CN101658837A - Preparation method of anticorrosive film for metal surface - Google Patents
Preparation method of anticorrosive film for metal surface Download PDFInfo
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- CN101658837A CN101658837A CN200910019178A CN200910019178A CN101658837A CN 101658837 A CN101658837 A CN 101658837A CN 200910019178 A CN200910019178 A CN 200910019178A CN 200910019178 A CN200910019178 A CN 200910019178A CN 101658837 A CN101658837 A CN 101658837A
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Abstract
The invention discloses a preparation method of a anticorrosive film for metal surface, which is characterized by comprising the following steps: dissolving dopamine in a aqueous solution of tris(hydroxymethyl)aminomethane hydrochloride or phosphate, stirring, dipping metal, contacting for 12-90 h and then taking out, flushing by deionized water, drying by nitrogen and then putting in a solution containing alkane thiol, carrying out water bathing at 20-30 DEG C for 24-48 h and then taking out, flushing by the solution containing the alkane thiol, drying by the nitrogen, and then forming an anticorrosive film on the surface of the metal. By adopting the method, a stable anticorrosive film layer can be formed on a metal substrate with strong cohesion; the preparation method does not need long reaction time and does not need to etch the metal; and the prepared metal surface anticorrosive film has good anticorrosive performance and high protection efficiency as high as 99%.
Description
Technical field
The present invention relates to a kind of method stable and anti-corrosion film that cohesive force is strong for preparing in the metal surface.
Background technology
Metal erosion is that metal is had an effect with corrosive medium in corrosive environment and made metal become the thermodynamics spontaneous process of the state of oxidation.It is reported that the annual economic loss that causes because of metal erosion accounts for 1.5～2.4% of gross national product.Therefore, corrosion of metal is related to whole national economy and economic sustainable development with protection.For the loss that corrosion is caused is reduced to bottom line, adopt metal surface treating method be at present most widely used general also be effective measures, mercaptan plays anticorrosion ability preferably owing to having long alkane chain, is used for preventing corrosion of metal widely.
It is 12 and 18 normal alkane mercaptan prevents the copper metal erosion in containing sodium acetate solution ability that Petrovic and Hukovic (2008) have studied carbon number.According to their voltammetry research, positive lauryl mercaptan and positive stearylmercaptan have effectively stoped the corrosion of copper matrix, and protection efficient has reached 99.93% and 99.97% respectively.But along with shuffling of current potential, alkanethiol breaks away to fall from the copper surface owing to the effect of electrochemistry desorption probably.Azzaroni and Cipollone (2001) report: in containing the borax buffer solution of cl anion, the formation of positive lauryl mercaptan film can effectively stop the formation of cupric oxide and the dissolving of copper, they also find simultaneously, and the effect of corrosion inhibition changes along with the variation of corroding anion concentration.People such as Tan have studied the H of benzenethiol film in 0.5 mol
2SO
4Maximum inhibition efficiency can reach 86.47% in the aqueous solution.
On the other hand, Nozawa (1997,1999) expression, the bilayer coating can increase the corrosion resistance of iron greatly.When carrying out the electrochemical impedance spectroscopy test in the NaCl of the 0.5 mol aqueous solution, the protection efficient of the positive stearylmercaptan monomolecular film that forms on the iron-based body has reached 76.3%.And after at first then using the hot silane treatment of triethoxy with 11-sulfydryl-1-tip-nip, protection efficient is increased to 88.0%.When the surface of handling with 11-sulfydryl-1-tip-nip uses 1 once more, two (triethylsilyl) ethane of 2-and use 5 * 10 subsequently
-4After the hot silane treatment of the triethoxy of mol, protection efficient further improves, and reaches 98.1%.
