CN101914771B - Inhibitor-supported carrier and preparation method and application thereof - Google Patents
Inhibitor-supported carrier and preparation method and application thereof Download PDFInfo
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- CN101914771B CN101914771B CN2010102143745A CN201010214374A CN101914771B CN 101914771 B CN101914771 B CN 101914771B CN 2010102143745 A CN2010102143745 A CN 2010102143745A CN 201010214374 A CN201010214374 A CN 201010214374A CN 101914771 B CN101914771 B CN 101914771B
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Abstract
The invention belongs to corrosion prevention technology of metal materials, in particular to an inhibitor-supported carrier and a preparation method and application thereof. The inhibitor-supported carrier comprises the following components in percentage by weight: 5 to 20 percent of acetic acid, 70 to 85 percent of water, 1 to 5 percent of carrier and the balance of supported inhibitor. The preparation method comprises the following steps of: dissolving 1 to 5 percent of chitosan solid in acid aqueous solution in percentage by weight, and uniformly stirring the solution with brute force so as to obtain a chitosan hydrosol carrier, wherein the acid aqueous solution is aqueous solution of acetic acid which comprises 5 to 20 percent of acetic acid and 70 to 85 percent of water. The inhibitor-supported chitosan hydrosol carrier supports the inhibitor and is directly coated on a corrosion-resistant metal device, or is used as an additive and added into an organic corrosion-resistant material inhibitor serving as a substrate, and then the organic corrosion-resistant material inhibitor is coated on the corrosion-resistant metal device. The inhibitor-supported carrier can be widely applied to corrosion prevention of metal materials. Because the chitosan is a natural material and has wide source, no toxins or pollution, the chitosan can prevent the metallic corrosion caused by microbes to a certain degree.
Description
Technical field
The invention belongs to the corrosion protection technology of metallic substance, specifically a kind of inhibitor-supported carrier and its preparation method and application.
Background technology
Metallic corrosion is human lives and modern industry, especially the important factor that facility destroys in ocean, the chemical engineering industry, corrosion not only causes the waste of material, because maintenance of the equipment is forced to stop production, more seriously causes catastrophic failure because corrosion causes oil, gas leakage.At present, prevent that caustic solution from having the several different methods such as external coating, surface treatment, electro-chemical protection, interpolation inhibiter.Add inhibiter can yet be regarded as a kind of simple process, with low cost, practical method.But; most inhibiter is for containing N, S, the equiatomic organic heterocyclic molecule of P; wherein; a considerable amount of inhibiter are insoluble or be insoluble in water; because solubleness is limited; this has limited the protection effect of inhibiter greatly; in addition; the inhibiter that adds is because the souring of current; be adsorbed on originally that the molecule of metallic surface is very fast to be washed away by current, and shortened the guard time of inhibiter, this just needs again to replenish in large quantities for a long time inhibiter; this has not only caused the waste of inhibiter, and wastes time and energy.So; develop and a kind of inhibitor molecular is had solublization, has a slow release effect simultaneously; can make the long-time inhibiter carrier that slowly discharges of inhibitor molecular of load; can greatly improve the protection effect of inhibiter, all have great importance for the protection that uses manpower and material resources sparingly with metallic substance.
Chitosan (chitosan) is a kind of natural cationic polyelectrolyte; its chemistry (1-4)-2-amino by name-2-deoxidation-callose; derive from the chitin in the shrimp crab shell; through chemical treatment; slough the ethanoyl on most of amino; being a kind of organic resource that extensively exists in the world, is the important component (approximately containing 10%～30%) of the shells such as arthropods such as shrimp, crab, insect, also is present in the zootic cell walls.Chitin is that nature output is only second to cellulosic second largest natural polymer renewable resources, and the source is abundant, low price, and nontoxic pollution-free has good biocompatibility and degradability.At present, be widely used in field of medicaments as medicinal slow release agent, control-released agent, solubility promoter, binder etc.Chinese patent CN1903367 has announced a kind of chitosan as 5 FU 5 fluorouracil pharmaceutical carrier method, Chinese patent CN1698901 has announced with chitosan and derivative thereof the method as the pharmaceutical carrier carrying red sage root extract, has realized solubilising and the control of red sage root activity extract are discharged.Simultaneously, chitosan pH less than 6 acidic solution in, the amino generation protonation reaction on the six-ring makes chitosan have positive polarity; Have good film-forming properties, easily form gel; Insoluble or insoluble medicine had good solublization; In addition, chitosan itself also has good bacteria resistance, and Chinese patent CN1664225 utilizes this character of chitosan to prepare a kind of chitosan antibacterial finishing agent, but aquagel is had no report at present as the inhibiter solid support material.
