CN105018999B - The method of aluminum alloy differential arc oxidation film growth in situ layered double hydroxide - Google Patents

The method of aluminum alloy differential arc oxidation film growth in situ layered double hydroxide Download PDF

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CN105018999B
CN105018999B CN201510400290.3A CN201510400290A CN105018999B CN 105018999 B CN105018999 B CN 105018999B CN 201510400290 A CN201510400290 A CN 201510400290A CN 105018999 B CN105018999 B CN 105018999B
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arc oxidation
differential arc
oxidation film
layered double
double hydroxide
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CN105018999A (en
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王艳秋
窦宝捷
邵亚薇
孟国哲
张涛
刘斌
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Harbin Engineering University
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Harbin Engineering University
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Abstract

The present invention is to provide a kind of method of aluminum alloy differential arc oxidation film growth in situ layered double hydroxide.Differential arc oxidation processing is carried out to aluminium alloy, the aluminium alloy of superficial growth differential arc oxidation film layer is obtained;Electrolyte composition includes 5g/L~10g/L sodium hydroxides, 5g/L~20g/L sodium metaaluminates, and the pulse current density of differential arc oxidation processing is 10A/dm2~30A/dm2;It is 1 by the amount ratio that the aluminium alloy of superficial growth differential arc oxidation film layer is placed in nitric acid metal salt and ammonium nitrate material:Reacted in 6 mixed solution.The present invention is constituted by adjusting micro-arc oxidation electrolyte, pulse power parameters, control differential arc oxidation film layer composition and architectural feature, is obtained and is beneficial to the basement membrane layer that layered double hydroxide is deposited;Effective reparation to micro-arc oxidation films layer defects is realized, improves differential arc oxidation film layer decay resistance.