Yet, the mercaptan film is adsorbed on the copper surface of face-centred cubic structure, all be the HNO that at first utilizes 7 mol
3Aqueous solution etching 10～15s for the iron of more difficult absorption-body-centered cubic structure, then is that cathode-current density is 1.0mAcm in the process of energising
-2Situation under, use HClO
4Aqueous solution etching 10min makes anti-corrosion film adsorb on its surface thereby produce more active surface like this, but this way badly damaged the mechanical property of metal, for later anticorrosive process has stayed hidden danger, and etching process is difficult to control.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anti-corrosion film on metal surface simple, that easily go, it can overcome the above-mentioned shortcoming of prior art.
A kind of preparation method of anti-corrosion film on metal surface, it is characterized in that dopamine is dissolved in three (methylol) aminomethane hydrochlorides or the phosphatic aqueous solution, stir, immerse metal, contact 12～90h takes out, use deionized water rinsing, put into the solution that contains alkanethiol behind the nitrogen drying, take out behind 20～30 ℃ of following water-bath 24～48h, with the above-mentioned solvent washing that contains alkanethiol solution, behind the nitrogen drying, can on the metal surface, form anti-corrosion film.
Use method of the present invention can on metal substrate, be easy to form stable anticorrosion film; cohesive force is strong, does not need the long reaction time simultaneously, and does not need metal is carried out etching; the Corrosion Protection of prepared anti-corrosion film on metal surface is good, and protection efficient is up to 99%.
Description of drawings
Fig. 1 is the x-ray photoelectron spectroscopy figure on the copper electrode surface of handling with dopamine (DA) and positive lauryl mercaptan in the present invention experiment.A, b, c are followed successively by the x-ray photoelectron spectroscopy figure of carbon, oxygen, nitrogen element in the poly-DA rete of absorption among the figure, and d, e are respectively the x-ray photoelectron spectroscopy figure of positive lauryl mercaptan rete nitrogen, element sulphur on the copper matrix that is coated with poly-DA.
Fig. 2 for handle with positive lauryl mercaptan with DA in the present invention experiment and untreated copper electrode three immerse AC impedance figure (Nyquist figure) in the seawater of sterilizing respectively.
Fig. 3 for handle with positive lauryl mercaptan with DA in the present invention experiment and untreated copper electrode three immerse AC impedance figure (Bode figure) in the seawater of sterilizing respectively.
Fig. 4 in the present invention experiment with DA and 11-sulfydryl-1-undecanoic acid (MUA) processing and untreated 304 stainless steel electrode threes immerse AC impedance figure (Nyquist figure) in the seawater of sterilizing respectively.
Fig. 5 in the present invention experiment with DA and MUA processing and untreated copper-nickel alloy electrode three immerse polarization curve in the seawater of sterilizing respectively.
The specific embodiment
The present invention is by the assistance of the poly-DA rete that easily absorption and cohesive force are strong, thereby the alkanethiol film that will have corrosion resistance is adsorbed on the metallic matrix that need not etching.
Embodiment one
At first configuration concentration be 10 mMs/liter three (methylol) aminomethane hydrochloride (Tris-HCl) aqueous solution 10ml, regulating pH with NaOH is 8.5, in the ratio of 2g/L DA is put into the above-mentioned aqueous solution then, stir 30min, the good copper matrix of will polishing again vertically immerses, take out behind the contact 24h, use deionized water rinsing, on the copper matrix surface, form poly-DA rete, put it into concentration through nitrogen bubble behind the nitrogen drying and be 10 mMs/liter the dichloromethane solution of the positive lauryl mercaptan of 20ml in, 25 ℃ of water-baths, take out behind the 24h, use washed with dichloromethane, nitrogen drying forms anti-corrosion film on the copper electrode surface thus.As shown in Figure 1, contain carbon, nitrogen, oxygen element in the poly-DA rete, the carbon peak value is at 284.7eV and 286.1eV, respectively corresponding C-C/C-H and C-N/C-O key, this mainly is because the carbon among the DA is in two kinds of different environment, in addition, the peak value of oxygen, nitrogen element correspondence is respectively 532.1eV and 400.9eV, compare with the typical bond energy of nitrogen and oxygen element, skew has taken place, this just shows that oxygen and nitrogen have played crucial effect in DA is bonded to the process of copper matrix.Figure d and e have shown nitrogen element and element sulphur, show that positive lauryl mercaptan adsorbs on the copper matrix that poly-DA coats really.