Summary of the invention
The object of the present invention is to provide a kind of wide material sources, low price, simple a kind of inhibitor-supported carrier of preparation and its preparation method and application.
For achieving the above object, the technical solution adopted in the present invention is:
Inhibitor-supported carrier: it is in 8% the aqueous acetic acid that the chitosan of 0.1g is dissolved in the 6m1 volume fraction, even through strong stirring in confined conditions, namely obtains chitosan water-sol carrier;
Described chitosan is that deacetylation is 90%～98%, molecular weight 200000～250000.
Described inhibiter is MBT.
The preparation method: inhibitor-supported carrier, it is in 8% the aqueous acetic acid that the chitosan of 0.1g is dissolved in the 6ml volume fraction, even through strong stirring in confined conditions, namely obtains chitosan water-sol carrier;
Described chitosan is that deacetylation is 90%～98%, molecular weight 200000～250000.
Described inhibiter is MBT.
Use: described inhibitor-supported carrier chitosan water-sol carrier, the metal device of inhibitor-supported rear direct coating corrosion prevention or the anti-corrosive organic coatings that adds to as substrate as additive lose the metal device that applies again corrosion prevention in the agent.Described coating is immersed in the ethanolic soln that contains with the mercaptan of 10～20 carbon atom carboxyls by the metal device of the inhibiter of supported carrier and was soaked 6-12 hour.
The present invention has following beneficial effect:
1. the present invention is acted on copper surface by the inhibiter of supported carrier, according to the anodic polarization curves test at copper surface, the protection efficient (PE) that is calculated by corrosion current can reach 97.70%.
2. the selected carrier chitosan of the present invention derives from natural product, and nontoxic pollution-free is without danger; Simultaneously chitosan itself also has bacteriostatic activity, for microbiological corrosion to a certain degree restraining effect is arranged also
3. the present invention is by the inhibiter of supported carrier, and raw material sources are extensive, and basic solvent is water, thereby the preparation method is simple to operate, and is with low cost, do not need specific installation.
Description of drawings
Fig. 1 is the anodic polarization curves figure of the inhibitor-supported hydrogel copper electrode of the prepared chitosan of the embodiment of the invention in 3.5%NaCl solution, and wherein, curve a corresponds to step 1 among the embodiment 1); B corresponds to step 2 among the embodiment 1); C corresponds to step 3 among the embodiment 1) in (1) do not add inhibiter; D corresponds to step 3 among the embodiment 1) in (3) coppersmith make the electrode sample;
Fig. 2 is that the inhibitor-supported hydrogel copper sheet of the prepared chitosan of the invention process sample soaks the digital photograph comparison diagram after 6 hours in the sulphate reducing bacteria inoculum, the digital photograph of A for just from the sulfate reduction bacteria culture fluid, taking out, B is the digital photograph of placing in air after above-mentioned copper sheet sample takes out 10 minutes, is followed successively by from left to right in the following case study on implementation 1 a) step 1), b) step 2), c) step 5 of not adding inhibiter) and d) step 5) the copper sheet sample.
Fig. 3 is the scanning electron microscope (SEM) photograph of the inhibitor-supported covering copper sample of the embodiment of the invention 2 chitosans, wherein the inhibitor-supported covering copper sample of (a) blank copper sample (b) chitosan.
Embodiment
Embodiment 1
Raw material: chitosan CS (molecular weight=2100kDa, deacetylation=90.6%) is available from Huantai Jinhu County crust Products Co., Ltd (Qingdao).11-carboxyl mercaptan does not carry out any processing and directly uses available from Sigma-Aldrich company.MBT and other reagent are analytical pure, available from Chemical Reagent Co., Ltd., Sinopharm Group.All aqueous solution all uses ultrapure water (Millipore) preparation.
