CN101851759A - Tannin corrosion inhibitor for protecting iron cultural relics - Google Patents
Tannin corrosion inhibitor for protecting iron cultural relics Download PDFInfo
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Abstract
The invention provides a tannin corrosion inhibitor for protecting iron cultural relics. The tannin corrosion inhibitor comprises 4 to 6mM of tannin, 0.04 to 0.06mM of Zn(H2PO4)2, 9 to 11mM of Na2SiO3 and 2 to 4M of ethanolamine and has the pH ranging from 11 to 12. The tannin corrosion inhibitor makes up the simple complexing function of the tannin, reduces the corrosion influence of acidic tannin on ironware bases, has corrosion inhibition effect obvious superior to the tannin and conforms to the principles of no change in original states of the relics, the minimum intervention and the like.
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 tannin corrosion inhibitor that is used for protecting ferruginous historical relics in more detail.
Background technology
Adopting materials such as phosphoric acid salt, chromic salt, Weibull that iron cultural relic by using is carried out the inhibition processing is to use traditional method more widely.
Weibull is not single compound, but a kind of polyphenol mixture, the chemical constitution more complicated is present in the bark and fruit of multiple trees such as Oak Tree, lacquer tree, and is different with raw material sources, roughly can divide two kinds: hydrolyzable tannin and condensed tannin.Wherein the hydrolyzable tannin is the tannin of using always, and molecular weight is 500-3000, has ester bond in its molecule, is the gallic acid ester of glucose, can be decomposed into gallic acid and series matter and carbohydrate under acid or alkali effect; Condensed tannin is the Flavonol derivative, and 2 of Flavonol combine with catechol or benzenetriol by C-C in the molecule, can not resolve into certifiable simple material by hydrolysis.The tanning leather ability and the reducing power of these two kinds of tannin are roughly suitable.Owing to contain a certain amount of bis-phenol or triphenol group, metal surface protection had important effect in the Weibull molecule.
Use Weibull report much more to be arranged as the protecting ferruginous historical relics material; as: " Liu Endi; two kinds of methods that the metal historical relic's protection is handled; second academic nd Annual Meeting collection of China Association for Preservation Technology of Cultural Relics; 2002; 39-42 " introduced Japan and India historical relic's protection expert and with the 5% Weibull aqueous solution ship engines of seawater salvaging have been soaked the inhibition processing down at 70 ℃, obtain better effects." Zhang Hengjin, Zhang Xiaolan, the protection research of iron cultural relic by using; second academic nd Annual Meeting collection of China Association for Preservation Technology of Cultural Relics; 2002,60-70 " adopt SODIUM PHOSPHATE, MONOBASIC, Sodium chromate and Weibull combination solution that the inhibition Passivation Treatment is carried out on the iron cultural relic by using surface, improved its corrosion resistance." poplar is busy busy, the protection of ironware and reparation, the academic nd Annual Meeting collection of China Association for Preservation Technology of Cultural Relics's first, 2001 " mentioned, and after ironware is finished dechlorination, rust cleaning, will show the primary shape of implements.If implements remain metal-cored, Weibull commonly used is handled, and it forms a kind of black on the ironware surface and stablizes tannate, makes implements and external environment isolated, has stoped the generation of corrosion reaction, handles implements surface, back blackout slightly.If implements corrode fully, there is no need to handle with Weibull." T.R.Ross, R.A.Franics.Thetreatment of rusted steel with mimosa tannin.Corrosion Science.1978,18 (4): 351-361. " infer that according to Infrared spectroscopy Weibull and iron ion form cancellated five-ring inner complex." Wang Jikui, Liu Baochun, Cai Lu, open thick, the Weibull chemical conversion film on .A3 steel surface, all peaks. Nanjing University of Chemical Technology's journal, 1996,18 (3): 54-57. " handle the Q235 carbon steel with tannic acid solution, obtained to have corrosion proof chemical conversion film on its surface.1999 and The National Museum of China in 2004 adopt Weibull as main inhibition material [seeing also national science and technology " 15 " Program for Tackling Key Problems problem " disease of metal species historical relic and the research of control thereof " P1-128 to 1-131] at protection end door cone drums and Yongji, Shanxi Pu ferry crossing car pusher, iron man, iron prop ironware group time.