As shown in table 1, the poly-DA rete for preparing on the copper matrix through above-mentioned steps demonstrates stronger hydrophily.Positive lauryl mercaptan is chemically bonded on the copper matrix that is coated with poly-DA by terminal sulfydryl after, contact angle is increased to 120 ° by 50 °, shows the end group-CH of positive lauryl mercaptan
3Point to outer surface, be shown as stronger hydrophobicity.Treated copper electrode demonstrates excellent corrosion resistance simultaneously.
Fig. 2 handles with positive lauryl mercaptan for DA and untreated copper electrode three is immersed the AC impedance figure (Nyquist figure) in the sterilization seawater respectively, and curve 1 is corresponding with blank copper matrix among the figure, curve 2 is corresponding with the copper matrix that poly-DA film coats, curve 3 and lauryl mercaptan just are adsorbed on that to be coated with the copper matrix that gathers the DA film corresponding.When forming above-mentioned two tunics on copper electrode surface, embody good anticorrosion ability.Corresponding ac impedance measurement result is impedance spectrogram (Nyquist figure), and this impedance spectrum all demonstrates an arc, and the chord length of this arc to the Z axle is corresponding to the film resistance R of electrode
f, R
fBig more erosion-resisting effect is good more.As can be seen from Figure 2, form poly-DA film, just compare with blank sample behind the lauryl mercaptan film, copper is all had certain anticorrosion ability, but after the positive lauryl mercaptan film with anticorrosion ability formed, anticorrosion ability increased obviously.
Fig. 3 be handle with positive lauryl mercaptan through DA and untreated copper electrode three immerse AC impedance figure (Bode figure) in the sterilization seawater respectively, curve 1 is corresponding with blank copper matrix among the figure, curve 2 is corresponding with the copper matrix that poly-DA film coats, curve 3 and lauryl mercaptan just are adsorbed on that to be coated with the copper matrix that gathers the DA film corresponding.The corrosion resisting property of electrode can be by the Impedance Membrane value of low frequency | and Z| characterizes, the Impedance Membrane value | and Z| is big more, and then the Corrosion Protection of electrode is good more.Also as can be seen, positive lauryl mercaptan film is after forming on the copper electrode that poly-DA coats from Fig. 3, and corrosion resistance is greatly improved.
Effect after table 1 copper electrode and the processing
| Handle | ??Cu | Cu+ gathers DA | Cu+ gathers the positive lauryl mercaptan of DA+ |
| Contact angle (degree) | ??91 | ??50 | ??120 |
Embodiment two
At first configuration concentration be 5 mMs/liter phosphate (Na
2HPO
4Or KH
2PO
4) aqueous solution 10ml, regulating pH with NaOH is 9, in the ratio of 0.2g/L DA is put into the above-mentioned aqueous solution then, stir 20min, the 304 good stainless steel bases of will polishing again vertically immerse, take out behind the contact 60h, use deionized water rinsing, put into concentration through nitrogen bubble behind the nitrogen drying and be 1 mM/liter the dichloromethane solution of 20ml 11-sulfydryl-1-undecanoic acid (MUA), 20 ℃ of water-baths are taken out behind the 48h, use washed with dichloromethane, nitrogen drying has formed anti-corrosion film on 304 stainless steel electrode surfaces thus.Fig. 4 handles for DA and MUA and untreated 304 stainless steel electrode threes are immersed the AC impedance figure (Nyquist figure) in the sterilization seawater respectively, and curve 1 is corresponding with blank 304 stainless steel bases among the figure, curve 2 is corresponding with 304 stainless steel bases of poly-DA film coating, curve 3 and MUA are adsorbed on that to be coated with 304 stainless steel bases that gather the DA film corresponding.Learn according to analysis introduction Fig. 2, when the MUA film after forming on 304 stainless steel bases that poly-DA coats, corrosion resistance also is greatly improved.