1) the experiment preparation of metallic copper electrode
Electrochemistry experiment is prepared by copper rod (diameter 8mm) with copper electrode, the fine copper rod is cut into the right cylinder of high 1cm, with Resins, epoxy sealing all around, one side connects copper conductor, another side is exposed, successively sand papering becomes minute surface with 2000# with 1200# before the experiment, puts into 85% phosphoric acid and soaks N 5 minutes
2Dry up.
2) copper electrode surface treatment:
Adopting band 11-carboxyl mercaptan (UPA), be made into the ethanolic soln of 5mM, with step 2) prepared copper electrode is immersed in to place in this solution and spends the night N
2Dry up; Because the mercaptan end group that is adsorbed onto on the copper sample is carboxyl, so that copper sample surface band negative electricity.
3) by inhibiter of supported carrier and preparation method thereof
(1) chitosan (CS, deacetylation are 90%, and molecular weight is 200,000) of 0.1g being dissolved in the 6ml volume fraction is 8% aqueous acetic acid, and in confined conditions, strong stirring is dissolved into the solution of transparent and homogeneous fully to chitosan.
(2) to the MBT that wherein adds 0.084g (MBI), strong stirring to inhibiter is uniformly dispersed and is milk yellow under the air tight condition.
(3) the chitosan water-sol that this is contained inhibiter drips the copper sample surface (MBI-CS/UPA copper electrode) that is coated onto above-mentioned absorption carboxyl mercaptan, and room temperature is dried the formation aquagel.Chitosan water-sol positively charged, copper belt transect negative electricity, because the electrostatic interaction between the two, so that chitosan gel rubber stably is adsorbed on copper sample surface.
4) electrochemical property test
What electro-chemical test adopted is a Room three-electrode system; respectively with step 1), step 2), the step 5 of not adding inhibiter) and step 5) prepared copper electrode is as working electrode; platinum filament is done electrode; Ag/AgCl (3M KCl) makes reference electrode; the electrolytic solution of testing is that massfraction is 3.5%NaCl solution; soaked 2 hours; after open circuit potential is stable; the test of beginning polarization curve; and obtain corrosion current according to curve calculation, calculate protection efficient (PE) calculation formula and be
PE(％)＝(1-i
corr/i
0 corr)×100％
Wherein, i
0 CorrBe step 1) the corrosion current numerical value of prepared blank copper electrode, i
CorrCorrosion current numerical value for copper electrode to be tested.According to a) polarization curve of blank copper electrode of curve shown in Figure 1, the i that records in this experiment
0 CorrNumerical value 2.530 * 10
-5A; Curve b) be step 2 among the embodiment 1) in the copper electrode polarization curve, its corrosion current numerical value i
CorrThe order of magnitude that descends is 4.567 * 10
-6A, reason is to cause cathodic current to descend because the self assembly molecule layer stops oxygen and moisture diffusion, protects accordingly efficient 81.95%; Curve c) be step 3 among the embodiment 1) in (1) do not add the copper electrode polarization curve of inhibiter, corrosion current numerical value i
Corr2.153 * 10
-6A, the corrosion current value is than i
0 CorrTwo orders of magnitude that descend, similarly, also because cathodic current descends causes, corresponding protection efficient brings up to 91.49%; Curve d) be step 3 among the embodiment 1) in (3) copper electrode polarization curve, corrosion current numerical value i
Corr5.814 * 10
-7A, best for wherein protecting effect, suppress simultaneously the effect of negative electrode and anodic reaction: slightly to shuffling, anodic current and cathodic electricity flow valuve reduce corrosion potential simultaneously.It is the same owing to the self assembly molecule layer stops due to oxygen and the moisture diffusion that cathodic process is suppressed reason.The existence of MBT in the composite membrane (anodic corrosion inhibitor) causes corrosion potential to be shuffled, and the anodic current value reduces simultaneously.The MBT molecule can be adsorbed onto the copper electrode surface, stops the copper atom anode dissolution, thereby suppresses anodic reaction, and corresponding protection efficient is 97.70%.
Difference from Example 1:
1) experiment is with the preparation of metallic copper electrode: testing used copper sample is a plurality of copper sheet samples of 20 * 30 * 5mm.