Using method for Weibull, J.B.Pelikan thinks need adopt different treatment processs at different situations, see also " J.B.Pelikan.Conservation of Iron with Tannin.Studies inConservation.1966,11 (3): 109-115. ".
(a) for the ironware that a small amount of corrosion is arranged.Clean surface at first, and clean with trichloromethane, zellon or tetracol phenixin, avoid using alkali lye, then it was cleaned in warm water 5-10 minute, take advantage of and wet brush continuously six times with tannic acid solution (200g Weibull, 1 liter of deionized water solution and the mixing of 150ml ethanol), dry one to two day, tawny corrosion meeting changed into black-and-blue, according to circumstances sealed with wax with lacquer or microlite at last and protected.
(b) for the serious ironware of corrosion.Cleaning surfaces, clean the back (same a), taking advantage of wets brushes four times continuously with tannic acid solution (200g Weibull, 1 liter of deionized water solution, 150ml ethanol and 100ml concentration are that 80-85% phosphoric acid mixes), after the thorough drying, remove loose iron rust, repeat the brushing operation with wire brush.Dip in scrub-brush afterwards and get the tannic acid solution that do not add phosphoric acid and (a) repeat at least to brush four times together.
With respect to the use of Weibull on iron cultural relic by using, Sodium hexametaphosphate 99 is used for the inhibition of desalting soln more, and corrosion mitigating effects such as chromic salt are good but inhibiter that toxicity is very big because sexavalent chrome has high toxicity and carinogenicity, see also " US.Public Health Service.Toxicological Profilefor Chromium[R] .Report No.ATSDR/TP288/10.1989. ", there is the problem of environmental pollution due to the discharge of wastewater in the production, so be subjected to the restriction of various countries' environmental regulation increasingly stringent, do not met environmental friendliness principle few use the existing to the utmost.There is saturate shortcoming in iron cultural relic by using after using Weibull, and its corrosion mitigating effect also lacks evaluation study, therefore, is necessary the corrosion mitigating effect of Weibull is estimated, and improves at its deficiency that changes the ironware outward appearance.
Summary of the invention
The present invention is based on Eleventh Five-Year Plan national science and technology supporting plan project 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 tannin corrosion inhibitor that is used for protecting ferruginous historical relics, to improve the defective that exists in the known technology.
For achieving the above object, the tannin corrosion inhibitor that is used for protecting ferruginous historical relics provided by the invention, it consists of: the Zn (H of the Weibull of 4-6mM, 0.04-0.06mM
2PO
4)
2, 9-11mM Na
2SiO
3With the thanomin of 2-4M, the pH of this inhibiter is 11-12.
Of the present inventionly preferably consist of Weibull 5mM, water glass 10mM, primary zinc phosphate 0.05mM, thanomin 3M.
The preferred inhibiter pH of the present invention is 12.0.
Tannin corrosion inhibitor provided by the invention has remedied the single complexing action of Weibull, has reduced the infection of acid Weibull to the ironware matrix, and corrosion mitigating effect obviously is better than Weibull, and meets historical relic's protection principles such as not changing historical relic original state, minimum of interference.
Description of drawings
Fig. 1 is the X-ray energy spectrum comparison diagram of Z30 grey cast iron corrosion mitigating effect; Wherein: a is blank sample, and b is not for adding inhibiter, and c is for adding tannin corrosion inhibitor, and d is for adding inhibiter of the present invention.
Fig. 2 is the X-ray energy spectrum comparison diagram of low silicon high-sulfur white cast iron corrosion mitigating effect; Wherein: a is blank sample, and b is not for adding inhibiter, and c is for adding tannin corrosion inhibitor, and d is for adding inhibiter of the present invention.
