CN106086835B - A kind of preparation method of aluminium and superhydrophobic surface of aluminum alloy - Google Patents

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

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CN106086835B
CN106086835B CN201610596941.5A CN201610596941A CN106086835B CN 106086835 B CN106086835 B CN 106086835B CN 201610596941 A CN201610596941 A CN 201610596941A CN 106086835 B CN106086835 B CN 106086835B
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aluminum alloy
mixed solution
preparation
aluminium
aluminum
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CN106086835A (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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    • 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
    • C23C18/1635—Composition of the substrate
    • C23C18/1637—Composition of the substrate metallic substrate
    • 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
    • C23C18/1646—Characteristics 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 methods of a kind of aluminium and superhydrophobic surface of aluminum alloy, belong to field of metal surface treatment.The method of the invention is the super hydrophobic surface for going out low-surface-energy dendritic crystalline micro-nano compound structure in aluminum or aluminum alloy surface structure by the preparation process of a step chemical deposition and modification; with the common method of fractional steps (such as chemical deposition or chemical etching; modify again) it compares; time used in this method is short; preparation efficiency is high, and pollution-free, conditioning apparatus is simple; it is low in cost, it is conducive to large-scale production.

Description

A kind of preparation method of aluminium and superhydrophobic surface of aluminum alloy
Technical field
The present invention relates to the preparation methods of a kind of aluminium and superhydrophobic surface of aluminum alloy, belong to field of metal surface treatment.
Background technique
The features such as aluminium and its alloy have density small, and intensity is high, and electrical and thermal conductivity is good, in building, traffic, aviation, machine The fields such as tool manufacture and household electrical appliances have a wide range of applications.Such as: the cooling fin of the indoor evaporator of air-conditioning and outdoor condenser with And its part conduit 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 Easily there is condensed water or icing, frosting in winter in the aluminum or aluminum alloy that a little occasions use, and less serious case causes indoor power failure, air-conditioning leakage Water, refrigeration and heating failure etc., severe one can cause transmission line of electricity fall bar, fall the accidents such as tower and air crash.Research shows that super-hydrophobic table Surface treatment can not only improve the deicing properties of aluminum or aluminum alloy, while also make it have anti-fouling and self-cleaning, anticorrosion, drop resistance etc. Function.
Super hydrophobic surface is that water contact angle is greater than 150 ° and surface of the roll angle less than 10 °.Super hydrophobic surface is thought in research Building must satisfy two conditions: surface must have micro-nano coarse structure and the material to have extremely low surface free energy. For metal especially alumina-base material, high surface activity, surface can be big, generally first need through method chemically or physically Modify surface roughening to obtain superhydrophobic characteristic with low-surface energy substance existing coarse structure again.Patent CN101007304, which is disclosed, is first placed in aluminium and aluminium alloy containing nitric acid and metal salt (mantoquita or nickel salt) solution using two-step method After middle corrosion 0.5-20 min, then modification (12-14 h) is impregnated through silane and can get the super-hydrophobic table that Maximum Contact angle is 165 ° Face, but the preparation time that this chemical attack adds the method impregnated and modified entire is too long, preparation efficiency is relatively low, in mixed liquor Nitric acid have stronger corrosivity.Patent CN104911599A, which is disclosed, a kind of increases temperature oxidation (100- using laser ablation 250 DEG C, 2-8 h) method prepare superhydrophobic surface of aluminum alloy, but this method is only applicable to regular aluminum alloy plate materials, Appointed condition used simultaneously and at high cost, preparation time is long, is unfavorable for scale.For the preparation work for simplifying super hydrophobic surface Skill, enables aluminum alloy to surface roughening progress synchronous with the process of low-surface-energy, and patent CN2012101423432 discloses aluminium conjunction Aluminium alloy is dipped in the mixed solution dissolved with hydrochloric acid, stearic acid and ethyl alcohol by the method for golden one step immersion treatment of super hydrophobic surface (30-70 DEG C of temperature, soaking time 5-25 min), taking-up be placed on cabinet-type electric furnace solidification (50-90 DEG C of temperature, time 30-90 Min super hydrophobic surface) is obtained, although preparation process is simplified, which impregnates the preparation work for obtaining super hydrophobic surface Skill condition is relatively high, and whole manufacturing cycle is longer.
Summary of the invention
The purpose of the present invention is to provide the preparation methods of a kind of aluminium and superhydrophobic surface of aluminum alloy, specifically include following step It is rapid:
(1) preparation of mixed solution: by CuCl2The in the mixed solvent for being dissolved in water and dehydrated alcohol obtains mixed solution A, mixes Close CuCl in solution A2Concentration be 0.2-0.25 mol/L, then n- dodecyl mereaptan is added dropwise in mixed solution A simultaneously dropwise It is sufficiently mixed to obtain mixed solution B, the additional amount of n- dodecyl mereaptan is the 0.8 ~ 1.2% of mixed solution A volume.
(2) pre-treatment: the greasy dirt and oxide layer on removal aluminum or aluminum alloy surface.