2) the metallic copper electrode corrodes with sulphate reducing bacteria:
(1) microbial culture
The sulfate reduction bacterial classification that this institute uses is taken from Bohai Sea bottom silt.The used seawater of culturing bacterium is taken from Huiquan Bay of Qingdao.
Bohai Sea bottom silt with the vial of high-temp steam sterilizing gathers adds the sulfate reduction bacterium culture medium again and cultivates.Consider that SRB is anaerobic bacterium, then logical nitrogen 1h uses paraffin sealing before cultivating.Place vial electro-heating standing-temperature cultivator under 30 ℃, to cultivate.The substratum that every interval 10d more renews is with the supply of the growth nutriment that guarantees SRB.
Substratum is composed as follows: 0.5g/L Na
2SO
4, 0.5g/L K
2HPO
4, 1.0g/L NH
4Cl, 0.1g/L CaCl
2, 2.0g/L MgSO
4, 4ml/L Sodium.alpha.-hydroxypropionate, 1.0g/L yeast powder.Mentioned reagent is dissolved in the 1L seawater, then the pH value of solution is transferred to about 7.2, and be divided in the vial of 250ml, tampon on the bottle plug is wrapped with tinfoil, 121 ℃ of sterilization 20min in pressure steam sterilization boiler.
(2) with sulphate reducing bacteria attack metal copper electrode: with step 1) the metallic copper electrode is immersed in 6h in the sulfate reduction bacteria culture fluid, and is after the ultrapure water flushing, after drying up with nitrogen, stand-by.
3) copper electrode surface treatment:
Adopting band 11-carboxyl mercaptan (UPA), be made into the ethanolic soln of 5mM, with step 2) prepared copper electrode is immersed in to place in this solution and spends the night N
2Dry up; Because the mercaptan end group that is adsorbed onto on the copper sample is carboxyl, so that copper sample surface band negative electricity.
4) by inhibiter of supported carrier and preparation method thereof
(1) chitosan (CS, deacetylation are 90%, and molecular weight is 200,000) of 0.1g being dissolved in the 6ml volume fraction is 8% aqueous acetic acid, and in confined conditions, strong stirring is dissolved into the solution of transparent and homogeneous fully to chitosan.
(2) to the MBT that wherein adds 0.084g (MBI), strong stirring to inhibiter is uniformly dispersed and is milk yellow under the air tight condition.
(3) the chitosan water-sol that this is contained inhibiter drips the copper sample surface (MBI-CS/UPA copper electrode) that is coated onto above-mentioned absorption carboxyl mercaptan, and room temperature is dried the formation aquagel.Chitosan water-sol positively charged, copper belt transect negative electricity, because the electrostatic interaction between the two, so that chitosan gel rubber stably is adsorbed on copper sample surface.
5. the copper sheet sample processing method is with the step 1 among the embodiment 1), step 2), the step 5 of not adding inhibiter) and step 5) coppersmith makes the electrode sample.Successively sand papering becomes minute surface with 2000# with 1200# before the experiment, puts into 85% phosphoric acid and soaks N 5 minutes
2Dry up.
6. above-mentioned copper sample is respectively charged into separately in the culture dish, pours the sulfate reduction bacteria culture fluid into, put into 30 ℃ of constant incubators and place to take out after 6 hours and take pictures, obtain contrast experiment's photo (referring to Fig. 2 A, B).
Wherein, a, b, c, d, e are respectively treatment process with the step 1 among the embodiment 1), separately chitosan, step 2), the step 5 of not adding inhibiter) and step 5) the copper sample.B, d, e copper specimen surface are coated with the sample of chitosan hydrogel film, and be all protected fine, substantially keep the true qualities of copper, and other all corroded blackening, especially surface coverage composite membrane arranged the copper sample from the appearance, preferably protected.But although variable color does not occur in immersion process the copper sample of surperficial independent covering chitosan hydrogel film, taking-up exposes 10min in air after, film body is with regard to the avidity owing to shortage and substrate, from the copper sur-face peeling.But, can see from the sur-face peeling part, the internal copper matrix still remains intact.
The inhibitor-supported covering copper sample of above-mentioned chitosan is carried out scanning electron microscopic observation, and under the comprehensive action of hydrogen sulfide, chlorion and hydroxide ion, the pure copper samples surface is because corrosion becomes uneven as shown in Figure 3.
