CN107475761A - The electropolymerization liquid and electropolymerization method of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface - Google Patents

The electropolymerization liquid and electropolymerization method of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface Download PDF

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Publication number
CN107475761A
CN107475761A CN201710725997.0A CN201710725997A CN107475761A CN 107475761 A CN107475761 A CN 107475761A CN 201710725997 A CN201710725997 A CN 201710725997A CN 107475761 A CN107475761 A CN 107475761A
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China
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electropolymerization
film
alloy surface
benzene sulfonate
dodecyl benzene
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王桂香
杨立娟
何津萌
吴倩
张晓红
吴春喜
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Harbin Engineering University
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Harbin Engineering University
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00Electrolytic coating other than with metals
    • C25D9/02Electrolytic coating other than with metals with organic materials
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The present invention is to provide a kind of electropolymerization liquid of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface and electropolymerization method.The pyrroles of certain mass and sodium salicylate are added to dissolving in distilled water according to certain order electrolyte is made, a certain amount of SDBS solution is added into electrolyte, the magnesium alloy substrate of pretreatment is put into electrolyte, using cyclic voltammetry, experiment parameter is set, film of poly pyrrole is prepared in Mg alloy surface electropolymerization.The present invention prepares sodium dodecyl benzene sulfonate-doped polypyrrole film using electropolymerization in Mg alloy surface.Polypyrrole purity prepared by the method is high, wastes less, operating method is simple, improves the decay resistance of magnesium alloy to a certain extent, and SDBS can effectively improve the adhesion of magnesium alloy substrate and polypyrrole film, widen the application field of magnesium alloy.

