CN101845635B - Compound silicate corrosion inhibitor for protecting ferruginous historical relics - Google Patents
Compound silicate corrosion inhibitor for protecting ferruginous historical relics Download PDFInfo
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- CN101845635B CN101845635B CN2009100809142A CN200910080914A CN101845635B CN 101845635 B CN101845635 B CN 101845635B CN 2009100809142 A CN2009100809142 A CN 2009100809142A CN 200910080914 A CN200910080914 A CN 200910080914A CN 101845635 B CN101845635 B CN 101845635B
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Abstract
The invention provides a compound silicate corrosion inhibitor for protecting ferruginous historical relics. Thecorrosion inhibitor takes sodium silicate as a main agent, is added with sodium gluconate and zinc sulfate, and is also added with sodium tungstate for further improving the corrosion inhibition effect of the corrosion inhibitor, wherein the sodium silicate content is 2 to 10 g/L; the sodium gluconate content is 0.1 to 0.3 g/L; the zinc sulfate content is 0.1 to 0.2 g/L; and the sodium tungstate content is 1 to 2 g/L. The compound silicate corrosion inhibitor has good corrosion inhibition effect on simulated ancient white cast iron, has significant corrosion inhibition effect on low-silicon low-sulfur white iron, and has the corrosion inhibition rate up to over 80 percent.
Description
Technical field
The present invention relates to a kind of inhibiter that is used for protecting ferruginous historical relics, relate to a kind of compound silicate corrosion inhibitor that is used for protecting ferruginous historical relics in more detail.
Background technology
Inhibiter (corrosion inhibitor): be meant and in medium, add the corrodibility that can reduce medium on a small quantity, make the material of metal corrosion.The influence to the electrochemical metal corrosion process in medium is divided into anode type, cathode type and hybrid corrosion inhibitor according to inhibiter.Anodic corrosion inhibitor comprises chromic salt, nitrate, nitrite, orthophosphoric acid salt, silicate, benzoate etc.They can increase anodic polarization, thereby corrosion potential is shuffled, and normally the negatively charged ion of anodic corrosion inhibitor is shifted to anode surface and made metal passivation.The cathode type inhibiter comprises poly-phosphate, zinc sulfate, acid calcium carbonate, arsonium ion, antimony ion etc.They make in medium, and the metallic corrosion current potential is negative to be moved, and increases the overpotential of hydrogen evolution in the acid solution, and cathodic process is slowed down.Cathode type inhibiter normally positively charged ion is shifted to cathode surface, and forms chemistry or electrochemistry precipitation membrane, the protection metal.Hybrid corrosion inhibitor such as compound nitrogenous, sulphur are as the nitrite of amine, imidazolines, quaternary ammonium salt and organic amine, mercaptan, thioether, thiocarbamide etc.Inhibiter has synergistic effect, and composite corrosion inhibitor generally will use in certain environment (medium), tangible corrosion mitigating effect is just arranged, so inhibiter must be estimated to corrosion inhibition in specified working medium.
A lot of industrial inhibiter also are applied to the protection of iron cultural relic by using.
Sodium Nitrite and Sodium chromate be commonly used be the iron cultural relic by using inhibiter.Sodium Nitrite and Sodium chromate belong to anodic corrosion inhibitor, have oxidisability, and its effect is to make the anode surface passivation.Density of corrosion inhibitor can work when about 0.1g/l.But chromic salt and nitrite pollute surrounding environment easily, therefore are restricted especially in recent years in the use.
Some positively charged ions can be diffused into anode surface in neutral solution, with the hydroxide ion reaction, generate precipitation, become protective layer.These positively charged ions comprise calcium ion, magnesium ion, zine ion, nickel ion, mn ion etc.Some metal ions such as arsenic, antimony etc. can form a skim at anode surface, reduce the generating rate of hydrogen or generate total amount.Beijing University of Chemical Technology is permitted the inhibition envelope maintaining method patent that pure grade has been applied for an iron cultural relic by using, the composite corrosion inhibitor that bottom adopts benzotriazole or sodium wolframate and sodium laurylsulfonate to form, surface layer adopts the polyurethane sealing that adds nano titanium oxide and silicon-dioxide to protect, and corrosion resisting property is good.
Phosphoric acid salt and polyphosphoric acid salt (Na
5CaP
6O
18) n
N+Also be protecting ferruginous historical relics inhibiter commonly used, can form the thicker protective membrane of one deck, stop anodic reaction on the implements surface.But all there are easy promotion biological growth in phosphoric acid salt and polyphosphoric acid salt, problem such as pollute.
Traditional vapour-phase inhibitor comprises dicyclohexyl amine nitrite salt, cyclohexylamine carbonate etc., the implements surface that is generally used for just having handled.Because factors such as health, safety, the use of this class inhibiter also is restricted.