(3) one step rapid chemical sedimentations and modification: the aluminum or aluminum alloy of pre-treatment is placed in mixed solution B after 5-10s It takes out, takes out quickly drying after being dipped in dehydrated alcohol.
Preferably, in the mixed solvent deionized water of the present invention and the volume ratio of dehydrated alcohol are 1:2.
Preferably, using sand paper removal surface of low-carbon steel oxide layer and greasy dirt in step (2) of the present invention, and in acetone It is dried up with being cleaned by ultrasonic in ethyl alcohol.
Technical method provided by the invention has the advantages that
(1) present invention employs copper chloride low in cost, nontoxic and pollution-free, n- dodecyl mereaptan, the mixing of ethyl alcohol and water Solution makes the construction of aluminum or aluminum alloy surface micro-nano coarse structure by the preparation process of a step rapid chemical sedimentation and modification And its chemical modification of low-surface-energy carries out simultaneously, greatly simplifies the preparation process of aluminium base super hydrophobic surface in this way, the system Standby process most short needs 5 seconds；In general, the time used in this preparation process is short, and preparation efficiency is high, nontoxic and pollution-free, Conditioning apparatus is simple, low in cost, is conducive to large-scale production.
(2) the method for the invention can be prepared on of different sizes, different aluminum or aluminum alloy surface with antifouling The super hydrophobic surface of the excellent properties such as self-cleaning and drag reduction, and by process optimization can prepare be 156 ° with water contact angle, When roll angle is 2 °, super-hydrophobic aluminum or aluminum alloy, anti-fouling and self-cleaning and resistance reducing performance behave oneself best.
Detailed description of the invention
Fig. 1 is the contact angle optical picture of superhydrophobic surface of aluminum alloy and water that embodiment 1 is prepared.
Fig. 2 is the contact angle optical picture of superhydrophobic surface of aluminum alloy and water that embodiment 2 is prepared.
Fig. 3 is the contact angle optical picture of metallic aluminum super-hydrophobic surface and water that embodiment 3 is prepared.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, but protection scope of the present invention is simultaneously It is not limited to the content.
Embodiment 1
The present embodiment provides a kind of preparation methods of superhydrophobic surface of aluminum alloy, specifically includes the following steps:
(1) preparation of mixed solution: by CuCl2It is dissolved in the mixed of water and dehydrated alcohol (water and dehydrated alcohol volume ratio 1:2) Mixed solution A, CuCl in mixed solution A are obtained in bonding solvent2Concentration be 0.2mol/L, then by positive 12 sulphur of 0.6ml Alcohol is added dropwise in 60ml mixed solution A dropwise and is sufficiently mixed to obtain mixed solution B, and the additional amount of n- dodecyl mereaptan is that mixing is molten The 1% of liquid A volume.
(2) it pre-treatment: after 600#SiC sand paper removal aluminium alloy (trade mark 6061) surface oxide layer and greasy dirt, successively sets Take out quickly drying within ultrasound 10 minutes in 99% acetone and 99% ethyl alcohol.
(3) one step rapid chemical sedimentations and modification: the aluminium alloy of processing is placed in mixed solution after 10s and is taken out, is dipped in Quickly drying is taken out after in dehydrated alcohol, to obtain the super-hydrophobic table of aluminium alloy with excellent anti-fouling and self-cleaning and resistance reducing performance Face, roll angle are 156 °, and contact angle is 2 ° (such as Fig. 1).
Embodiment 2
The present embodiment provides a kind of preparation methods of superhydrophobic surface of aluminum alloy, specifically includes the following steps:
(1) preparation of mixed solution: CuCl2It is dissolved in mixed solvent (water and the dehydrated alcohol volume ratio of water and dehydrated alcohol Mixed solution A, CuCl in mixed solution A are obtained in 1:2)2Concentration be 0.25 mol/L, then by positive 12 sulphur of 0.48ml Alcohol is added dropwise in 60ml mixed solution A dropwise and is sufficiently mixed to obtain mixed solution B, and the additional amount of n- dodecyl mereaptan is that mixing is molten The 0.8% of liquid A volume.
(2) it pre-treatment: after 600#SiC sand paper removal aluminium alloy (trade mark 6061) surface oxide layer and greasy dirt, successively sets Take out quickly drying within ultrasound 5 minutes in 99% acetone and 99% ethyl alcohol.
(3) rapid chemical sedimentation and modification: the aluminium alloy of pre-treatment is placed in mixed solution after 5 s and is taken out, nothing is dipped in Quickly drying is taken out after in water-ethanol, to obtain the super-hydrophobic table of aluminium alloy with excellent anti-fouling and self-cleaning and resistance reducing performance Face, roll angle are 152 °, and contact angle is 3 ° (such as Fig. 2).
Embodiment 3
The present embodiment provides a kind of preparation methods of metallic aluminum super-hydrophobic surface, specifically includes the following steps:
(1) preparation of mixed solution: CuCl2It is dissolved in the mixing of water and dehydrated alcohol (water and dehydrated alcohol volume ratio 1:2) Mixed solution A, CuCl in mixed solution A are obtained in solvent2Concentration be 0.23 mol/L, then by positive 12 sulphur of 0.72ml Alcohol is added dropwise in 60ml mixed solution A dropwise and is sufficiently mixed to obtain mixed solution B, and the additional amount of n- dodecyl mereaptan is that mixing is molten The 1.2% of liquid A volume.
(2) pre-treatment: with 800#SiC sand paper removal fine aluminium piece surface oxide layer and greasy dirt after, be sequentially placed into 99% acetone and Take out quickly drying within ultrasound 10 minutes in 99% ethyl alcohol.
(3) one step rapid chemical sedimentations and modification: the aluminium flake of processing is placed in mixed solution after 5 s and is taken out, nothing is dipped in Quickly drying is taken out after in water-ethanol, to obtain the super-hydrophobic table of aluminium alloy with excellent anti-fouling and self-cleaning and resistance reducing performance Face, roll angle are 154 °, and contact angle is 2 ° (such as Fig. 3).

