CN102621093A - Action of spectrum on researching metal and alloy corrosion inhibitor and preferential surface optimizing technology - Google Patents
Action of spectrum on researching metal and alloy corrosion inhibitor and preferential surface optimizing technology Download PDFInfo
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- CN102621093A CN102621093A CN2012100912198A CN201210091219A CN102621093A CN 102621093 A CN102621093 A CN 102621093A CN 2012100912198 A CN2012100912198 A CN 2012100912198A CN 201210091219 A CN201210091219 A CN 201210091219A CN 102621093 A CN102621093 A CN 102621093A
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Abstract
The invention relates to an action of spectrum on researching a metal and alloy corrosion inhibitor and a preferential surface optimizing technology. The invention belongs to the technical field of the combination of spectroscopy and metal corrosion and protection technology. A spectral electrolytic cell is fixed, a semicircular silicon column 2 is used as a carrier, the surface of the semicircular silicon column is chemically plated, metal of a researched target is electrodeposited and consists of an electrode 1 (copper conductor 8 is connected), a counter electrode pure platinum electrode 3, a reference saturation calomel electrode 4, a nitrogen (N2) inlet and an N2 outlet, then the spectral electrolytic cell is placed in a fully-reflection light path, then the inhibitor solution is injected into the spectral electrolytic cell through a solution port 7 to be held for hours, so that inhibitor molecules are automatically assembled on the surface of the electrodes. Potential modulation analysis on a sample is performed through an in-situ surface enhanced infrared spectrum. Compared with traditional technologies, metal nano film is plated on the infrared window semicircular silicon column to be used as an electrode, the in-situ surface enhanced infrared technology is also used for researching adsorption configuration of different inhibitor molecules on the surface of the metal along the potential variation so as to know the action process of the inhibitor, so that more effective and wider application of the technology in resisting corrosion and protecting metal or alloy can be realized.
Description
Technical field
The present invention relates to utilize infrared spectroscopic study inhibition molecule to adsorb configuration, thereby understand the inhibition mechanism of corrosion inhibiter, obtain and select the corrosion inhibiter method according to qualifications, belong to spectroscopy and the corrosion of metal field that combines with guard technology in the metal surface.
Background technology
Produce and real life in, all kinds of and metal is ubiquitous, be indispensable material.China is annual because the economic loss that metal erosion causes surpasses 500,000,000,000 Renminbi, on using, is one of problem demanding prompt solution.How effectively to reduce the loss that metal erosion brings, wherein effective method is in corrosion environment, adds corrosion inhibiter, prolongs metal serviceable life.
In recent years metal inhibitor has been obtained very big development on using; Corrosion inhibiter is studied as a kind of effective ways that slow down even suppress metal erosion widely; But so far, many corrosion inhibiter mechanisms of action or process do not have clear and definite explanation as yet, the exploitation of the novel corrosion inhibitor that has had a strong impact on.
Spectral technique is the important means of research interfacial structure and process; In the research method of common on-the-spot spectroelectrochemistry; SERS method (surface enhanced raman spectroscopy is abbreviated as SERS) and surface infrared spectrum (surface enhanced infrared absorption spectroscopy is abbreviated as SEIRAS) can directly provide the surface adsorption species; And with the details of metal surface effect; For the evaluation surface absorbed layer is formed, and adsorbing species, for it is through which kind of mode and surface action directly favourable evidence to be provided.But SERS base treatment mode is complicated, is difficult for repetition, and instrument and equipment is more expensive; To common metal, for example: Ferrious material, reinforced effects are not strong; Limited should technology expansion and application (Z.Q. Tian, B. Ren, D.Y. Wu; Surface-enhanced Raman scattering:From noble to transition metals and from rough surfaces to ordered nanostructures, J Phys Chem B 106 (2002) 9463-83.).
As the correlation technique of SERS, that attenuated total reflection pattern surface-reinforced infrared spectrum has is highly sensitive, surface choosing rule is simple, substrate preparation is simple and easy, do not receive the advantage of solution confused basically.To the adsorption structure of research molecule, special advantages is arranged to explaining the structure-activity relationship aspect in the metal surface.But; Should technology use less (S.J. Huo at present at corrosion of metal and protection field; J.Y. Wang, J.L. Yao, W.B. Cai; Exploring Electrosorption at Iron Electrode with in Situ Surface-Enhanced Infrared Absorption Spectroscopy, Anal Chem 82 (2010) 5117-24).The key of this technology is to build light path system and spectrum tool device, and the preparation of film in the infrared window substrate.It is to be noted: nanoporous metal membrane is prone to oxidized in air, in the solution phase transition behavior, uses flow pumps, and the minimizing air contacts with metal film.