Fig. 3 is the X-ray energy spectrum comparison diagram of low silicon low-sulfur white cast iron corrosion mitigating effect; Wherein: a is for adding tannin corrosion inhibitor, and b is for adding inhibiter of the present invention.
Fig. 4 is the electrokinetic potential polarization curve test pattern in the corrosion system of the 3.5%NaCl aqueous solution; Wherein: a is the Z30 grey cast iron, and b is low silicon high-sulfur white cast iron, and c adds tannin corrosion inhibitor for low silicon low-sulfur white cast iron, and d is for adding inhibiter of the present invention.
Fig. 5 is in the corrosion system of the 3.5%NaCl aqueous solution, alternating-current impedance baud (EIS) figure of cast iron sample before and after the pre-film of inhibiter of the present invention; Wherein: a is low silicon low-sulfur white pig iron, and b is low silicon high-sulfur white pig iron.
Fig. 6 is in the corrosion system of the 3.5%NaCl aqueous solution, alternating-current impedance Nyquist (Nyquist) the complex plane figure of cast iron sample before and after the pre-film of inhibiter of the present invention; Wherein: before a is the pre-film of low-sulfur white pig iron, after b is the pre-film of low-sulfur white pig iron, before c is the pre-film of high-sulfur white pig iron, after d is the pre-film of high-sulfur white pig iron.
Fig. 7 is the secondary electron image of slow-releasing agent system rete of the present invention cross section scanning electronic microscope.
Fig. 8 adopts the sample after inhibiter of the present invention is handled to contrast photo in the front and back of outside atmosphere light exposure test after 25 days; Wherein: a threw the photo of sample in first day, and b is the photo after 25 days.
Fig. 9 is the photo that passes through the irony hexagonal axle sleeve after Weibull and inhibiter of the present invention are handled respectively; Wherein, a handles through Weibull, and b handles through inhibiter of the present invention.
Embodiment
The embodiment of inhibiter of the present invention can adopt spraying and soak two kinds of implementing process of pre-film.For collection ironware protection suggestion spraying coating process, for the bigger outdoor ironware suggestion employing sealing paste method of applying of preservation circumstance of temperature difference ironware is carried out the pre-film of inhibition and handle.
Inhibition mechanism about inhibiter of the present invention
Fe is a VIII group 4 transition metal element, and its valence electron is arranged and is 3d
64s
2, easily accept electronics, many groups that have lone-pair electron are produced absorption.Fe loses 2 4S
2Electronics shows divalent (Fe
2+); Fe loses 2 4S
2Electronics and 1 3d
1Electronics forms half-full structure, shows 3 valency (Fe
3+).Because all there is unoccupied orbital in these two kinds of valence state atoms, therefore all easily accept electronics, produce absorption with band lone-pair electron group.Thanomin in the tannin corrosion inhibitor of the present invention has the nitrogen oxygen groups of band lone-pair electron, theoretically metallic iron and band rust ironware protection is all had better effects.
Thanomin in the tannin corrosion inhibitor system of the present invention is colourless thick liquid, strong basicity, and low toxicity, its main functional group is amino (NH
2) and hydroxyl (OH), the lone-pair electron of Sauerstoffatom can be simultaneously and iron surface generation chemisorption on nitrogen-atoms and the hydroxyl on the amino, forms more stable five-ring inner complex.In addition, thanomin also can pass through the nitrogen oxygen at molecule two ends as bridge, with ferric ion (Fe
3+) or ferrous ion (Fe
2+) form the long-chain inner complex, strengthen corrosion resistance to the metallic surface.Phosphoric acid salt in the system, silicate are anodic corrosion inhibitor, and they can cover the metal anode surface, make metal passivation, thereby increase anodic polarization, and corrosion potential is shuffled.Zinc salt in the system is the cathode type inhibiter, belongs to precipitation membranous type inhibiter again, it can with the hydroxide ion reaction that generates in the cathodic process, generate the zinc hydroxide precipitation membrane, the overpotential of hydrogen is increased, suppress cathodic reaction, thereby suppress corrosion of metal.In a word, tannin corrosion inhibitor of the present invention is alkalescence (pH is about 12.0) under alkaline matter effects such as thanomin, reduced the infection that the acidity of Weibull causes the iron-based body, the tannate that forms has the complexing corrosion inhibition similar to Weibull, all the other components are brought into play the effect that suppresses ironware anode and cathodic reaction simultaneously in the system, remedied the single complexing action of Weibull system, corrosion inhibition is significantly improved.
