CN112176380A - Electrochemical protection method for metal cultural relics - Google Patents

Electrochemical protection method for metal cultural relics Download PDF

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Publication number
CN112176380A
CN112176380A CN202011058766.7A CN202011058766A CN112176380A CN 112176380 A CN112176380 A CN 112176380A CN 202011058766 A CN202011058766 A CN 202011058766A CN 112176380 A CN112176380 A CN 112176380A
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China
Prior art keywords
metal
metal cultural
cultural relic
relic
relics
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CN202011058766.7A
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Chinese (zh)
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王万斌
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
    • B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
    • B22F2007/068—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts repairing articles

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

The invention discloses an electrochemical protection method for a metal cultural relic, and relates to the technical field of cultural relic protection. The electrochemical protection method for the metal cultural relics comprises the four steps of primary filling and repairing of the cultural relics, coating of aluminum powder paint, connection of an electrochemical device and electrification and reduction. The electrochemical protection method for the metal cultural relics coats the aluminum powder paint containing the aluminum powder before the metal cultural relics are subjected to electrification reduction, so that the corrosion of hydrochloric acid in a solution to metal oxides on the surfaces of the metal cultural relics in the electrification reduction process can be reduced, ferric ions can be reduced into ferrous ions, the chemical reaction conditions are reduced, and the reaction is quicker and more effective.