Claims (3)

1. the preparation method of a kind of aluminium and superhydrophobic surface of aluminum alloy, which is characterized in that specifically includes the following steps:
(1) preparation of mixed solution: by CuCl2The in the mixed solvent for being dissolved in water and dehydrated alcohol obtains mixed solution A, mixes molten CuCl in liquid A2Concentration be 0.2 ~ 0.25 mol/L, then n- dodecyl mereaptan is added dropwise to dropwise in mixed solution A and sufficiently It is mixed to get mixed solution B, the additional amount of n- dodecyl mereaptan is the 0.8 ~ 1.2% of mixed solution A volume；
(2) pre-treatment: the greasy dirt and oxide layer on removal aluminum or aluminum alloy surface；
(3) one step rapid chemical sedimentations and modification: the aluminum or aluminum alloy of pre-treatment being placed in mixed solution B after 5-10s and is taken out, Quickly drying is taken out after being dipped in dehydrated alcohol.
2. the preparation method of aluminium and superhydrophobic surface of aluminum alloy according to claim 1, it is characterised in that: in the mixed solvent is gone The volume ratio of ionized water and dehydrated alcohol is 1:2.
3. the preparation method of aluminium and superhydrophobic surface of aluminum alloy according to claim 1, it is characterised in that: step is adopted in (2) Aluminium and aluminum alloy surface oxide layer and greasy dirt are removed with sand paper, and is cleaned by ultrasonic drying in acetone and ethyl alcohol.
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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CN106513267B (en) * 2016-11-17 2019-06-21 榆林学院 A kind of aluminium powder doped aluminium 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
CN107761085B (en) * 2017-10-31 2021-01-29 哈尔滨工业大学 Method for preparing aluminum-based super-hydrophobic surface by one-step method

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CN101942654B (en) * 2010-10-27 2012-07-18 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

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