Description

The electropolymerization liquid of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface and Electropolymerization method
Technical field
The present invention relates to a kind of Magnesiumalloy surface modifying processing method, and specifically one kind is in Mg alloy surface shape Into the electropolymerization liquid of electropolymerization film.The present invention also relates to a kind of electropolymerization method that electropolymerization film is formed in Mg alloy surface.
Background technology
Magnesium alloy rich reserves, it is that (content in the earth's crust is about for content is only second to aluminium and iron in the earth's crust metallic element 2.00%, content in the seawater is also very high, about 0.13%).Magnesium is also that China's yield is most, Alloyapplication is most extensive simultaneously Metallics.Moreover, magnesium alloy has, density is small, intensity is high, shock absorbing performance is good, modulus of elasticity is big, specific strength is high, structure The features such as excellent performance, easily deformable processing and welding fabrication.But because magnesium and magnesium alloy property are active, easily with other groups Knit and react to form corrosion galvanic cell, cause to corrode.The corrosion of magnesium alloy causes the application of magnesium and magnesium alloy to receive necessarily Limitation.Therefore it is necessary that protection is carried out to magnesium and Mg alloy surface.
It recent studies have shown that, conducting polymer is existing as the electrology characteristic of metal and the optical characteristics of inorganic semiconductor, also With polymer distinctive excellent mechanical performance and processing characteristics, while also good electrochemical redox activity.Lead Electric polymer has very big potentiality to be exploited in terms of metal protection.First, conductive polymer membrane has certain to metal surface Protective effect, the surface of Korrosionsmedium contact magnesium alloy can be prevented, be effectively improved the corrosion potential of magnesium alloy, drop Low corrosion electric current.The main film of poly pyrrole that comes from of the raising of corrosive nature is acted on the mechanical masking of Mg alloy surface.Its It is secondary, compared with other protecting metallic surface methods, conducting polymer as metal protecting film protrude the advantages of be to polymerize Thing film is conducting film.And conventional anode oxide film or chemical composition coating is insulating film layer.Wherein, polypyrrole (PPy) is easy Synthesis, the stability of equipment operation simply, after film forming are relatively preferable, and polymerized monomer is pyrroles, and environmental pollution is small.Therefore it is poly- Pyrroles is considered as the conducting polymer for most having development and application prospect for anti-corrosion film on metal surface layer.
The content of the invention
It is an object of the invention to provide a kind of decay resistance that can improve magnesium alloy, improves polypyrrole film and is closed with magnesium The electropolymerization liquid of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface of golden basal body binding force.The purpose of the present invention Also reside in and a kind of electropolymerization method of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface is provided.
The electropolymerization liquid of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface of the present invention to by pyrroles and In the aqueous solution of sodium salicylate, add what neopelex solution was formulated.
Pyrrole monomer concentration is 0.01~0.15mol/L, and the concentration of neopelex is 0.01~0.2mol/L.
The electropolymerization method of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface of the present invention is:To by pyrrole Cough up in the aqueous solution with sodium salicylate, add the electropolymerization liquid that neopelex solution is formulated, wherein pyrroles is single Bulk concentration is 0.01~0.15mol/L, and the concentration of neopelex is 0.01~0.2mol/L;The magnesium that will have been pre-processed Alloy is put into electropolymerization liquid, and film of poly pyrrole is formed in Mg alloy surface using cyclic voltammetry.
The scanning voltage scope of the cyclic voltammetry is -0.5~2V, and the scan period is 2~10, sweep speed is 2~ 10mV/s。
The invention provides a kind of preparation of the electropolymerization of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface Method, electrolyte is made into using a certain amount of SDBS is added in the solution being made into pyrrole monomer and sodium salicylate, to magnesium alloy It is surface-treated, improves the decay resistance of magnesium alloy to a certain extent, effectively increase polypyrrole film and magnesium alloy The adhesion of matrix.And sodium dodecyl benzene sulfonate-doped film of poly pyrrole is readily synthesized, equipment operation is simple, after film forming Stability is relatively preferable, and polymerized monomer is pyrroles, and environmental pollution is small.
Technical scheme mainly includes:
1) pre-process:Mechanical grinding → ultrasonic cleaning → alkali cleaning → deionization washing → acid-wash activation → deionization washing → Cold wind dries up.Mechanical grinding is carried out to magnesium alloy substrate using 320 mesh, 600 mesh, 1000 mesh sand paper successively, until magnesium alloy table Face does not have obvious cut and groove, bright, untill smooth.After polishing is completed, matrix is immersed in absolute alcohol and surpassed Sound wave cleans, and removes the impurity such as the grains of sand iron filings on surface.Then alkali cleaning degreasing is carried out, alkali cleaning degreasing condition is arranged to water-bath 20- 80 DEG C, time 2-5min.After alkali cleaning degreasing, deionized water rinsing is used.Acid-wash activation, pH=2~3, time 20- are carried out again 40s, with deionized water rinsing, cold wind drying.
2) required pyrroles, sodium salicylate, SDBS quality are calculated.Sodium salicylate is first weighed, adds distilled water dissolving; Use again and weigh pyrrole monomer, and pyrrole monomer is dissolved with distilled water;Load weighted SDBS is dissolved in distilled water.By pyrrole monomer Solution is made into electrolyte after being mixed with sodium salicylate solution.SDBS solution is added into electrolyte, ultrasonic vibration 2-8min, is made molten Liquid is well mixed.
3) magnesium alloy cleared up is put in the electrolytic solution, be connected on electrochemical workstation, use cyclic voltammetry, if Experiment parameter is put, film of poly pyrrole is prepared in Mg alloy surface.
A kind of electropolymerization preparation method of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface of the present invention, is adopted Electrolyte is made into a certain amount of SDBS is added in the solution being made into pyrrole monomer and sodium salicylate, surface is carried out to magnesium alloy Pretreatment, the decay resistance of magnesium alloy is improved to a certain extent, effectively increase polypyrrole film and magnesium alloy substrate Adhesion.
The sodium dodecyl benzene sulfonate-doped film of poly pyrrole face crack of Mg alloy surface prepared by the present invention is more, and surface is put down Whole property is low, and anticorrosion effect is preferable, and adhesion significantly improves.
Brief description of the drawings
Fig. 1 is the sodium dodecyl benzene sulfonate-doped film of poly pyrrole infrared spectrogram of Mg alloy surface;
Fig. 2 is the sodium dodecyl benzene sulfonate-doped film of poly pyrrole surface topography map of Mg alloy surface;
Fig. 3 is electrochemical tests of the Mg alloy surface film of poly pyrrole in 3.5%NaCl solution;
Fig. 4 a- Fig. 4 b are Mg alloy surface polypyrrole film adhesion test charts, and wherein Fig. 4 a are PPy films;Fig. 4 b are SDBS/ PPy films.
Embodiment
The present invention is described in detail for citing below.
Part I:Electrolyte is prepared, the pyrroles of certain mass and sodium salicylate are added to steaming according to certain order Electrolyte is made in dissolving in distilled water, and a certain amount of SDBS solution is then added into electrolyte.Pyrrole monomer concentration be 0.01~ 0.15mol/L, SDBS concentration are 0.01~0.2mol/L.
Part II:It is thin that sodium dodecyl benzene sulfonate-doped polypyrrole prepared using electropolymerization technology on magnesium alloy substrate The method of film, including the polishing of magnesium alloy substrate, this experiment is polished matrix using CW series water-resistant type sand paper, by It is thick to arrive carefully, polished successively using 320 mesh, 600 mesh, 1000 mesh, until Mg alloy surface does not have obvious cut and groove, light It is bright, untill smooth.After polishing is completed, matrix is immersed ultrasonic wave cleaning is carried out in absolute alcohol, remove the grains of sand iron on surface The impurity such as bits.Then alkali cleaning degreasing is carried out, alkali cleaning degreasing condition is arranged to 59 DEG C of water-bath, time 4min.After alkali cleaning degreasing, use Deionized water rinsing.Acid-wash activation, pH=2.5, time 30s, with deionized water rinsing, cold wind drying are carried out again.It will locate in advance The magnesium alloy managed is put in the electrolytic solution, is connected on electrochemical workstation, using cyclic voltammetry, sets experiment parameter, Mg alloy surface prepares film of poly pyrrole.The main component of electrolyte is pyrroles, sodium salicylate, SDBS.
Part III:It will be seen from figure 1 that SDBS/PPy films are in 1147cm-1Place has more S=O absorption vibration peak, Show that neopelex has been doped in polypyrrole film.Fig. 2 is the surface topography map of SDBS/PPy films.Detergent alkylate The film of poly pyrrole face crack of sulfonic acid natrium doping increases, and surface is compared with out-of-flatness.Fig. 3 is SDBS/PPy films in 3.5wt%NaCl Electrochemical tests in solution.As seen from Figure 3, SDBS/PPy films serve certain protective effect to magnesium alloy.Fig. 4 For Mg alloy surface polypyrrole film adhesion test chart.Intrinsic polypyrrole film is in the edge of line and friendship it can be seen from Fig. 4 a Crunode goes out to have the film separation of small pieces, and the area that comes off is 5% or so;And adulterate neopelex polypyrrole film (Fig. 4 b) After combined power test, scribing edge is smooth, film layer dropping situations does not occur.Therefore, neopelex is adulterated Polypyrrole film significantly improves the adhesion of polypyrrole film and magnesium alloy substrate.
In summary, the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface prepared using the present invention, tool There is certain decay resistance, and effectively increase the adhesion of polypyrrole film and magnesium alloy substrate.And detergent alkylate sulphur Sour natrium doping film of poly pyrrole is readily synthesized, and equipment operation is simple, and the stability after film forming is relatively preferable, and polymerized monomer is Pyrroles, environmental pollution are small.
Had according to the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface provided by the invention and widely should Use prospect.

