CN100464011C - Method for oxidizing cultural relics in ironware - Google Patents
Method for oxidizing cultural relics in ironware Download PDFInfo
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- CN100464011C CN100464011C CNB2004101026289A CN200410102628A CN100464011C CN 100464011 C CN100464011 C CN 100464011C CN B2004101026289 A CNB2004101026289 A CN B2004101026289A CN 200410102628 A CN200410102628 A CN 200410102628A CN 100464011 C CN100464011 C CN 100464011C
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Abstract
This invention describes a process for the dechlorination of iron antiquities, comprising the steps of: adding a cleaning agent and an amine inhibitor to an alkaline solution to prepare an alkaline dechlorination cleaning solution, and carrying out the cathode polarization dechlorination of iron antiquities in the said solution at a constant electric potential. This invention overcomes such problems as a certain degree of corrosion existing in the traditional dechlorination processes for iron antiquities or the damage to the intrinsic appearances of iron antiquities led by the abscission of the rusty layer resulting from hydrogen evolution caused by high local current in the electrochemical reduction method, and provides a rapid, effective and more protective process for the dechlorination of iron antiquities.
Description
Technical field
The present invention relates to a kind of guard method to ironware cultural relic, mainly is the dechlorination treatment process of ironware cultural relic.
Background technology
The ironware cultural relic of salvaging from the seabed, the ironware cultural relic that is unearthed from the wetland environment and the collection ironware cultural relic that borders on the sea be the residual a large amount of muriate of outside surface not only; and a large amount of chlorions is also contained in its inside; because the chlorion radius is little; so its penetrativity and electronegativity are all very strong; it can destroy or the substituted metal oxide compound in oxonium ion; form soluble salt; make cultural artifact surface can not form compact protective film; thereby make local corrosion proceed, the corrosion product in the short period of time in cast iron expands rapidly and causes the permanent destruction of historical relic.So remove Cl
-Be to stop ironware cultural relic to continue to take place the corrosive important step.Slough that the common method of chlorion mainly contains distilled water washing out method, NaOH infusion method, Sodium Benzoate method, LiOH method, alkaline sulfite reduction method, electrochemical reducing etc. in the ironware cultural relic.General distilled water cleans or the basic solution infusion method time also can make ironware cultural relic be subjected to further corrosion than the water in long and the solution, also can make the graphite district on ironware surface softening in the treating processes, surface after the processing is easy to suffer erosion and damage and (see N.A.North, I.D.Macleod.Conversation of Metals, Conservation of Marine Archaeological Objects.Butterworths, London, 1987, pp.214～219.); Though alkaline sulfite reduction method dechlorination effect is better, when surpassing 1.5mm, ironware cultural relic corrosion layer thickness handles then fully dechlorination, simultaneously SO with the alkaline sulfite reduction method
3 2-Be easy to oxidized and lose reducing power, SO
3 2-Also can disturb Cl
-Analysis accuracy of analysis is reduced; People such as Zhu Hongfan, Zhou Hao is in " historical relic's protection and archaeology science, 1995:7 (1) " in a kind of desalination purging method of unearthed ironware cultural relic is disclosed, this method is soaked with composite alkaline cleaning fluid, the scavenging solution main component is silicate corrosion inhibitor, clean-out system and washing assistant etc., improve to some extent than traditional immersion dechlorination method, but infusion method dechlorination speed is still very slow; Peel off in a large number and the original appearance of historical relic is destroyed and adopt common electrochemical reducing (departments in charge of cultural and historical relics are commonly referred to electrolytic process) that rusty scale that evolving hydrogen reaction makes historical relic easily takes place.
Summary of the invention
The invention solves in the oxidizing cultural relics in ironware process because of surface corrosion or react and destroy the problem of historical relic original appearance, provide a kind of fast, effectively, dechlorination more thoroughly and more helps the dechlorination method that historical relic is preserved.