Experiment condition and method
(1) scanning electronic microscope and X-ray energy spectrum analyser (SEM-EDS)
Hitachi S-3600N scanning electronic microscope, analytical voltage 20KV; The Genesis 2000XMS of U.S. EDAX company type X-ray energy spectrometer.
(2) weightless test
Weight-loss method can directly draw the quality that metal reduces because of corrosion under the corrosive medium effect, can calculate at the trial by it between in average corrosion rate, calculate the inhibition efficiency of inhibiter then, thus the corrosion inhibition of evaluation inhibiter.Because this method reliable results, favorable reproducibility has become the main method of evaluating the inhibiter corrosion inhibition.But it is applicable to the measurement of general corrosion.
Erosion rate calculating method is carried out by " the machinery industry standard JB/T60-7492 of the People's Republic of China (PRC), preparation, cleaning and the evaluation of corrosion sample ".
Iron plate sample mass loss value calculation formula is as follows:
ΔW＝W
1-W
2 (2-1)
Wherein, Δ W-mass loss amount (g); W
1Quality (g) before-sample corrosion test; W
2-sample is through corrosion test, and the quality (g) behind the removal corrosion product;
Iron plate sample mean erosion rate formula is as follows:
R＝K·ΔW/STD (2-2)
In the formula: the revised erosion rate of R-(millimeter/year, mm/a); K-8.76 * 10
4Δ W-mass loss amount (g); The S-specimen surface amasss (cm
2), be accurate to 0.01cm
2The T-corrosion test time (h), be accurate to 0.01h; D-sample density (g/cm
3).
The corrosion inhibition rate method of calculation
η＝(R
0-R)×100％/R
0 (2-3)
In the formula: η-corrosion inhibition rate (%); R
0The erosion rate of-blank sample (mm/a); R-adds the erosion rate (mm/a) behind the inhibiter.
(3) method of polarization curve
Method of polarization curve is to be used for measuring corrosion speed, the electrochemical method of research electrode process mechanism and various influence factors.Can judge the feature and the controlled step of electrode reaction according to polarization curve, measure the kinetic parameter of electrode reaction, as exchange current density, transmission coefficient and anode and cathode Tafel constant etc.
(4) AC impedence method
AC impedence method is a kind of Electrochemical Measurement Technology commonly used, the electrochemical response when being based on measurement system being applied perturbation by a small margin, and the influence of counter electrode process is less.This technology is the important tool of research kinetics of electrode process and electrode surface phenomenon.The outstanding feature of alternating-current impedance method is the information that interfacial state and process are provided from multiple angles, is convenient to analyze the ironware mechanism of corrosion.The raw data of each survey frequency point has all comprised and has applied signal voltage (or electric current) to the phase displacement of the signalling current (or voltage) that records and the amplitude of impedance.
Experimental result and discussion
Through shaker test, the four component compound systems that consist of Weibull (5mM), water glass (10mM), primary zinc phosphate (0.05mM) and thanomin (3M) composition that the present invention is preferable compare research with the 2mM tannic acid solution.Wherein 2mM tannic acid solution pH is 3.1, and Weibull compound corrosion inhibitor system pH is 12.0.