Description

The method of aluminum alloy differential arc oxidation film growth in situ layered double hydroxide
Technical field
The present invention relates to a kind of method for generating Corrosion Resistant Film in aluminum alloy surface, specifically a kind of aluminium alloy is micro- The method of arc oxide-film growth in situ layered double hydroxide.
Background technology
Differential arc oxidization technique is a kind of metal surface treatment process fast-developing in recent years, and the technology can be in aluminium, magnesium, titanium The differential arc oxidation film layer with superior abrasion resistance, insulating properties, and the film layer and base are obtained by growth in situ Deng valve metal surface There is stronger adhesion between body, therefore be used widely as wear-resisting, electric protection, Biofunctional coatings.Differential of the arc oxygen It is-to aoxidize-to melt-During Quenching acquisition by repeatedly puncturing in metal surface to change film layer, therefore is existed largely inside film layer Discharge micropore and micro-crack, application of the influence differential arc oxidation film layer under corrosive environment.
It is a kind of inorganic material for having very much an application value that layered double hydroxide, which is also known as hydrotalcite-based compound, its Structure isWherein M2+For Ni2+、Mg2+、Zn2+、Co2+、Cu2+Deng divalent metal sun Ion, M3+For Al3+、Cr3+、Fe3+、Se3+Deng trivalent metal cation, An-For CO3 2-、NO3 -、Cl-、SO4 2-Deng anion.These Special structure makes such material have many unique properties, by regulating and controlling to hydrotalcite preparation technology, can prepare Hydrotalcite functional material with different purposes and performance, has great application in the field such as catalysis, absorption, medicine, anti-corrosion Potentiality.Hydro-thermal method be synthesize layered double hydroxide common method, by HTHP can effectively control crystalline phase and Crystallite dimension.This method is to contain the metal ion steady oxide or hydroxide for being constituted neatly stone veneer, such as A12O3、MgO、 Mg(OH)2、Al(OH)3Deng hydro-thermal process being carried out at high temperature under high pressure together with mixed ammonium/alkali solutions, by metal oxide and hydrogen-oxygen Compound carries out atomic rearrangement and obtains hydrotalcite.Therefore, the key of Hydrothermal Synthesiss hydrotalcite is the metal for constituting neatly stone veneer The pH value of ion stabilized oxide or hydroxide and solution.Aluminum alloy differential arc oxidation film layer main component is A12O3, it contains The height of amount directly affects the growth of layered double hydroxide, while the architectural feature of micro-arc oxidation films is to layered bi-metal The growth effect of hydroxide is notable.
The relevant report of the current preparation method on aluminum alloy differential arc oxidation-layered double hydroxide composite film It is very limited.
The content of the invention
Film layer defect can effectively be closed it is an object of the invention to provide one kind, improve the resistance to of differential arc oxidation film layer The method of the aluminum alloy differential arc oxidation film growth in situ layered double hydroxide of corrosive nature.
The object of the present invention is achieved like this:
Aluminium alloy is placed in electrolyte as anode, using graphite cake as negative electrode, carries out differential arc oxidation processing, obtain table Look unfamiliar the aluminium alloy of long differential arc oxidation film layer;The electrolyte composition includes 5g/L~10g/L sodium hydroxides, 5g/L~20g/L Sodium metaaluminate, the pulse current density of the differential arc oxidation processing is 10A/dm2~30A/dm2, the differential arc oxidation film layer generated Thickness in 10~100 μm, surface roughness at 1.5~5 μm;
The aluminium alloy of the superficial growth differential arc oxidation film layer is placed in into mixed solution to be reacted, the mixed solution is It is 1 by the amount ratio of nitric acid metal salt and ammonium nitrate material:6 mixed solutions prepared, the pH value of mixed solution is 7~11, wherein The concentration of nitric acid metal salt is 0.01mol/L~0.2mol/L.
The present invention can also include:
1st, the reaction is carried out under the water-bath heating condition of room temperature to 100 DEG C, and the reaction time is 6~96 hours.
2nd, the reaction is carried out under conditions of 100 DEG C~200 DEG C are heated in closed reactor, by baking oven, during reaction Between be 1~48 hour.
The present invention by adjust micro-arc oxidation electrolyte constitute, pulse power parameters, control differential arc oxidation film layer composition and Architectural feature, obtains and is beneficial to the basement membrane layer that layered double hydroxide is deposited, method of the invention is for micro-arc oxidation films Effective reparation of layer defects, improvement film layer decay resistance tool are of great significance.
The principal character of the present invention is embodied in:
(1) micro-arc oxidation electrolyte is constituted:5g/L~10g/L sodium hydroxides and 5g/L~20g/L sodium metaaluminates, high concentration Sodium hydroxide can be performed etching to aluminium alloy, be conducive to obtaining the higher micro-arc oxidation films of surface roughness, high concentration meta-aluminic acid Sodium can ensure film layer A12O3Content and purity, are conducive to layered double hydroxide in its surface homoepitaxial.
(2) regulation control pulse power current density:10A/dm2~30A/dm2, the thickness of film layer is controlled at 10~100 μm In the range of, surface roughness is in 1.5~5 μ ms, and the high roughness micro-arc oxidation films obtained under this process conditions are more sharp In layered double hydroxide staggeredly growing on its surface, in a corrosive environment, gained layered double hydroxide It is easily formed " labyrinth effect " and hinders erosion carbon dioxide infiltration, realize improves to differential arc oxidation film layer decay resistance.
