistance reducing performance behave oneself best.
Accompanying drawing explanation
Fig. 1 is the contact angle optical picture of the superhydrophobic surface of aluminum alloy for preparing of embodiment 1 and water.
Fig. 2 is the contact angle optical picture of the superhydrophobic surface of aluminum alloy for preparing of embodiment 2 and water.
Fig. 3 is the contact angle optical picture of the metallic aluminum super-hydrophobic surface for preparing of embodiment 3 and water.
Detailed description of the invention
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings, but protection scope of the present invention is also It is not limited to described content.
Embodiment 1
The present embodiment provides the preparation method of a kind of superhydrophobic surface of aluminum alloy, specifically includes following steps:
(1) preparation of mixed solution: by CuCl2The mixing being dissolved in water and dehydrated alcohol (water and dehydrated alcohol volume ratio 1:2) is molten Agent obtains mixed solution A, CuCl in mixed solution A2Concentration be 0.2mol/L, then by the n-dodecyl mereaptan of 0.6ml by Being added dropwise in 60ml mixed solution A and be sufficiently mixed and obtain mixed solution B, the addition of n-dodecyl mereaptan is mixed solution A The 1% of volume.
(2) pre-treatment: after removing aluminium alloy (trade mark 6061) surface oxide layer and greasy dirt with 600#SiC sand paper, put successively Within ultrasonic 10 minutes in 99% acetone and 99% ethanol, take out and quickly dry up.
(3) one step rapid chemical depositions and modification: the aluminium alloy of process is placed in mixed solution and takes out after 10s, be dipped in After in dehydrated alcohol, taking-up quickly dries up, thus obtains anti-fouling and self-cleaning and the super-hydrophobic table of aluminium alloy of resistance reducing performance with excellence Face, its roll angle is 156 °, and contact angle is 2 ° (such as Fig. 1).
Embodiment 2
The present embodiment provides the preparation method of a kind of superhydrophobic surface of aluminum alloy, specifically includes following steps:
(1) preparation of mixed solution: CuCl2It is dissolved in the mixed solvent (water and dehydrated alcohol volume ratio 1:2) of water and dehydrated alcohol In obtain mixed solution A, CuCl in mixed solution A2Concentration be 0.25 mol/L, then by 0.48ml n-dodecyl mereaptan by Being added dropwise in 60ml mixed solution A and be sufficiently mixed and obtain mixed solution B, the addition of n-dodecyl mereaptan is mixed solution A The 0.8% of volume.
(2) pre-treatment: after removing aluminium alloy (trade mark 6061) surface oxide layer and greasy dirt with 600#SiC sand paper, put successively Within ultrasonic 5 minutes in 99% acetone and 99% ethanol, take out and quickly dry up.
(3) rapid chemical deposition and modification: the aluminium alloy of pre-treatment is placed in mixed solution and takes out after 5 s, be dipped in nothing After in water-ethanol, taking-up quickly dries up, thus obtains anti-fouling and self-cleaning and the super-hydrophobic table of aluminium alloy of resistance reducing performance with excellence Face, its roll angle is 152 °, and contact angle is 3 ° (such as Fig. 2).
Embodiment 3
The present embodiment provides the preparation method of a kind of metallic aluminum super-hydrophobic surface, specifically includes following steps:
(1) preparation of mixed solution: CuCl2It is dissolved in water and the mixed solvent of dehydrated alcohol (water and dehydrated alcohol volume ratio 1:2) In obtain mixed solution A, CuCl in mixed solution A2Concentration be 0.23 mol/L, then by 0.72ml n-dodecyl mereaptan by Being added dropwise in 60ml mixed solution A and be sufficiently mixed and obtain mixed solution B, the addition of n-dodecyl mereaptan is mixed solution A The 1.2% of volume.
(2) pre-treatment: after removing fine aluminium sheet surface oxide layer and greasy dirt with 800#SiC sand paper, be sequentially placed into 99% acetone and Within in 99% ethanol ultrasonic 10 minutes, take out and quickly dry up.
(3) one step rapid chemical depositions and modification: the aluminium flake of process is placed in mixed solution and takes out after 5 s, be dipped in nothing After in water-ethanol, taking-up quickly dries up, thus obtains anti-fouling and self-cleaning and the super-hydrophobic table of aluminium alloy of resistance reducing performance with excellence Face, its roll angle is 154 °, and contact angle is 2 ° (such as Fig. 3).