Weightless test
As shown in table 1, weightless test is the result show: in 3.5%NaCl aqueous corrosion system, (1) for five kinds of experiment materials, the inhibition efficiency of Weibull compound corrosion inhibitor and all obviously be better than Weibull at test piece upper surface film-formation result; (2) the Weibull compound corrosion inhibitor is splendid to low-sulfur cast iron corrosion mitigating effect, lower slightly to high-sulfur cast iron corrosion mitigating effect, promptly high to the corrosion inhibition rate of Z30 grey cast iron (low-sulfur), low silicon low-sulfur white pig iron, low silicon low-sulfur graphitic pig iron, reach 99.01%, 99.63% and 94.93% respectively, but the corrosion inhibition rate for low silicon high-sulfur white pig iron and low silicon high-sulfur graphitic pig iron is lower slightly, be respectively 60.88% and 76.80%, this and S cause that easily the ironware corrosion has certain relation.
Table 1, Weibull and Weibull compound system are to the inhibition efficiency (room temperature, 7 days) of five kinds of ironware samples
SEM-EDS analyzes
Totally three kinds of samples of Z30 grey cast iron (Fig. 1), low silicon high-sulfur white pig iron (Fig. 2) and low silicon low-sulfur white pig iron (Fig. 3) before and after respectively inhibition being handled carries out the SEM-EDS analysis.Corrosive medium in the wherein inhibition treating processes is 3.5%NaCl, and etching time is 168h, has tested respectively and has not added inhibiter (blank sample) and add Weibull, three kinds of systems of Weibull compound corrosion inhibitor respectively.
Sample constituent content (wt%) after table 2, Weibull and the inhibition of Weibull compound corrosion inhibitor
(Z30 grey cast iron)
As seen from Figure 1, do not add in the corrosion system of inhibiter, tangible crevice corrosion and pitting attack (shown in Fig. 1 b) appear in Z30 cast iron specimen surface; Add in the corrosion system of Weibull, similar to visual inspection, Z30 specimen surface under the scanning electron microscopic observation presents mottled film forming pattern (shown in Fig. 1 c), with power spectrum different zones is carried out ultimate analysis, find mainly to be divided into not film forming district (oxygen level 2.66%) and film forming district (oxygen level 38.98%), rete easily peels off; Add in the corrosion system of inhibiter of the present invention, (Fig. 1 a) does not have obviously difference to Z30 specimen surface (seeing also Fig. 1 d), and corrosion mitigating effect is very obvious, and the power spectrum ultimate analysis shows that the phosphorus content of rete is obviously higher with blank sample.
The Z30 grey cast iron is closely similar among low silicon high-sulfur white pig iron among Fig. 2 and the SEM-EDS analytical results of the low silicon low-sulfur white pig iron among Fig. 3 and Fig. 1, sample after the Weibull inhibition presents mottled rete, film forming insecure (shown in Fig. 2 c and Fig. 3 a), inhibiter of the present invention has very excellent corrosion mitigating effect, the sample film forming after the inhibition even, stable (shown in Fig. 2 d and Fig. 3 b).
Electrochemical process
The test of electrokinetic potential polarization curve
Adopting Z30 grey cast iron, low silicon high-sulfur white pig iron and low silicon low-sulfur white pig iron respectively is working electrode, saturated calomel electrode is a reference electrode, platinum electrode is a supporting electrode, in the 3.5%NaCl solution of 3.5%NaCl solution (blank) and adding Weibull or Weibull compound corrosion inhibitor, carry out electrokinetic potential scanning respectively, obtain the electrokinetic potential polarization curve.With current potential V is the y axle, and the logarithm lg I of current density is the mapping of x axle.The corrosion mitigating effect of the more various inhibiter of graph curve by different inhibiter.Sweep velocity 2mV/s, sweep limit is-1.2～0.6V.
Shown in Fig. 4 a, for the Z30 grey cast iron, the corrosion potential of Weibull is more higher than blank sample, and passivation phenomenon do not occur, shows that its inhibition mechanism is the deposition membranous type.Under identical corrosion potential, corrosion current and blank sample are more or less the same, and show that its corrosion inhibition to Z30 grey cast iron sample is more limited.The blank sample of the blunt current ratio of dimension of the Weibull improvement prescription of interpolation water glass, primary zinc phosphate and thanomin and Weibull all have lower by a relatively large margin, and passivation phenomenon occurs, and corrosion potential is negative to be moved, and of short duration accelerated corrosion of initial stage forms passive film rapidly.After increasing polarizing voltage, erosion rate slowly increases until broken passivation.These three kinds of systems also show similar phenomenon (seeing also Fig. 4 b and Fig. 4 c) for high and low sulphur white cast iron.In a word, the electrokinetic potential polarographic analysis is the result show, the Weibull compound corrosion inhibitor all is significantly improved than blank and Weibull aspect corrosion mitigating effect.