Beneficial effects of the present invention:The present invention is constituted by adjusting micro-arc oxidation electrolyte, pulse power parameters, is controlled micro- Arc oxidation film layer is constituted and architectural feature, is obtained and is beneficial to the basement membrane layer that layered double hydroxide is deposited;Pass through key-course The parameter such as shape double-metal hydroxide preparation solution composition, hydrothermal synthesis reaction temperature and time, drying temperature and time, is prepared micro- Arc oxidation-layered double hydroxide composite film, realizes effective reparation to micro-arc oxidation films layer defects, improves differential of the arc oxygen Change film layer decay resistance.
Brief description of the drawings
It is multiple that Fig. 1 prepares differential arc oxidation-layered double hydroxide using different hydrothermal temperatures in aluminum alloy surface Close the dynamic potential polarization curve of film layer (corrosive medium that experiment is used is 3.5%NaCl solution).
It is multiple that Fig. 2 prepares differential arc oxidation-layered double hydroxide using different the hydro-thermal reaction times in aluminum alloy surface Close the dynamic potential polarization curve of film layer (corrosive medium that experiment is used is 3.5%NaCl solution).
Embodiment
Illustrate below and the present invention is described in more detail.
Embodiment 1:
From nickel nitrate in aluminum alloy differential arc oxidation film Surface Creation layered double hydroxide, realize to differential arc oxidation The reparation of film layer defect.
1. the preparation of aluminum alloy differential arc oxidation film layer:Aluminum alloy surface is carbonized through 150#, 400#, 1000#, 2000# first Silica sand paper is polished, acetone and deionized water processing;Select micro-arc oxidation electrolyte composition:8g/L sodium hydroxides, 10g/L meta-aluminic acids Sodium, pulse power current density:15A/dm2, thicknesses of layers:In 30 μ ms, surface roughness:3.2μm;
2. the preparation of layered double hydroxide preparation solution:Nitric acid nickel concentration is that 0.03mol/L, ammonium nitrate concn are 0.18mol/L, uses ammoniacal liquor to adjust the pH value of mixed solution for 9;
3. the preparation of differential arc oxidation-layered double hydroxide composite film:The surface that step 1 is obtained carries the differential of the arc The mixed solution that the aluminium alloy of oxide-film is obtained with step 2 is placed in closed reactor, then respectively at 40 DEG C, 80 DEG C, 180 DEG C Under the conditions of react 6h, react 1h, 12h, 48h respectively under the conditions of 80 DEG C, then aluminium alloy is taken out, after ethanol cleaning, obtain aluminium Alloy differential arc oxidation-layered double hydroxide composite film.
Fig. 1 dynamic potential polarization curve shows, increases with hydrothermal temperature, aluminum alloy differential arc oxidation film layer anode pole and Cathode reaction process is suppressed simultaneously, corrosion current reduction, illustrates to realize to aluminum alloy differential arc by hydrothermal synthesis reaction The reparation of oxidation film layer defective locations, and hydrothermal temperature influences larger to repairing effect.It can be seen that use hydrothermal synthesis reaction Method, which prepares aluminum alloy differential arc oxidation-hydrotalcite composite film, can realize differential arc oxidation film layer defect repair, hydrothermal temperature It is more suitable at 80 DEG C~180 DEG C to control.
Fig. 2 dynamic potential polarization curve shows, increases with the hydro-thermal reaction time, aluminum alloy differential arc oxidation film layer anode pole and Cathode reaction process is suppressed simultaneously, corrosion current reduction, illustrates the increase with the reaction time, aluminum alloy differential arc oxidation film layer The repairing effect enhancing of defective locations, the hydro-thermal reaction time should control more suitable in 12h~48h.
Embodiment 2:
Difference from Example 1 is:
From magnesium nitrate in aluminum alloy differential arc oxidation film Surface Creation layered double hydroxide, realize to differential arc oxidation The reparation of film layer.
1. the preparation of aluminum alloy differential arc oxidation film layer:Aluminum alloy surface is carbonized through 150#, 400#, 1000#, 2000# first Silica sand paper is polished, acetone and deionized water processing;Select micro-arc oxidation electrolyte composition:8g/L sodium hydroxides, 10g/L meta-aluminic acids Sodium, pulse power current density:15A/dm2, thicknesses of layers:In 30 μ ms, surface roughness:3.2μm;
2. the preparation of layered double hydroxide preparation solution:Nitric acid magnesium density is that 0.02mol/L, ammonium nitrate concn are 0.12mol/L, uses ammoniacal liquor to adjust the pH value of mixed solution for 9;
3. the preparation of differential arc oxidation-layered double hydroxide composite film:The surface that step 1 is obtained carries the differential of the arc The mixed solution that the aluminium alloy of oxide-film is obtained with step 2 is placed in closed reactor, then temperature be 40 DEG C, 80 DEG C, 180 DEG C conditioned response 6h, reacts 1h, 12h, 48h respectively under the conditions of 80 DEG C, then aluminium alloy is taken out, and is being obtained after ethanol cleaning Aluminum alloy differential arc oxidation-layered double hydroxide composite film.
Experimental result:Increase with hydrothermal temperature, aluminum alloy differential arc oxidation film layer anode pole and cathode reaction process are same When be suppressed, corrosion current reduction and increases, aluminum alloy differential arc oxidation film layer anode pole and negative electrode are anti-with the hydro-thermal reaction time Process is answered to be similarly subjected to suppression, corrosion current reduction, this explanation can prepare differential arc oxidation-stratiform by hydrothermal synthesis reaction Double-metal hydroxide composite film, realizes the reparation to aluminum alloy differential arc oxidation film layer defective locations.