Description

Electrochemical protection method for metal cultural relics
Technical Field
The invention relates to the technical field of cultural relic protection, in particular to an electrochemical protection method for a metal cultural relic.
Background
The cultural relic protection refers to a series of measures for preventing historical relics with historical value, cultural value and scientific value from being damaged, and the process is called cultural relic protection.
The traditional cultural relic protection method is mainly characterized in that the surface of the cultural relic is coated with antioxidant materials such as resin and the like to seal the cultural relic, so that the further corrosion of the cultural relic is reduced. When the metal cultural relic defect is treated, the metal cultural relic defect is repaired by adopting a resin bonding mode, the repairing effect is poor, and the retention time after the repairing is short. Background sources are as follows: the protection of cultural relics in China, the official website of the central government of the people's republic of China [ quoted date 2014-09-20 ].
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an electrochemical protection method for a metal cultural relic, which solves the problems of weak protection of the traditional method for metal temperature, short retention time and poor repair effect of the traditional repair method.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: a method for electrochemically protecting a metal cultural relic comprises the following steps:
s1, adding metal powder with the same material and density as the metal cultural relic into the defect part of the metal cultural relic to be repaired, and then dripping a small amount of dilute hydrochloric acid for die casting, and brushing dilute sulfuric acid on the defect part before repairing if the metal cultural relic is an ironware;
s2, coating a layer of aluminum paint on the metal cultural relic and then airing the metal cultural relic;
s3, communicating the dried metal cultural relics in the S2 with a negative electrode of an electrochemical device, and immersing the metal cultural relics and an iron block in a solution containing electrolyte after a positive electrode of the electrochemical device is communicated with the iron block;
and S4, determining the time for ending the electrification according to the restored degree of the surface of the cultural relic after the electrification.
Preferably, the metal cultural relics are ironware.
Preferably, the metal cultural relics are cuprammrons.
Preferably, the voltage of the electrochemical device is 12V.
Preferably, the electrolyte is a weak acid.
Preferably, the electrolyte is hydrochloric acid.
Preferably, the weak acid is glutamic acid.
Preferably, the aluminum powder paint consists of aluminum powder and resin paint.
Preferably, the electrolyte amount of the electrolyte-containing solution is adjusted according to the corrosion condition of the metal cultural relics.
Preferably, the current of the electrochemical device is less than 10A.
(III) advantageous effects
The invention provides an electrochemical protection method for a metal cultural relic. The method has the following beneficial effects:
the electrochemical protection method for the metal cultural relics coats the aluminum powder paint containing the aluminum powder before the metal cultural relics are subjected to power-on reduction, so that the corrosion of hydrochloric acid in a solution to metal oxides on the surfaces of the metal cultural relics in the power-on reduction process can be reduced, ferric ions can be reduced into ferrous ions, the chemical reaction conditions are reduced, and the reaction is quicker and more effective.
Drawings
FIG. 1 is a schematic diagram of the principle of retarding the reaction rate of iron oxide and acid in aluminum paint;
FIG. 2 is a schematic diagram of a chemical reaction in which ferric ions are reduced to ferrous ions by aluminum;
FIG. 3 is a schematic diagram of a chemical reaction of divalent iron ions reduced by aluminum to elemental iron;
FIG. 4 is a schematic diagram of the reaction speed of copper oxide and acid retarded by aluminum paint;
FIG. 5 is a schematic diagram of the chemical reaction of copper ions reduced by aluminum to elemental copper;
FIG. 6 is a schematic view of the structure of an electrochemical device according to the present invention.
Detailed Description
The described embodiments are only some embodiments of the invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: ironware cultural relic repair
The method comprises the following steps: brushing dilute sulfuric acid on the defect part of the metal cultural relic before repairing, adding metal powder with the same material and density as the metal cultural relic into the defect part of the metal cultural relic to be repaired, and then dripping a small amount of dilute hydrochloric acid for die casting;
step two: coating a layer of aluminum powder paint on the metal cultural relic and then airing;
step three: communicating the dried metal cultural relics in the step two with a negative electrode of an electrochemical device, and immersing the metal cultural relics and the iron blocks in a solution containing glutamic acid or other weak acids after a positive electrode of the electrochemical device is communicated with the iron blocks;
step four: and determining the time for ending the energization according to the degree of restoration of the surface of the cultural relic after the energization.
The following reactions occur:
reaction 1: reacting ferric oxide, ferroferric oxide and acid
FeO+2H+＝Fe2++H2O
Fe2O3+6H+＝2Fe3++3H2O
Fe3O4+8H+＝2Fe3++Fe2++4H2O
Reaction 2: reduction of ferric ions to ferrous ions by aluminium
3Fe3++Al＝3Fe2++Al3+
Reaction 3: reduction of ferrous ions to elemental iron by aluminum
3Fe2++2Al＝2Al3++3Fe↓
Reaction 4: the divalent iron ions obtain electrons at the cathode and are reduced into iron simple substance
Fe2++2e-＝Fe↓
Reaction 5: the anode iron block loses electrons and is oxidized into ferrous ions
Fe-2e-＝Fe2+
The iron simple substance generated in the reaction 3 and the reaction 4 can be attached to the surface where the original iron oxide is located again, so that the iron ware cultural relics can be repaired. In the reaction process, hydrochloric acid can cause certain corrosion to the iron simple substance of the cultural relic, but aluminum in the aluminum powder paint coated on the surface of the cultural relic in the step two can effectively delay the corrosion of hydrochloric acid to the iron simple substance of the cultural relic (as shown in figure 1), resin paint contained in the aluminum powder paint can play a role of a molecular sieve, a small amount of hydrochloric acid and water molecules are contained in the corroded metal cultural relic, meanwhile, the aluminum simple substance in the aluminum powder paint can reduce ferric ions into ferrous ions (as shown in figure 2), the oxidability of the ferrous ions is lower than that of the ferric ions, and the ferric ions are more easily reduced into the iron simple substance at the cathode in the electrochemical reaction in the step three.