AC impedence method
Electrochemical impedance spectroscopy is a strong instrument of estimating the rete corrosion resistance nature, the pairing corrosion electrochemistry information of matrix in the time of can obtaining to corrode according to the shape of impedance spectrum below film surface and the rete.
Electrochemical impedance spectroscopy: GAMRY PCI 4-750 electrochemical workstation, the perturbation signal adopts the sine wave of amplitude 20mv.3 * 10
5～1 * 10
-2In the range of frequency of Hz from high frequency to low frequency sweep, measure and at room temperature with under the open circuit potential carry out.Adopt three electrode test systems, mercurous chloride electrode is a reference electrode, and platinum electrode is a supporting electrode, and low silicon high-sulfur white pig iron is working electrode, and the sample measurement area is 12.56cm
2, ionogen is a 3.5%NaCl solution, adds the Weibull compound corrosion inhibitor.
As illustrated in Figures 5 and 6; among the Bode figure and Nyquist of low silicon low-sulfur white pig iron and low silicon high-sulfur white pig iron electrochemical impedance spectroscopy before and after pre-film; the mould value of Z is before low frequency end and front end all are higher than pre-film far away behind the pre-film; the protective membrane that explanation forms in the iron-based surface has very strong provide protection to matrix, can play corrosion-resisting function.
The mensuration of the composite inhibition system of Weibull film forming thickness
Z30 grey cast iron sample is soaked pre-one week of film in inhibiter, cut off the fritter of 0.8x0.5cm,, inlay with Resins, epoxy is cold with single face metal spraying 90 seconds in the anhydrous state incision.Use 240 orders, 400 orders, 1000 order sand paperings successively, after 6 μ m, 3 μ m, the polishing of 0.05 μ m diamond abrasive, with its cross section of scanning electron microscope analysis.Can show that as Fig. 7 ferrous metal base layer and gilding layer are high-visible under Electronic Speculum, part is the inhibition film forming layer between matrix and the gilding layer, and through measuring, the composite inhibition system of Weibull film forming thickness is about 1.5 μ m.
Inhibiter protects agent with envelope and combines evaluation test
The step that protecting ferruginous historical relics normally protects according to rust cleaning, desalination, inhibition, envelope is implemented, and considers that protecting ferruginous historical relics handles the actually operating situation, to inhibiter with seal the corrosion inhibition that investigation after protecting agent and combining more can reflect all kinds of inhibiter.In view of this consideration, (250 * 100 * 3mm) go up evenly spraying one time, after 2 hours, spray one time dry 24 hours at interval again at Z30 cast iron sample with Weibull (1#) and Weibull compound corrosion inhibitor (2#) respectively with spray gun.The unified then fluorocarbon material envelope that evenly sprays is thereon protected agent (fluorine carbon varnish: solidifying agent=3: 1 v/v), after 2 hours, is sprayed one time dry 24 hours at interval again.Sample is 3 parallel samples.For comparing, directly do not spray the fluorocarbon material envelope and protect together sample presentation test after the agent carrying out cast iron test piece that inhibition handles, be designated as 0#.Sample after handling is carried out the test of being exposed to the sun of aging salt-fog test such as anti-neutral salt spray (GB/T 1771-2007), freeze-thawing resistant, wetting phase ultraviolet ageing, sticking power and outside atmosphere respectively.Its result is as shown in table 3.
Table 3, inhibiter protect agent with envelope and combine the evaluation test list of materials
Aging salt-fog test
Sample after handling is carried out anti-neutral salt spray, freeze-thawing resistant, wetting phase ultraviolet ageing and adhesion test respectively, and experimental data sees Table 4.