Embodiment three
At first configuration concentration be 10 mMs/liter the aqueous solution 10ml of three (methylol) aminomethane hydrochloride (Tris-HCl), regulating pH with NaOH is 8, in the ratio of 1g/L DA is put into the above-mentioned aqueous solution then, stir 40min, the good copper-nickel alloy matrix of will polishing again vertically immerses, take out behind the contact 48h, use deionized water rinsing, put into concentration through nitrogen bubble behind the nitrogen drying and be 2 mMs/liter the dichloromethane solution of 20ml MUA, 30 ℃ of water-baths are taken out behind the 24h, use washed with dichloromethane, nitrogen drying has formed anti-corrosion film at the copper-nickel alloy electrode surface thus.Fig. 5 for handle through DA and MUA and untreated copper-nickel alloy electrode three immerse polarization curve in the sterilization seawater respectively, curve 1 is corresponding with blank copper-nickel alloy matrix among the figure, curve 2 is corresponding with the copper-nickel alloy matrix that poly-DA film coats, curve 3 and MUA are adsorbed on that to be coated with the copper-nickel alloy matrix that gathers the DA film corresponding.As we can see from the figure, be adsorbed on the copper-nickel alloy matrix that coats poly-DA as MUA after, compare with blank sample, corrosion electric current density about 2～3 orders of magnitude that descended, this just illustrates that the MUA film has the significant protection effect to copper-nickel alloy.
The preparation method of anti-corrosion film of the present invention also can play similar anticorrosion ability to stainless steel, NiTi alloy, the titanium of gold, silver, platinum, cadmium, aluminium, zinc, kirsite, other models.
The copper electrode of above-mentioned Experiment Preparation, 304 stainless steel electrodes, copper-nickel alloy electrode all are applied in the sterilization seawater, and before carrying out electro-chemical test, with the non-working surface epoxy sealing, electrode area is 1cm
2, before experimentizing, copper, 304 stainless steels, copper-nickel alloy all use 400
#, 800
#, 1200
#, 2000
#Abrasive paper for metallograph polish successively, polish, use washed with de-ionized water, carry out oil removing successively with acetone, absolute ethyl alcohol then, rinse well with deionized water at last and get final product.
The test of employing electrochemical AC impedance, its determining instrument is German ZAHNER-IM6E, and the mensuration frequency range is 10mHz～100kHz, and the pumping signal peak value is 5mV; The sweep speed of polarization curve is 2mV/s.Adopt the three-electrode system of standard in the experiment, working electrode is copper, 304 stainless steels or copper-nickel alloy electrode, and auxiliary electrode and reference electrode are respectively Pt electrode and saturated calomel electrode.The measurement of ac impedance spectroscopy and polarization curve is all handled DA with positive lauryl mercaptan or MUA and untreated copper, 304 stainless steels, copper-nickel alloy electrode are immersed in and carry out under OCP behind the 2h in the sterilization seawater.All electrode is vertically immersed during test in the sterilization seawater, the degree of depth of immersed in liquid level and reference electrode, auxiliary electrode are identical, are about 2cm.
Claims (7)
1. the preparation method of an anti-corrosion film on metal surface, it is characterized in that dopamine is dissolved in three (methylol) aminomethane hydrochlorides or the phosphatic aqueous solution, stir, immerse metal, contact 12～90h takes out, use deionized water rinsing, put into the solution that contains alkanethiol behind the nitrogen drying, take out behind 20～30 ℃ of following water-bath 24～48h, with the above-mentioned solvent washing that contains alkanethiol solution, behind the nitrogen drying, can on the metal surface, form anti-corrosion film.
2. method according to claim 1 is characterized in that the concentration of described dopamine in three (methylol) aminomethane hydrochlorides or aqueous phosphatic is 0.2～2g/L, and described mixing time is 20min～60min.
3. method according to claim 1, the concentration that it is characterized in that described three (methylol) aminomethane hydrochlorides or aqueous phosphatic be 5～20 mMs/liter, the pH value is 5～10.