Claims (5)

1. a kind of method of aluminum alloy differential arc oxidation film growth in situ layered double hydroxide, it is characterized in that:By aluminium alloy It is placed in electrolyte as anode, using graphite cake as negative electrode, carries out differential arc oxidation processing, obtain superficial growth micro-arc oxidation films The aluminium alloy of layer;The electrolyte composition includes 5g/L~10g/L sodium hydroxides, 5g/L~20g/L sodium metaaluminates, in 10A/ dm2~30A/dm2In the range of regulation control pulse power current density, make the thickness of generated differential arc oxidation film layer 10 ~100 μm, surface roughness is at 1.5~5 μm;
The aluminium alloy of the superficial growth differential arc oxidation film layer is placed in into mixed solution to be reacted, the mixed solution is by nitre The amount ratio of acid metal salt and ammonium nitrate material is 1:6 mixed solutions prepared, the pH value of mixed solution is 7~11, wherein nitric acid The concentration of metal salt is 0.01mol/L~0.2mol/L.
2. the method for aluminum alloy differential arc oxidation film growth in situ layered double hydroxide according to claim 1, its It is characterized in:The reaction is carried out under the water-bath heating condition of room temperature to 100 DEG C, and the reaction time is 6~96 hours.
3. the method for aluminum alloy differential arc oxidation film growth in situ layered double hydroxide according to claim 1, its It is characterized in:The reaction is carried out under conditions of 100 DEG C~200 DEG C are heated in closed reactor, by baking oven, and the reaction time is 1~48 hour.
4. the method for aluminum alloy differential arc oxidation film growth in situ layered double hydroxide according to claim 3, its It is characterized in:Reaction temperature is controlled at 80 DEG C~180 DEG C.
5. the method for the aluminum alloy differential arc oxidation film growth in situ layered double hydroxide according to claim 3 or 4, It is characterized in that:Reaction time was controlled at 12~48 hours.
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CN105839163B (en) * 2016-05-24 2018-06-08 江苏理工学院 For the electrolyte of 7075 aluminium alloy laser coupled microplasma arcs oxidation
CN108251839B (en) * 2018-04-17 2019-10-15 福州大学 A kind of preparation method of magnesium nickel hydrotalcite/differential arc oxidation composite coating
CN108914184B (en) * 2018-08-01 2019-08-09 福州大学 A kind of low energy consumption aluminum alloy differential arc oxidation film layer preparation method
CN109853022A (en) * 2019-03-21 2019-06-07 福州大学 A kind of preparation method of the anti-corrosion Mg-Al LDH/MAO composite coating of aluminium alloy
CN110093647B (en) * 2019-04-08 2021-07-13 中国科学院上海硅酸盐研究所 Method for preparing layered double hydroxide corrosion-resistant coating on surface of magnesium and magnesium alloy in situ

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CN100406388C (en) * 2005-12-19 2008-07-30 北京化工大学 Vertically oriented hydrotalcite film in nano and micron composite structure and its preparing process
CN100463858C (en) * 2006-04-12 2009-02-25 北京化工大学 Ultra-hydrophobic lamellar dihydroxyl composite metal oxide thin film and preparing method thereof
CN102634835B (en) * 2012-04-28 2015-01-14 北京化工大学 Anticorrosive layered double-hydroxy composite metal hydroxide film and preparation method thereof
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