Claims (4)

1. a kind of electropolymerization liquid of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface, is to be characterized in:Be to by In the aqueous solution of pyrroles and sodium salicylate, add what neopelex solution was formulated.
2. the electropolymerization liquid of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface according to claim 1, It is to be characterized in:Pyrrole monomer concentration is 0.01~0.15mol/L, and the concentration of neopelex is 0.01~0.2mol/ L。
3. a kind of electropolymerization method of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface, it is characterized in that:Xiang You In the aqueous solution of pyrroles and sodium salicylate, the electropolymerization liquid that neopelex solution is formulated, wherein pyrroles are added Monomer concentration is 0.01~0.15mol/L, and the concentration of neopelex is 0.01~0.2mol/L;By what is pre-processed Magnesium alloy is put into electropolymerization liquid, and film of poly pyrrole is formed in Mg alloy surface using cyclic voltammetry.
4. the electropolymerization side of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface according to claim 3 Method, it is characterized in that:The scanning voltage scope of the cyclic voltammetry is -0.5~2V, and the scan period is 2~10, and sweep speed is 2~10mV/s.
CN201710725997.0A 2017-08-22 2017-08-22 The electropolymerization liquid and electropolymerization method of the sodium dodecyl benzene sulfonate-doped film of poly pyrrole of Mg alloy surface Pending CN107475761A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN108285740A (en) * 2018-01-24 2018-07-17 河海大学 A kind of ocean steel member multilayer super thick anticorrosion coat and preparation method thereof
CN111636085A (en) * 2020-06-10 2020-09-08 深圳大学 Anticorrosive coating and preparation method thereof

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CN102312376A (en) * 2011-07-07 2012-01-11 武汉纺织大学 Preparation method of composite conductive fabric with spray polymerization
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CN106011975A (en) * 2016-07-13 2016-10-12 厦门大学 Preparation method for polypyrrole-poly-dopamine composite coating
CN106086978A (en) * 2016-06-14 2016-11-09 北京工业大学 A kind of preparation method of the loaded palladium catalyst electrode based on Graphene/polypyrrole modifying
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CN104577111A (en) * 2013-10-21 2015-04-29 中国科学院物理研究所 Composite material containing fluorine-containing titanium phosphate compound as well as preparation method and application of composite material
CN106086978A (en) * 2016-06-14 2016-11-09 北京工业大学 A kind of preparation method of the loaded palladium catalyst electrode based on Graphene/polypyrrole modifying
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CN106380599A (en) * 2016-08-31 2017-02-08 昆明理工大学 Preparation method and applications of cauliflower sodium p-toluene sulfonate doped polypyrrole

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108285740A (en) * 2018-01-24 2018-07-17 河海大学 A kind of ocean steel member multilayer super thick anticorrosion coat and preparation method thereof
CN111636085A (en) * 2020-06-10 2020-09-08 深圳大学 Anticorrosive coating and preparation method thereof

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