The present invention proposes to prepare the surface-reinforced infrared spectrum base metal film with reinforced effects, and utilizes the surface to strengthen infrared technique research inhibitor film, and the absorption change of configuration in the metal surface before and after the self assembly is explained inhibition mechanism.Understand the mechanism of action of corrosion inhibiter molecule, to explaining the structure-activity relationship of corrosion inhibiter, significant, for the development of new corrosion inhibiter lays the foundation, also be that a kind of corrosion inhibiter is preferably changed technology.
Summary of the invention
The objective of the invention is to through plating nano thin-film on the semicircle silicon post of infrared window; Obtain that reliability is higher, the better membrane electrode of reinforced effects; Utilize in-situ surface strengthen infrared technique research inhibition molecule in the metal surface with the absorption configuration of potential change; Explain inhibition mechanism, to obtain preferredization corrosion inhibiter new technology.
The present invention reaches through following technical scheme and measure.
With semicircle silicon post as research carrier; At first at the silicon face chemical gilding; Again the silicon post is installed in the spectrum electrolytic cell of design voluntarily; And the fixed spectrum electrolytic cell is in the light path of total reflection; The metal of electro-deposition research object utilizes the liquid changing device that flows, and corrosion inhibitor solution is comprised inorganic and organic or organic polymer class: inorganic inhibitor (as: chromate, nitrite, molybdate, Quadrafos, zinc salt etc.) and organic inhibitor (as: phosphonic acids and salt thereof, phosphine carboxylic acid, mercaptobenzothiazoler, benzotriazole, lignosulfonate etc. contain the heterogeneous ring compound of oxynitrides) etc.; The injection spectrum tool also left standstill several hours, made corrosion inhibiter molecule in the battery surface self assembly.The utilization in-situ surface strengthens infrared spectrum technology, and above-mentioned sample is carried out the current potential Modulation analysis.
Description of drawings
Figs in its embodiment, can further obtain explanation.
Fig. 1, spectrum electrolytic cell synoptic diagram.1-working electrode among the figure, 2-semicircle silicon post, the pure platinum electrode of 3-, 4-saturated calomel electrode (SCE), the 5-air intake opening, the 6-gas vent, 7-solution is imported and exported, the 8-copper conductor.
Fig. 2, infrared light path, 1-infrared beam, 2-spectrum electrolytic cell, 3-catoptron, 4-concave mirror, 5-catoptron, 6-catoptron, 7-infrared detector;
Fig. 3 explains the instance corrosion inhibiter 2-amino-5-sulfydryl-1,3 of present technique, the schematic arrangement of 4-thiadiazoles, 1-sulphur atom wherein, 2-carbon atom, 3-nitrogen-atoms, 4-nitrogen-atoms, 5-carbon atom, 6-sulphur atom, 7-nitrogen-atoms.
Fig. 4,2-amino-5-sulfydryl-1,3,4-thiadiazoles molecule be the adsorption structure synoptic diagram during electronegative potential on cobalt surface.
Fig. 5,2-amino-5-sulfydryl-1,3, the synoptic diagram of the 4-thiadiazoles molecule complex that noble potential generates on the cobalt surface.
Fig. 6, in-situ surface strengthens infrared spectrum and sample is carried out the current potential Modulation analysis.The current potential of working electrode is followed successively by-1.0 V from low to high ,-0.8 V, and-0.6 V ,-0.4 V when-0.2 V and 0 V, gathers corresponding infrared spectrum respectively.
Following instantiation combines accompanying drawing, and the corrosion inhibiter mechanism of action and correlation technique are further obtained explaining.
Embodiment
A. solution preparation:
1.The chemical gilding plating bath:
A:?(0.01－0.04?M)?H
2AuCl
6?+?(0.02－0.04?M)?NaOH;
B:?(0.1－0.3?M)?NH
4Cl?+ (0.3－0.5?M)?Na
2SO
3?+?(0.1－0.3?M)?Na
2S
2O
3 .5H
2O
The A+B mixed diluting is the Au plating bath, M-(mol, down together)
2.The electrodeposit metals plating bath:
Constitute by following reagent: (10
-3-10
-2M) X
2(SO
4)
x(10
-3-10
-2M) H
3BO
3And (10
-4-10
-3M) H
2SO
4
(X can be metallic element Fe, Co, Ni, Cu, Zn in the following formula)
Temperature: 15-35 ℃
Cathode-current density: 0.5-5 A/dm
2
3.The electrodeposit metals alloy electroplating bath:
Constitute by following reagent: (10
-3-10
-2M) X
2(SO
4)
x(10
-3-10
-2M) Y
2(SO
4)
y(10
-3-10
-4M) H
3BO
3(10
-3-10
-4M) NaCl
(X, Y can be metallic element Fe, Co, Ni, Cu, Zn in the following formula)
Temperature: 20-40 ℃
Cathode-current density: 0.2-5 A/dm
2
4.Corrosion inhibitor solution:
(0.001-0.5 M) corrosion inhibiter+supporting electrolyte (acidity, neutrality, alkalescence all can)
B. the preparation of electrode
1.Double cylindrical silicon baseplane, the aluminum oxide polishing powder with diameter 1 μ m, 0.3 μ m and 0.05 μ m carries out mechanical buffing successively, and replaces the ultrasonic cleaning surface with deionized water and acetone, removes surface and oil contaminant, oxide, until surface hydrophobicity.The silicon post of polishing is placed H
2SO
4 :H
2O
2In the solution of (V/V-volume ratio)=4:1-2:1, soaked 20-40 minute, realize surface hydroxylation, at this moment surperficial total hydrophilic.With semicircle silicon post baseplane, at NH
4In the F solution, etching 1-3 minute, this moment, even minute bubbles appearred in silicon face, and ultrapure water is rinsed well, and this moment, the surface was hydrophobic fully.With the semicircle silicon post that etching is finished, place the mixed solution of the HF 50 μ l of chemical gilding solution 3-5 ml and 2%, the control temperature is 45 ℃-55 ℃, deposits 3-5 minute.