Table 1: comparison of electric energy required by reducing ferric ions and ferrous ions with the same molar weight into iron simple substance at cathode
Ferric ion Ferrous iron ion Saving of electric energy
0.439kw·h/mol 0.224kw·h/mol 0.215kw·h/mol
1/3 moles of aluminum are required per mole of ferric ions reduced to ferrous ions, i.e. 9g/mol, 9g of aluminum takes 0.174 yuan. Compared with the method that ferric ions are directly reduced into ferrous ions by electrifying, 0.041 yuan/mol is saved. (the unit price of aluminum is calculated by 19.38 yuan/kg, and the electricity charge is 1 yuan/kw.h).
Example two: copper ware cultural relic restoration
The method comprises the following steps: brushing dilute sulfuric acid on the defect part of the metal cultural relic before repairing, adding metal powder with the same material and density as the metal cultural relic into the defect part of the metal cultural relic to be repaired, and then dripping a small amount of dilute hydrochloric acid for die casting;
step two: coating a layer of aluminum powder paint on the metal cultural relic and then airing;
step three: connecting the dried metal cultural relics in the step two with a negative electrode of an electrochemical device, and immersing the metal cultural relics and the iron blocks in a solution containing hydrochloric acid after a positive electrode of the electrochemical device is connected with the iron blocks;
step four: and determining the time for ending the energization according to the degree of restoration of the surface of the cultural relic after the energization.
The following reactions occur:
reaction 6: reaction of copper oxide, patina and hydrochloric acid
CuO+2HCl＝CuCl2+H2O
Cu2(OH)2CO3+4HCl＝2CuCl2+3H2O+CO2↑
Reaction 7: reduction of divalent copper ions to elemental copper by aluminum
3Cu2++2Al＝2Al3++3Cu↓
Reaction 8: divalent copper ions obtain electrons at the cathode and are reduced into copper simple substance
Cu2++2e-＝Cu↓
The copper simple substance generated in the reaction 7 and the reaction 8 can be attached to the surface where the original copper oxide and the original patina are positioned again, so that the copper cultural relics can be repaired. In the reaction process, hydrochloric acid can cause certain corrosion to copper oxide of the cultural relics, but aluminum in the aluminum powder paint coated on the surface of the cultural relics in the step two can effectively delay the corrosion of the hydrochloric acid to the copper oxide in the cultural relics (as shown in figure 4), resin paint contained in the aluminum powder paint can play a role of a molecular sieve, a small amount of hydrochloric acid and water molecules are contained in the corroded metal cultural relics, meanwhile, aluminum simple substances in the aluminum powder paint can reduce copper ions into simple substance copper (as shown in figure 5), and the electric energy required by the electrochemical reaction in the step three is reduced.
In conclusion, the electrochemical protection method for the metal cultural relics coats the aluminum powder paint containing the aluminum powder before the metal cultural relics are subjected to electrification reduction, so that the corrosion of hydrochloric acid in a solution to metal oxides on the surfaces of the metal cultural relics in the electrification reduction process can be reduced, ferric ions can be reduced into ferrous ions, the chemical reaction conditions are reduced, and the reaction is faster and more effective.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1. The electrochemical protection method for the metal cultural relics is characterized by comprising the following steps:
s1, adding metal powder with the same material and density as the metal cultural relic into the defect part of the metal cultural relic to be repaired, and then dripping a small amount of dilute hydrochloric acid for die casting, and brushing dilute sulfuric acid on the defect part before repairing if the metal cultural relic is an ironware;
s2, coating a layer of aluminum paint on the metal cultural relic and then airing the metal cultural relic;
s3, communicating the dried metal cultural relics in the S2 with a negative electrode of an electrochemical device, and immersing the metal cultural relics and an iron block in a solution containing electrolyte after a positive electrode of the electrochemical device is communicated with the iron block;
and S4, determining the time for ending the electrification according to the restored degree of the surface of the cultural relic after the electrification.
2. The method for electrochemically protecting a metal cultural relic, according to claim 1, characterized in that: the metal cultural relics are ironware.
3. The method for electrochemically protecting a metal cultural relic, according to claim 1, characterized in that: the metal cultural relics are copper ware.
4. The method for electrochemically protecting a metal cultural relic, according to any one of claims 1 to 3, wherein: the voltage of the electrochemical device was 12V.
5. The method for electrochemically protecting a metal cultural relic, according to claim 2, characterized in that: the electrolyte is a weak acid.
6. The method for electrochemically protecting a metal cultural relic, according to claim 3, characterized in that: the electrolyte is hydrochloric acid.
7. The method for electrochemically protecting a metal cultural relic, according to claim 5, characterized in that: the weak acid is glutamic acid.
8. The method for electrochemically protecting a metal cultural relic, according to claim 1, characterized in that: the aluminum powder paint consists of aluminum powder and resin paint.
9. The method for electrochemically protecting a metal cultural relic, according to claim 1, characterized in that: the electrolyte amount of the electrolyte-containing solution is adjusted according to the corrosion condition of the metal cultural relics.
10. The method for electrochemically protecting a metal cultural relic, according to claim 4, characterized in that: the electrochemical device has a current of less than 10A.
CN202011058766.7A 2020-09-30 2020-09-30 Electrochemical protection method for metal cultural relics Withdrawn CN112176380A (en)

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Application Number Priority Date Filing Date Title
CN202011058766.7A CN112176380A (en) 2020-09-30 2020-09-30 Electrochemical protection method for metal cultural relics

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113403081A (en) * 2021-06-17 2021-09-17 王万斌 Protection method for unearthed cultural relics

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113403081A (en) * 2021-06-17 2021-09-17 王万斌 Protection method for unearthed cultural relics

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Application publication date: 20210105