Weibull and gallic acid one class are widely used in the inhibiter of historical relic, and Weibull can react with lepidocrocite, generate amorphous compound, increase the solidity to corrosion of treat surface.But there are some researches show that they are vesicular structures at the compound that iron surface forms, and have photosensitivity, do not have enough further corrosive effects that prevents, just darker color makes that further corrosion is invisible.Weibull is for the not effect of implements surface of the serious corrosion of protection, and only the implements for treat surface formation continuous oxide layer have derusting action.
The practical application report of silicate corrosion inhibitor in historical relic's protection seldom.Cai Lankun etc. have studied the interface corrosion inhibition of ironware preprocessing solution mesosilicic acid salt.Replace iron cultural relic by using to study with carbon steel, water glass is after steel surface absorption, and the hydrous iron oxide generation chemical reaction surperficial with it forms the protective membrane of even compact.The hydrous oxide of steel surface helps the silicate film forming.Aspect practical application, they have handled two boundary tablets with the composite washing lotion of having added silicate corrosion inhibitor, and silicate corrosion inhibitor has slowed down the atomospheric corrosion in the cleaning process, helps further rotproofing.
Utilize silicate to make inhibiter, be mainly used at first and carry the anticorrosion of drinking water pipeline.From the appearance of the efficient organic inhibitor agent seventies, give the condition created of promoting the use of of silicate, particularly worked out composite slow-corrosion scale resistor prescription in recent years both at home and abroad based on silicate, enlarged the use range of silicate.Silicate is as inhibiter, and major advantage is: totally nontoxic under normal working concentration does not produce environment and pollutes; Not the microbial nutrition source, do not encourage microbial reproduction; Be applicable to high Cl
-The processing of ionic concn water quality; Processing ease is safe from danger; Raw material sources are abundant, and are cheap; Silicate can react with ferric iron, generates precipitation membrane, can realize the protection of part band rust.But its defective is a silicate forms the silicon dirt that is difficult to remove easily, and is difficult for suppressing, and therefore uses silicate corrosion inhibitor separately, and corrosion mitigating effect is undesirable.And the practical application report of silicate corrosion inhibitor in historical relic's protection seldom.
Summary of the invention
The present invention is based on national science and technology supporting plan problem " research of iron cultural relic by using comprehensive protecting technology " (project number: patent application 2006BAK20B03).
The object of the present invention is to provide a kind of compound silicate corrosion inhibitor that is used for protecting ferruginous historical relics, the defective that produces when overcoming single use silicate corrosion inhibitor.
For achieving the above object, the compound silicate corrosion inhibitor that is used for protecting ferruginous historical relics provided by the invention is a host with the water glass; add Sunmorl N 60S and zinc sulfate, wherein, water glass content is 2-10g/L; the gluconic acid sodium content is 0.1-0.3g/L, and zinc sulfate content is 0.1-0.2g/L.The sodium wolframate that more preferably can also add 1-2g/L.
The water glass that the present invention adopts more preferably is a non-hydrate sodium metasilicate.
Embodiment
Silicate is as the iron cultural relic by using inhibiter, and major advantage is: silicate can react with ferric iron, generates precipitation membrane, can realize the protection of part band rust.But silicate forms the silicon dirt that is difficult to remove easily, and is difficult for suppressing, and corrosion mitigating effect is undesirable.The composite uses of inhibiter such as normal and poly-phosphate, organic phospho acid, aluminate, zinc salt.
The inhibition mechanism of silicate corrosion inhibitor a kind ofly thinks that silicate is electronegative colloidal particle in water, combines with metallic surface dissolved iron ion to form silicic acid gel, covers the metallic surface and plays corrosion inhibition, so silicate is to precipitate the membranous type inhibiter.Another kind of viewpoint thinks that original corrosion product and silicate form a kind of adsorptivity mixture protective membrane in the water, and this film divides two-layer, and bottom is made of corrosion product, and the upper strata is the adsorptivity mixture that metal hydroxides and silica gel are condensed into.
Water glass uses separately as inhibiter, can play the certain protection effect, but because the time of formation protective membrane is longer, and the protective membrane of formation is porous, so water glass and the composite use of other inhibiter, is the direction of silicate corrosion inhibitor development.The present invention selects the host of non-hydrate sodium metasilicate as the inhibition system for use.The molecular formula of non-hydrate sodium metasilicate is Na
2SiO
39H2O, crystal water content reaches 58%, solubleness (20 ℃) 38g/100g water, dissolution rate is very fast.
Sunmorl N 60S is a nontoxicity environmental friendliness inhibiter, its biggest advantage be with water in calcium, iron ion form the complex compound protective membrane, be that a kind of precipitation is by the membranous type inhibiter.Sunmorl N 60S is a kind of multi-hydroxy carboxy acid's salt, can cooperate with multiple inhibiter to form synergistic effect.