Seen that by the film thickness data it is the thinnest directly to seal the 0# specimen surface film thickness that protects, and is 3.1 μ m, that the thickest is 2# sample 25.7 μ m, and film thickness is followed successively by 2#＞1#＞0# by thick to approaching order; Salt fog data by unified 23.4 hours see, anti-neutral salt spray ability is by being followed successively by 2#＞1#=0# to weak ordering by force; See that by the freeze-thawing resistant experimental data freeze-thawing resistant ability is by being followed successively by 2#＞1#＞0# to weak ordering by force; See that by wetting phase ultraviolet ageing experimental data the moisture-proof phase ultraviolet ageing ability of each sample is all stronger, and is no abnormal in 226 hours; Seen that by the sticking power experimental data sticking power reaches 0 grade, sticking power is good.Comprehensive every test data as can be seen, the protective film thickness of the sample (1-2#) after Weibull or Weibull compound corrosion inhibitor are handled and corrosion resistance are all greater than the sample of handling without inhibition (0#); The corrosion inhibition of 2# inhibiter all is better than traditional inhibition material Weibull.
The aging salt-fog test result of table 4, Weibull and Weibull compound corrosion inhibitor
The atmospheric exposure test
Sample after handling is tanned by the sun the field in Atmosphere of Beijing carry out the outside atmosphere light exposure test, protect agent with the investigation inhibiter with envelope and combine effect, inquire into the inhibiter evaluation method.The front and back contrast photo of outside atmosphere light exposure test after 25 days seen Fig. 8 a and Fig. 8 b.Can find out obviously that by figure corrosion resistance is followed successively by: the anti-corrosion capability that 2#＞1#＞0#, inhibiter promptly of the present invention and anti-corrosion capability after envelope is protected agent and combine are better than Weibull and envelope after protecting agent and combining, and all be better than sealing anti-corrosion capability after protecting that agent is independent and spraying.
The application test of inhibiter on iron cultural relic by using
Adopt portable sandblast machine, with 40-60 order granulated glass sphere is the sand material, and derusting by sandblast is carried out in the part, two sides of a Han dynasty irony hexagonal axle sleeve, until exposing the fine and close rusty scale of even grey black, evenly brush Weibull and inhibiter of the present invention then, observe after 72 hours (seeing also Fig. 9).Find that yellow corrosion (shown in Fig. 9 a) appears in the ironware part after the Weibull inhibition, the ironware surface after inhibiter of the present invention is handled evenly corrosion phenomena (shown in Fig. 9 b) do not occur.The application test of two kinds of inhibiter on iron cultural relic by using shows that the corrosion mitigating effect of Weibull compound corrosion inhibitor obviously is better than Weibull.
By Z30 grey cast iron and four kinds of simulation iron cultural relic by using samples are carried out weightless test; the micro-composition analysis of scanning electron microscope; electrochemical analysis; aging salt-fog test; atmospheric exposure test and the applied research on iron cultural relic by using; the corrosion inhibition that has compared known Weibull and tannin corrosion inhibitor of the present invention; the result shows; tannin corrosion inhibitor of the present invention has remedied the single complexing action of Weibull; reduced the infection of acid Weibull to the ironware matrix; corrosion mitigating effect obviously is better than Weibull, and meets and do not change the historical relic original state; historical relic's protection principles such as minimum of interference.
Claims (3)
1. tannin corrosion inhibitor that is used for protecting ferruginous historical relics, by:
Zn (the H of the Weibull of 4-6mM, 0.04-0.06mM
2PO
4)
2, 9-11mM Na
2SiO
3Form with the thanomin of 2-4M, the pH of this inhibiter is 11-12.
2. tannin corrosion inhibitor as claimed in claim 1, wherein, Weibull is that 5mM, water glass are that 10mM, primary zinc phosphate are that 0.05mM, thanomin are 3M.
3. tannin corrosion inhibitor as claimed in claim 1, wherein, the pH of inhibiter is 12.0.
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