The preparation metal film electrode: assembling spectrum electrolytic cell, with the gold-plated semicircle silicon post of surface chemistry as working electrode, electro-deposition research object metal.The metal nano membrane electrode that make this moment is that dummy and electrode surface metal cover densification and free of pinholes.The electrode that makes was statically placed in the corrosion inhibitor solution 2-8 hour.What made this moment is the metal nano membrane electrode that finishing has corrosion inhibiter.
C. test process
The test process of following instantiation can combine accompanying drawing that the corrosion inhibiter mechanism of action and correlation technique are further specified.
Experiment is carried out in the three-electrode system spectrum tool of single-minded particular design voluntarily; Its structure is as shown in Figure 1; Working electrode 1; Being included as unassembled and being assembled with the electrode (it is a semicircle silicon post 2) of corrosion inhibiter molecule respectively, is pure platinum electrode 3 to electrode, and contrast electrode is a saturated calomel electrode (SCE) 4.After electrode preparation finishes, spectrum tool is put into infrared chamber, and regulate light path, make detecting device detect the repeatedly infrared light (see figure 2) of reflection.
In-situ surface strengthens the infrared spectrum order as follows:
1. the infrared spectrum of the metal electrode of unassembled corrosion inhibiter molecule under the open-circuit condition is composed as environmental change water.
2. the infrared spectrum of the metal electrode of unassembled corrosion inhibiter molecule under current potential modulation-1.0 V is composed as reference.
The solution of 3. unassembled corrosion inhibiter molecule is derived from solution turnover 7 with changing the liquid flow pumps, and changes to the corrosion inhibitor solution except oxygen, open circuit self assembly 4 hours; Remain on during assembling in the spectrum tool by feeding gas port 5; Annotate high pure nitrogen, and, discharge by gas outlet 6.
4. working electrode 1 is external by copper conductor 8, and the current potential that puts on working electrode is followed successively by-1.0 V from low to high ,-0.8 V, and-0.6 V ,-0.4 V when-0.2 V and 0 V, and gathers corresponding infrared spectrum (see figure 6) respectively.The gained spectrogram is deducted Environmental Water spectrum 1. respectively, composes with the reference 2..Obtain the molecular information of corrosion inhibiter molecular adsorption in the metal surface.
5. combine supplementary means such as density Functional Calculation that each spectrum peak is belonged to; And analyze with potential change; The absorption change of configuration of corrosion inhibiter molecule makes the corrosion inhibiter mechanism of action obtain explaining, is one of technology understanding the corrosion inhibiter parameter optimisation procedure.
With corrosion inhibiter 2-amino-5-sulfydryl-1,3,4-thiadiazoles molecular adsorption is an example in the metallic cobalt surface, can find out that according to Fig. 6 along with current potential is shuffled, each peak intensity changes, and the peak position also is subjected to displacement, particularly 1550cm
-1Move to 1514 cm gradually
-1(Fig. 6), spectrum peak ownership provides 2-amino-5-sulfydryl-1,3, and the 4-thiadiazoles is at the inhibition mechanism on cobalt surface, that is:
1. at electronegative potential 2-amino-5-sulfydryl-1,3, the 4-thiadiazoles is adsorbed in cobalt surface (see figure 4) through amino N end in the molecule with the inclination mode.
2. at noble potential 2-amino-5-sulfydryl-1,3,4-thiadiazoles and cobalt form fine and close surface metal complex compound and play the corrosion inhibition (see figure 5).