Simultaneously, pure copper samples is also observed sulphate reducing bacteria, and sulphate reducing bacteria shows as some black shade under the bombardment effect of electronics, is the profile of sulfate-reducing bacteria.But, the inhibitor-supported covering copper sample of chitosan is not observed the shade of any sulphate reducing bacteria, but under the condition of Electronic Speculum, see or the film of surface uniform, have no defective, thereby as seen, composite membrane is not only from can self keep stable under corrosive environment, simultaneously, can effectively kill the sulphate reducing bacteria that is attached to the copper surface.
Above-described embodiment is the better embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (5)
1. inhibitor-supported carrier is characterized in that:
Inhibitor-supported carrier: it is in 8% the aqueous acetic acid that the chitosan of 0.1g is dissolved in the 6ml volume fraction, even through strong stirring in confined conditions, namely obtains chitosan water-sol carrier;
Described chitosan is that deacetylation is 90%～98%, molecular weight 200000～250000.
2. by inhibitor-supported carrier claimed in claim 1, it is characterized in that: described inhibiter is MBT.
3. preparation method by inhibitor-supported carrier claimed in claim 1, it is characterized in that: inhibitor-supported carrier, it is in 8% the aqueous acetic acid that the chitosan of 0.1g is dissolved in the 6ml volume fraction, in confined conditions, even through strong stirring, namely obtain chitosan water-sol carrier;
Described chitosan is that deacetylation is 90%～98%, molecular weight 200000～250000.
4. by the preparation method of inhibitor-supported carrier claimed in claim 3, it is characterized in that: described inhibiter is MBT.
5. application by inhibitor-supported carrier claimed in claim 1, it is characterized in that: described inhibitor-supported carrier chitosan water-sol carrier, the metal device of inhibitor-supported rear direct coating corrosion prevention or the anti-corrosive organic coatings that adds to as substrate as additive lose the metal device that applies again corrosion prevention in the agent;
Described coating is immersed in the ethanolic soln that contains with the mercaptan of 10～20 carbon atom carboxyls by the metal device of the inhibiter of supported carrier and was soaked 6-12 hour.
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| CN106833079A (en) * | 2016-12-26 | 2017-06-13 | 中国科学院海洋研究所 | A kind of Porous Chitosan Microspheres for coating corrosion inhibiter and its preparation and application |
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| CN102409331B (en) * | 2011-09-23 | 2014-04-23 | 安徽工业大学 | Chitosan modified surface treatment liquid for galvanized color-coated board and preparation method thereof |
| CN103113490A (en) * | 2011-11-17 | 2013-05-22 | 中国科学院海洋研究所 | Water-soluble chitosan phosphate, and preparation application and thereof |
| US9771483B2 (en) * | 2013-04-19 | 2017-09-26 | The Boeing Company | Systems, compositions, and methods for corrosion inhibition |
| CN105885502B (en) * | 2016-05-07 | 2019-01-29 | 浙江大学自贡创新中心 | The preparation method of inexpensive corrosion inhibiter support structures |
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| CN1593385A (en) * | 2004-06-22 | 2005-03-16 | 天津大学 | Gel capable of injecting temperature sensitive complex and its preparation method |
| CN101176789A (en) * | 2006-11-11 | 2008-05-14 | 中国海洋大学 | Method for preparing temperature sensitive sustained-release gel of chitosan fat complexes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1593385A (en) * | 2004-06-22 | 2005-03-16 | 天津大学 | Gel capable of injecting temperature sensitive complex and its preparation method |
| CN101176789A (en) * | 2006-11-11 | 2008-05-14 | 中国海洋大学 | Method for preparing temperature sensitive sustained-release gel of chitosan fat complexes |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106833079A (en) * | 2016-12-26 | 2017-06-13 | 中国科学院海洋研究所 | A kind of Porous Chitosan Microspheres for coating corrosion inhibiter and its preparation and application |
| CN106833079B (en) * | 2016-12-26 | 2019-06-11 | 中国科学院海洋研究所 | A kind of Porous Chitosan Microspheres coating corrosion inhibiter and its preparation and application |
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