4. method according to claim 1 is characterized in that described metal is gold, silver, platinum, cadmium, copper, copper alloy, aluminium, zinc, kirsite, stainless steel, NiTi alloy or titanium.
5. method according to claim 1, the general formula that it is characterized in that described alkanethiol is R (CH
2)
nSH, R is methyl, hydroxyl or carboxyl in the formula, and n is 6～21.
6. method according to claim 1, it is characterized in that the concentration of described alkanethiol in alkanethiol solution be 1～50 mM/liter.
7. method according to claim 1 is characterized in that solvent in the described alkanethiol solution is one or more in ethanol, ethylene glycol, hexane, furans, oxolane, benzene, dimethylbenzene, acetonitrile, carrene, ethyl acetate, ether and the carbon tetrachloride.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012007199A1 (en) | 2010-07-16 | 2012-01-19 | Biopolymer Technology Of Sweden Ab | Corrosion inhibiting coating based on cerium oxide and a catecholic polymer |
| CN102961893A (en) * | 2012-11-07 | 2013-03-13 | 清华大学 | Super-hydrophobic and super-oleophylic oil-water separating mesh membrane and preparation method thereof |
| CN103469286A (en) * | 2013-09-13 | 2013-12-25 | 中国海洋大学 | Organic-inorganic composite coating on metal surface and preparation process thereof |
| CN105418821A (en) * | 2015-12-21 | 2016-03-23 | 青岛理工大学 | Functional protecting surface material with good adhesive performance and preparation method for function protecting surface material |
| WO2021116205A1 (en) | 2019-12-09 | 2021-06-17 | Biopolymer Products Of Sweden Ab | Coating for corrosion protection |
| CN113578706A (en) * | 2021-07-26 | 2021-11-02 | 青海大学 | Method for preparing corrosion-resistant composite coating by using layer-by-layer self-assembly technology |
| CN113913816A (en) * | 2021-10-14 | 2022-01-11 | 吉林大学 | Method for enhancing corrosion resistance of pure copper |
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2009
- 2009-09-24 CN CN200910019178A patent/CN101658837A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012007199A1 (en) | 2010-07-16 | 2012-01-19 | Biopolymer Technology Of Sweden Ab | Corrosion inhibiting coating based on cerium oxide and a catecholic polymer |
| US9617433B2 (en) | 2010-07-16 | 2017-04-11 | Biopolymer Technology Of Sweden Ab | Corrosion inhibiting coating based on cerium oxide and a catecholic polymer |
| CN102961893A (en) * | 2012-11-07 | 2013-03-13 | 清华大学 | Super-hydrophobic and super-oleophylic oil-water separating mesh membrane and preparation method thereof |
| CN102961893B (en) * | 2012-11-07 | 2014-11-26 | 清华大学 | Super-hydrophobic and super-oleophylic oil-water separating mesh membrane and preparation method thereof |
| CN103469286A (en) * | 2013-09-13 | 2013-12-25 | 中国海洋大学 | Organic-inorganic composite coating on metal surface and preparation process thereof |
| CN103469286B (en) * | 2013-09-13 | 2016-08-17 | 中国海洋大学 | A kind of metal surface Organic-inorganic composite coating and preparation technology thereof |
| CN105418821A (en) * | 2015-12-21 | 2016-03-23 | 青岛理工大学 | Functional protecting surface material with good adhesive performance and preparation method for function protecting surface material |
| WO2021116205A1 (en) | 2019-12-09 | 2021-06-17 | Biopolymer Products Of Sweden Ab | Coating for corrosion protection |
| CN113578706A (en) * | 2021-07-26 | 2021-11-02 | 青海大学 | Method for preparing corrosion-resistant composite coating by using layer-by-layer self-assembly technology |
| CN113913816A (en) * | 2021-10-14 | 2022-01-11 | 吉林大学 | Method for enhancing corrosion resistance of pure copper |
| CN113913816B (en) * | 2021-10-14 | 2023-06-30 | 吉林大学 | Method for enhancing corrosion resistance of pure copper |
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Application publication date: 20100303 |