Above description of test, in-situ surface strengthen infrared spectrum, the information of corrosion inhibiter molecule that can the detecting electrode surface-assembled, and explain the absorption configuration of the organic inhibition agent molecule of a fixed structure in the metal surface.Promptly through on the semicircular silicon post of infrared window; The plating nano thin-film; Obtain higher, the better membrane electrode of reinforced effects of reliability, strengthen infrared technique with in-situ surface again, research absorption corrosion inhibiter molecule in the metal surface with the variation of current potential; Be to understand the strong instrument of corrosion inhibiter mechanism, this technology is more conducive to metal or alloy corrosion protection and the widespread use of protecting.
Claims (3)
1. one kind with the spectroscopy means that combine with corrosion of metal, study surperficial corrosion inhibiter, are used to optimize the method for protection metal and alloy; It is characterized in that with semicircle silicon post be the research carrier; Its surface chemistry is gold-plated, this cylinder is installed in the spectrum electrolytic cell of single-minded design, and the fixed spectrum electrolytic cell is in the light path of total reflection again; The metal of electro-deposition research object; The liquid changing device that utilize to flow comprises inorganic and organic corrosion inhibitor solution or organic polymer class solution injects spectrum tool and left standstill several hours, makes inhibition molecule in the battery surface self assembly;
The utilization in-situ surface strengthens infrared spectrum technology above-mentioned sample is carried out the current potential Modulation analysis, obtains actual parameter, thereby strengthen corrosion inhibiter is selected.
2. according to claim 1ly a kind ofly study surperficial corrosion inhibiter, be used to optimize the method for protection metal and alloy with the spectroscopy means that combine with corrosion of metal; The metal that it is characterized in that manufacturing experimently electro-deposition can be Fe, Co, Ni; Cu, each metalloid such as Zn and alloy thereof.
3. according to claim 1; 2 is described a kind of with the spectroscopy means that combine with corrosion of metal; Study surperficial corrosion inhibiter, be used to optimize the method for protection metal and alloy, it is characterized in that surperficial corrosion inhibiter; Comprise all kinds of inorganic (as: chromate, nitrite, molybdate, Quadrafos, zinc salt etc.); And organic inhibitor (as: phosphonic acids and salt thereof, phosphine carboxylic acid, mercaptobenzothiazoler, benzotriazole, lignosulfonate etc. contain the heterogeneous ring compound of oxynitrides etc.), and surperficial corrosion inhibiter becomes the technology that can select according to qualifications in to trial-production metal and alloy protecting application.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103033474A (en) * | 2012-12-10 | 2013-04-10 | 中南大学 | Electrochemical-optical combined in-situ study spectral cell |
| CN108795498A (en) * | 2018-05-17 | 2018-11-13 | 宜兴市星光宝亿化工有限公司 | A kind of oil refining corrosion inhibiter and preparation method thereof |
| CN111122546A (en) * | 2020-01-02 | 2020-05-08 | 北京科技大学 | Qualitative and semi-quantitative detection method of corrosion inhibitor molecules |
| CN111337449A (en) * | 2020-02-29 | 2020-06-26 | 同济大学 | Aptamer infrared spectrum sensor for detecting ATZ and detection method |
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| JP2003035661A (en) * | 2001-07-23 | 2003-02-07 | Konica Corp | Method and apparatus for measurement of infrared absorption spectrum by attenuated total reflection method |
| CN101029867A (en) * | 2007-03-29 | 2007-09-05 | 复旦大学 | Surface-reinforced infrared spectrum optical device |
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2012
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| JP2003035661A (en) * | 2001-07-23 | 2003-02-07 | Konica Corp | Method and apparatus for measurement of infrared absorption spectrum by attenuated total reflection method |
| CN101029867A (en) * | 2007-03-29 | 2007-09-05 | 复旦大学 | Surface-reinforced infrared spectrum optical device |
| WO2009031662A1 (en) * | 2007-09-07 | 2009-03-12 | National Institute For Materials Science | Surface enhanced infrared absorption sensor and process for rpoducing the surface enhanced infrared absorption sensor |
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Non-Patent Citations (1)
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103033474A (en) * | 2012-12-10 | 2013-04-10 | 中南大学 | Electrochemical-optical combined in-situ study spectral cell |
| CN103033474B (en) * | 2012-12-10 | 2016-06-08 | 中南大学 | Electrochemistry optics coupling on-spot study spectrum tool |
| CN108795498A (en) * | 2018-05-17 | 2018-11-13 | 宜兴市星光宝亿化工有限公司 | A kind of oil refining corrosion inhibiter and preparation method thereof |
| CN111122546A (en) * | 2020-01-02 | 2020-05-08 | 北京科技大学 | Qualitative and semi-quantitative detection method of corrosion inhibitor molecules |
| CN111337449A (en) * | 2020-02-29 | 2020-06-26 | 同济大学 | Aptamer infrared spectrum sensor for detecting ATZ and detection method |
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Application publication date: 20120801 |