The main points of invention: the present invention includes in the basic solution and to add clean-out system and amine inhibitor is prepared into alkaline composite dechlorination scavenging solution, in this solution, under the constant potential condition ironware cultural relic is carried out cathodic polarization dechlorination process:
1, the preparation of alkaline composite dechlorination scavenging solution: at mass percent concentration is that to add mass percent concentration in 2% sodium hydroxide (NaOH) basic solution be 0.1～0.5% anion surfactant, mass percentage concentration is 0.1～0.5% nonionogenic tenside, mass percentage concentration is 0.01～0.1% washing assistant, and concentration of volume percent is 2～5% amine inhibitor, is re-dubbed the dechlorination scavenging solution;
2, constant potential cathodic polarization dechlorination: will treat that the ironware cultural relic that dechlorination is handled is immersed in the electrolyzer that the composite dechlorination scavenging solution of step 1 is housed, with the stainless steel is supporting electrode (anode), treat that the ironware cultural relic that dechlorination is handled is working electrode (negative electrode), size and corrosive situation according to implements are adjusted the constant certain value between-1.1～1.2V of current potential, working electrode and supporting electrode the exposed area ratio be about 1:5, change solution according to the concentration that detects chlorion in the solution, when the content constant of chlorion was lower than 5ppm, the dechlorination processing finished.
Anion surfactant, nonionogenic tenside and washing assistant play cleanup actions such as decontamination, emulsification, dispersion in above-mentioned alkaline composite dechlorination scavenging solution, so adopt tensio-active agent and washing assistant commonly used to get final product, as: dodecyl Sodium Benzoate, polyoxyethylene nonylphenol ether and tripoly phosphate sodium STPP etc.
Above-mentioned amine inhibitor is: quadrol.
The invention effect:
The alkaline composite dechlorination scavenging solution that the present invention adopts, when ironware cultural relic is carried out the constant potential cathodic polarization, wherein anion surfactant, nonionogenic tenside and washing assistant can be removed dirt and the floating rust that implements show well, remove the obstacle on surface for moving out of chlorion in the corrosion product layer; Nitrogen-atoms in the amine inhibitor can with the iron ion generation chelatropic reaction in the corrosion product layer, reduce the implements surface charge density and help moving out of chlorion, and the inner complex that generates covers the implements surface and makes the implements surface solid anti-corrosion, help handling the further preservation of back implements, prolong the life-span of historical relic.Then further accelerated chlorion by the moving out of corrosion product layer with the constant potential cathodic polarization, and potentiostatic method can make more each position of implements obtain uniform current density than galvanostatic method, dechlorination is more thorough.Table 1 is that test piece is through the dechlorination test effect of different dechlorination methods at different time.Wherein test used sample for the identical naked cast iron sample of size lacing film 10 months in the 3.5%NaCl aqueous solution, generated the test piece of thicker rusty scale.Take out the concentration that a small amount of scavenging solution is measured chlorion in the different time.
Table 1
As seen from Table 1 in method of the present invention, than through general basic solution infusion method and its dechlorination speed of electrolytic process is faster, dechlorination effect is better, the test piece surface after the processing is solid anti-corrosion, helps the further preservation of implements.
Embodiment:
Enforcement of the present invention comprises:
The preparation of the composite dechlorination scavenging solution of alkalescence: at mass percent concentration is that to add mass percent concentration in 2% the NaOH basic solution be 0.1～0.5% anion surfactant, mass percentage concentration is 0.1～0.5% nonionogenic tenside, mass percentage concentration is 0.01～0.1% washing assistant, and concentration of volume percent is 2～5% amine inhibitor, accurately join in the basic solution of 2%NaOH behind various clean-out systems of weighing and the inhibiter, mix and promptly make alkaline composite dechlorination scavenging solution.
Wherein anion surfactant is preferably: Sodium dodecylbenzene sulfonate or sodium lauryl sulphate or month water glass or trolamine; Nonionogenic tenside is: polyoxyethylene nonylphenol ether; Washing assistant is: tripoly phosphate sodium STPP or yellow soda ash or tertiary sodium phosphate; Inhibiter is: quadrol.