Claims (3)

1. an aluminum and the preparation method of superhydrophobic surface of aluminum alloy, it is characterised in that specifically include following steps:
(1) preparation of mixed solution: by CuCl2It is dissolved in the mixed solvent of water and dehydrated alcohol and obtains mixed solution A, mix molten CuCl in liquid A2Concentration be 0.2 ~ 0.25 mol/L, then n-dodecyl mereaptan is dropwise added dropwise in mixed solution A and fully Being mixed to get mixed solution B, the addition of n-dodecyl mereaptan is the 0.8 ~ 1.2% of mixed solution A volume;
(2) pre-treatment: remove greasy dirt and the oxide layer on aluminum or aluminum alloy surface;
(3) one step rapid chemical depositions and modification: the aluminum or aluminum alloy of pre-treatment is placed in mixed solution B and takes out after 5-10s, Take out after being dipped in dehydrated alcohol and quickly dry up.
Aluminum and the preparation method of superhydrophobic surface of aluminum alloy the most according to claim 1, it is characterised in that: in mixed solvent Ionized water is 1:2 with the volume ratio of dehydrated alcohol.
Aluminum and the preparation method of superhydrophobic surface of aluminum alloy the most according to claim 1, it is characterised in that: step is adopted in (2) Remove surface of low-carbon steel oxide layer and greasy dirt with sand paper, and ultrasonic cleaning dries up in acetone and ethanol.
CN201610596941.5A 2016-07-27 2016-07-27 A kind of preparation method of aluminium and superhydrophobic surface of aluminum alloy Active CN106086835B (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106513267A (en) * 2016-11-17 2017-03-22 榆林学院 Aluminum powder doped aluminum oxide hydrophobic film and preparation method thereof
CN107164746A (en) * 2017-04-27 2017-09-15 武汉科技大学 The preparation method on drag reduction copper surface
CN107761085A (en) * 2017-10-31 2018-03-06 哈尔滨工业大学 A kind of method that one-step method prepares aluminium base super hydrophobic surface

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101942654A (en) * 2010-10-27 2011-01-12 东南大学 Method for immersing superhydrophobic surface of aluminum alloy in one step
CN102051612A (en) * 2010-12-02 2011-05-11 西北工业大学 Method for preparing super-hydrophobic lubricant coating on surface of light metal
CN102677058A (en) * 2012-05-28 2012-09-19 大连理工大学 Method for etching and preparing ultra-hydrophobic aluminum surface by using saline solution containing copper ions and chloride ions
CN104846376A (en) * 2015-05-29 2015-08-19 清华大学 Preparation method of metal-based super-hydrophobic surface
US20160153094A1 (en) * 2014-12-01 2016-06-02 Anish Tuteja Salt Based Etching of Metals and Alloys for Fabricating Superhydrophobic and Superoleophobic Surfaces

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101942654A (en) * 2010-10-27 2011-01-12 东南大学 Method for immersing superhydrophobic surface of aluminum alloy in one step
CN102051612A (en) * 2010-12-02 2011-05-11 西北工业大学 Method for preparing super-hydrophobic lubricant coating on surface of light metal
CN102677058A (en) * 2012-05-28 2012-09-19 大连理工大学 Method for etching and preparing ultra-hydrophobic aluminum surface by using saline solution containing copper ions and chloride ions
US20160153094A1 (en) * 2014-12-01 2016-06-02 Anish Tuteja Salt Based Etching of Metals and Alloys for Fabricating Superhydrophobic and Superoleophobic Surfaces
CN104846376A (en) * 2015-05-29 2015-08-19 清华大学 Preparation method of metal-based super-hydrophobic surface

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106513267A (en) * 2016-11-17 2017-03-22 榆林学院 Aluminum powder doped aluminum oxide hydrophobic film and preparation method thereof
CN107164746A (en) * 2017-04-27 2017-09-15 武汉科技大学 The preparation method on drag reduction copper surface
CN107761085A (en) * 2017-10-31 2018-03-06 哈尔滨工业大学 A kind of method that one-step method prepares aluminium base super hydrophobic surface

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