Zinc sulfate is precipitation membranous type inhibiter.It is generally acknowledged that dissolved oxygen is oxidized to Fe with Cast Iron Surface
2+(part is Fe
3+), the Zn in the solution
2+With OH
-In conjunction with forming Zn (OH)
2, be deposited in the metallic surface.
Sodium wolframate is almost non-toxic, belongs to the environmental friendliness inhibiter.Tungstate ion in the solution at first is adsorbed on Cast Iron Surface, and the iron ion that generates with anodic reaction forms the passive film that the diffusion of ferrous ion is had barrier effect, thereby plays corrosion inhibition.
In the water glass inhibiter, add Sunmorl N 60S, zinc sulfate and sodium wolframate and can effectively remedy the defective of water glass protective layer, play synergy, improve the corrosion inhibition rate of water glass inhibiter.
After below research was added Sunmorl N 60S, zinc sulfate and sodium wolframate successively in water glass inhibition system, the silicate corrosion inhibitor moiety was to the influence of corrosion mitigating effect.The results are shown in Table 1.As can be seen from Table 1, adding composite component can make the corrosion mitigating effect of water glass obviously improve.Sodium gluconate, zinc sulfate and sodium wolframate have remedied the defective of water glass inhibition rete effectively at the protective membrane that Cast Iron Surface forms, thereby make the corrosion mitigating effect of water glass significantly improve.
The adding of zinc sulfate significantly improves the corrosion mitigating effect of silicate inhibition system.For determining the composition of inhibition system, studied of the influence of zinc sulfate addition to inhibition system corrosion mitigating effect.The results are shown in Table 2.When the sulfuric acid zinc concentration was low, the corrosion inhibition rate of inhibition system was lower, can not play effective corrosion inhibition.Therefore the sulfuric acid zinc concentration should be not less than 0.1g/L in the compound system.
In order to study the corrosion inhibition of silicate inhibition system to the ancient cast iron historical relic better, the present invention has studied the corrosion inhibition of the cast iron print that silicate inhibition system manufactures simulation ancient cast iron composition.The results are shown in Table 3.With Na
2SiO
3/ Sunmorl N 60S/ZnSO
4/ sodium wolframate system has been investigated its corrosion mitigating effect to low silicon low-sulfur white pig iron and low silicon high-sulfur white pig iron as inhibiter.The result shows that this inhibition system all has corrosion inhibition preferably for simulation white cast iron in ancient times, and particularly remarkable for the corrosion mitigating effect of low silicon low-sulfur white pig iron, corrosion inhibition rate reaches 89%.
Claims (3)
1. a compound silicate corrosion inhibitor that is used for protecting ferruginous historical relics is a host with the water glass, adds Sunmorl N 60S and zinc sulfate, and wherein, water glass content is 2-6g/L, and the gluconic acid sodium content is 0.1-0.3g/L, and zinc sulfate content is 0.1-0.2g/L.
2. compound silicate corrosion inhibitor as claimed in claim 1 wherein, contains the sodium wolframate of 1-2g/L.
3. compound silicate corrosion inhibitor as claimed in claim 1, wherein, water glass is a non-hydrate sodium metasilicate.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009100809142A CN101845635B (en) | 2009-03-25 | 2009-03-25 | Compound silicate corrosion inhibitor for protecting ferruginous historical relics |
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| CN2009100809142A CN101845635B (en) | 2009-03-25 | 2009-03-25 | Compound silicate corrosion inhibitor for protecting ferruginous historical relics |
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| CN101845635B true CN101845635B (en) | 2011-12-28 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102828187B (en) * | 2012-09-20 | 2014-08-13 | 昌邑市龙港无机硅有限公司 | Novel antirust agent for marine machinery and method for preparing same |
| CN105036365A (en) * | 2015-06-30 | 2015-11-11 | 苏州佑君环境科技有限公司 | Draught fan dedusting stripping scale inhibitor and preparation method thereof |
| CN106757070A (en) * | 2016-11-27 | 2017-05-31 | 湖南金裕化工有限公司 | Environmentally friendly restrainer and preparation method thereof |
| CN108035701B (en) * | 2017-12-15 | 2021-12-10 | 西南石油大学 | Corrosion inhibitor for air flooding and use method and application thereof |
| CN111470840B (en) * | 2020-04-23 | 2022-05-31 | 中国文化遗产研究院 | Stone cultural relic surface crack repairing material and preparation method thereof |
| CN113529089B (en) * | 2021-07-02 | 2023-06-06 | 北京首融汇科技发展有限公司 | Environment-friendly gas phase corrosion inhibitor and gas phase rust-proof material |
| CN115074738B (en) * | 2022-06-13 | 2024-03-08 | 山东国智新材料科技有限公司 | Environment-friendly multi-element composite vapor phase corrosion inhibitor and preparation method thereof |
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