Constant potential cathodic polarization dechlorination process: the device that holds solution is an electrolyzer, the CONTROLLED POTENTIAL device is a potentiostat, the supporting electrode of electrochemistry dechlorination system is stainless steel (anode), working electrode is an ironware cultural relic (negative electrode) for the treatment of that dechlorination is handled, working electrode and supporting electrode the exposed area ratio be about 1:5.Supporting electrode and working electrode can be placed the electrolyzer two ends, also supporting electrode can be placed the both sides (two stainless-steel sheets) of working electrode; The lead of junction circuit is copper conductor, and the lead that is exposed in the solution will be sealed with silica gel; Will treat the ironware cultural relic handled of dechlorination be immersed in the electrolyzer that alkaline composite dechlorination scavenging solution is housed, make the dechlorination current potential make it constant a certain value between-1.1～1.2V according to the size and the adjustment of corrosive situation of implements.Change solution according to the concentration that detects chlorion in the solution, take out the concentration that a small amount of scavenging solution is measured chlorion in the different time, the concentration of chlorion adopts AgNO
3Potentiometric titration analysis continuously.Constant when being lower than 5ppm within several weeks when the content of chlorion, the dechlorination processing finishes, and cleans clean-out system and the inhibiter and the alkali lye of implements remained on surface afterwards with distilled water, with the implements oven dry, is kept in the exsiccant environment again.
When ironware cultural relic being carried out the constant potential cathodic polarization with the composite dechlorination scavenging solution of alkalescence of the present invention, anion surfactant wherein, nonionogenic tenside and washing assistant have performances such as excellent decontamination, emulsification, dispersion, can remove dirt and floating rust that implements show well, remove the obstacle on surface for moving out of chlorion in the corrosion product layer; Nitrogen-atoms in the amine inhibitor can with the iron ion generation chelatropic reaction in the corrosion product layer, reduce the implements surface charge density and help moving out of chlorion, and the inner complex that generates covers the implements surface and makes the implements surface solid anti-corrosion, help handling the further preservation of back implements, and prolong its life-span; Then further accelerated chlorion by the moving out of corrosion product layer with the constant potential cathodic polarization, and potentiostatic method can make more each position of implements obtain uniform current density than galvanostatic method.
Embodiment 1
Weighing anionic surfactant sodium dodecylbenzene sulfonate and each 1g of nonionogenic tenside OP-10 and washing assistant tripoly phosphate sodium STPP 0.1g, the capacity of putting into is the beaker of 1L, add the NaOH solution and the 20ml quadrol of the mass percent concentration 2% of 980ml again in beaker, stirring mixes solution.Pending simulation cast iron historical relic is put into the beaker that alkaline composite dechlorination scavenging solution is housed, pending test piece links to each other with the negative pole of potentiostat, stainless steel anode links to each other with the positive pole of potentiostat, maintain a certain distance between anode and the negative electrode, after connecting circuit, opening potentiostat, to regulate current potential constant in-1.15V, in a week that begins to handle, measure chlorine ion concentration in the solution every 24h, later on can be every three days, three days or all chlorine ion concentrations of measuring in the solution, change solution as required, constant when being lower than 5ppm within two weeks when the content of chlorion, dechlorination is handled and can be finished.Test piece after the dechlorination processing is taken out from solution, wash test piece to the residue on test piece surface repeatedly with distilled water and remove fully, then test piece is placed in the baking oven or and dries, at last the test piece that disposes is kept in drying, the clean environment with blower.
Embodiment 2
Weighing anionic and each 2g of nonionogenic tenside OP-10 and washing assistant yellow soda ash 0.05g, the capacity of putting into is the beaker of 1L, add the NaOH solution and the 40ml quadrol of the mass percent concentration 2% of 960ml again in beaker, stirring mixes solution.Pending simulation cast iron historical relic is put into the beaker that alkaline composite dechlorination scavenging solution is housed, pending test piece links to each other with the negative pole of potentiostat, stainless steel anode links to each other with the positive pole of potentiostat, maintain a certain distance between anode and the negative electrode, after connecting circuit, opening potentiostat, to regulate current potential constant in-1.10V, in a week that begins to handle, measure chlorine ion concentration in the solution every 24h, later on can be every three days, three days or all chlorine ion concentrations of measuring in the solution, change solution as required, constant when being lower than 5ppm within two weeks when the content of chlorion, dechlorination is handled and can be finished.Test piece after the dechlorination processing is taken out from solution, wash test piece to the residue on test piece surface repeatedly with distilled water and remove fully, then test piece is placed in the baking oven or and dries, at last the test piece that disposes is kept in drying, the clean environment with blower.
Embodiment 3
Weighing anion surfactant moon water glass and each 5g of nonionogenic tenside OP-10 and washing assistant tertiary sodium phosphate 0.5g, the capacity of putting into is the beaker of 1L, the mass percent concentration that adds 950ml again in beaker is solution and the 50ml quadrol of 2%NaOH, stirs solution is mixed.Pending simulation cast iron historical relic is put into the beaker that alkaline composite dechlorination scavenging solution is housed, pending test piece links to each other with the negative pole of potentiostat, stainless steel anode links to each other with the positive pole of potentiostat, maintain a certain distance between anode and the negative electrode, after connecting circuit, opening potentiostat, to regulate current potential constant in-1.20V, in a week that begins to handle, measure chlorine ion concentration in the solution every 24h, later on can be every three days, three days or all chlorine ion concentrations of measuring in the solution, change solution as required, constant when being lower than 5ppm within two weeks when the content of chlorion, dechlorination is handled and can be finished.Test piece after the dechlorination processing is taken out from solution, wash test piece to the residue on test piece surface repeatedly with distilled water and remove fully, then test piece is placed in the baking oven or and dries, at last the test piece that disposes is kept in drying, the clean environment with blower.
Claims (1)
1. method for oxidizing cultural relics in ironware with ironware cultural relic constant potential cathodic polarization in alkaline cleaning fluid, is characterized in that:
(1) be that to add mass percent concentration in 2% the alkaline solution of sodium hydroxide be 0.1～0.5% anion surfactant at mass percent concentration, mass percentage concentration is 0.1～0.5% nonionogenic tenside, mass percentage concentration is 0.01～0.1% washing assistant, and concentration of volume percent is 2～5% amine inhibitor, is re-dubbed the dechlorination scavenging solution; Described anion surfactant is Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, month water glass or trolamine; Described nonionogenic tenside is OP-10; Described washing assistant is tripoly phosphate sodium STPP, yellow soda ash or tertiary sodium phosphate; Described amine inhibitor is a quadrol;
(2) will treat that the ironware cultural relic that dechlorination is handled is immersed in the electrolyzer that the composite dechlorination scavenging solution of step (1) is housed, with the stainless steel is anode, treat that the ironware cultural relic that dechlorination is handled is a negative electrode, size and corrosive situation according to implements are adjusted the constant certain value between-1.1～1.2V of current potential, negative electrode is 1:5 with anodic exposed area ratio, change solution according to the concentration that detects chlorion in the solution, when the content constant of chlorion was lower than 5ppm, the dechlorination processing finished.
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| CNB2004101026289A CN100464011C (en) | 2004-12-29 | 2004-12-29 | Method for oxidizing cultural relics in ironware |
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| CNB2004101026289A CN100464011C (en) | 2004-12-29 | 2004-12-29 | Method for oxidizing cultural relics in ironware |
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| CN100464011C true CN100464011C (en) | 2009-02-25 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108642556A (en) * | 2018-05-28 | 2018-10-12 | 成都兴天诚节能建材有限公司 | A kind of recovery and treatment method of scrap steel |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673639A (en) * | 2017-10-31 | 2018-02-09 | 攀钢集团攀枝花钢铁研究院有限公司 | A kind of dechlorination method for titanium extraction tailings |
| CN108456892A (en) * | 2018-05-29 | 2018-08-28 | 陕西师范大学 | A kind of method of band the rust desalination of iron cultural relic one-step method and inhibition |
| CN114737200B (en) * | 2022-04-20 | 2024-05-28 | 国家纳米科学中心 | Dechlorination and corrosion inhibition method for iron articles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276133A (en) * | 1978-09-21 | 1981-06-30 | Sumitomo Industries, Ltd. | Method for continuous electrolytic descaling of steel wire by non-contact current flow |
| EP0319313A2 (en) * | 1987-12-03 | 1989-06-07 | Kawasaki Steel Corporation | Process for descaling cold rolled and annealed steel |
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2004
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4276133A (en) * | 1978-09-21 | 1981-06-30 | Sumitomo Industries, Ltd. | Method for continuous electrolytic descaling of steel wire by non-contact current flow |
| EP0319313A2 (en) * | 1987-12-03 | 1989-06-07 | Kawasaki Steel Corporation | Process for descaling cold rolled and annealed steel |
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|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108642556A (en) * | 2018-05-28 | 2018-10-12 | 成都兴天诚节能建材有限公司 | A kind of recovery and treatment method of scrap steel |
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