CN112877701B - Gilding copper image surface repairing method and repairing agent - Google Patents
Gilding copper image surface repairing method and repairing agent Download PDFInfo
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- CN112877701B CN112877701B CN202110036561.7A CN202110036561A CN112877701B CN 112877701 B CN112877701 B CN 112877701B CN 202110036561 A CN202110036561 A CN 202110036561A CN 112877701 B CN112877701 B CN 112877701B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/10—Other heavy metals
- C23G1/103—Other heavy metals copper or alloys of copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/40—Metallic substrate based on other transition elements
- B05D2202/45—Metallic substrate based on other transition elements based on Cu
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2502/00—Acrylic polymers
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- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
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Abstract
The invention discloses a repairing method and a repairing agent for a gilding copper image surface. The repairing agent of the invention adopts the natural plant aloe extract as the gel material, has no toxicity to human body and no pollution to environment, and the problem of poor permeability of aloe gel is solved by adding the polyvinylpyrrolidone. Aiming at different corrosion situations of gilding copper modeling, the rust remover with different components is arranged, the combination of sodium glutamate and acetic acid can effectively remove green rust and blue rust corrosion, the combination of thiourea and citric acid can effectively remove red rust, and the combination of the 4 components can effectively remove mixed rust.
Description
Technical Field
The invention belongs to the technical field of copper image repairing protection, and particularly relates to a gilding copper image surface repairing method and a repairing agent.
Background
The copper statue is originally originated in ancient India, mostly casted in images such as Sakyamuni, Guanyin and the like, is originally handed to China in the period of West Han, tends to be formed in the periods of two Jinyin in the south and north, tends to be mature in Tang and Song, is widely casted in the period of clearness, and the surface modification methods of the copper statue comprise inlaying, gilding, bronzing, tinning and the like; gold light of the gilded bronze ware flashes, and the golden bronze ware has more ornamental value.
However, gilded copper statues are buried in the underground for a long time and are influenced by the buried environment, and when the gilded copper statues come out of the earth, the surface often appears greenish blue embroidery or red embroidery, and along with a clay layer which is difficult to remove, the archaeological study and the appearance of cultural relics are seriously influenced. Therefore, the surface cleaning and repairing of gilded copper images is an important work.
The method for cleaning the rusty surface of the golden copper statue comprises the following steps: 1. the rust is removed by adopting a physical cleaning method, such as knife carving, micro electric knife grinding and the like which are simplest by a physical friction method, and the method has the advantages of wide application range and easy mastering; the defects of time and labor waste, incapability of realizing high cleanness and easy scratching of the surface of the object. 2. The chemical cleaning method adopts acid, alkali, chelating agent, complexing agent, surfactant and the like to react with the corrosion components, has the advantages of capability of cleaning cultural relics in a large area and high cleaning efficiency, but for gilding copper imaging, the lower part of a gilding layer is often accompanied with corrosion, and chemical cleaning liquid is easy to permeate to cause the falling of the gilding layer. 3. The ultrasonic cleaning method has high cleaning efficiency and good cleaning effect, can clean micro areas which cannot be reached by physical cleaning and chemical cleaning, but is only suitable for cleaning gilding copper images with slight corrosion and good bottom plate, and often causes surface gilding shedding or shattering for cleaning gilding copper images with severe corrosion.
The limited-positioning cleaning of gilding copper images by using a gel composite chemical cleaning agent is a unique method for solving the problems, and related technical reports exist, however, the method of using a single gel and a single cleaning agent in a composite mode at present has the problems that the viscosity of the gel is not enough, the gel is easy to diffuse, the cleaning agent is released too slowly, the cleaning effect is not good, and the gel is easy to adhere to the surface of a container and is not easy to be clear.
Disclosure of Invention
The invention aims to provide a repair method for a gilding copper imaging surface and a repair agent for different corrosion conditions.
A gilding copper image surface repairing method comprises the following steps:
(1) judging the type of corrosion on the surface of the gold-plated copper image, selecting a repairing agent, and if blue rust and/or green rust accounts for more than 70% of the corrosion area, adopting a No. 1 repairing agent; if the red rust occupies more than 70% of the rust area, a No. 2 repairing agent is adopted; if the rust has blue rust and/or green rust and red rust, and the rust areas respectively account for more than 30 percent, adopting a No. 3 repairing agent;
(2) applying a repairing agent on the rusted surface of the golden copper statue, keeping for 2-6h, wiping off a large repairing agent by using a cotton swab, and wiping off a small repairing agent remained on the surface by using cotton;
(3) cleaning repairing agent residues attached to the surface of the golden copper image with ethanol, and naturally drying at room temperature;
(4) and (3) sealing and protecting the gilded copper statue after rust removal by using acrylic resin solution.
The acrylic resin is Paraloid B-72.
The sealing and protecting method in the step (4) comprises the following steps: dipping 2% acrylic resin solution with a brush, uniformly brushing in one direction for 3-5 times, standing for 18-30h, drying and curing.
The No. 1 repairing agent comprises the following components in parts by weight: 80-120 parts of aloe gel, 3-10 parts of polyvinylpyrrolidone, 2-8 parts of sodium glutamate and 2-8 parts of acetic acid.
The No. 2 repairing agent comprises the following components in parts by weight: 80-120 parts of aloe gel, 3-10 parts of polyvinylpyrrolidone, 2-8 parts of thiourea and 2-8 parts of citric acid.
The No. 3 repairing agent comprises the following components in parts by weight: 80-120 parts of aloe gel, 3-10 parts of polyvinylpyrrolidone, 1-4 parts of sodium glutamate, 1-4 parts of acetic acid, 1-4 parts of thiourea and 1-4 parts of citric acid.
The extraction method of the aloe gel comprises the following steps: taking aloe leaves, peeling off leaf skin, taking out internal gel, pulping, putting the pulp into 70% ethanol solution, performing ultrasonic extraction for 2 times at an initial temperature of 60 ℃ and an ultrasonic frequency of 25KHz for 25min each time, adding 0.6% activated carbon for decolorization, stirring at room temperature for 30min, filtering off the activated carbon, performing reduced pressure distillation to remove the ethanol solvent, and reducing the water content to be less than 75% to obtain gel, thus obtaining the aloe leaf juice.
The invention has the beneficial effects that: the repairing agent of the invention adopts natural plant aloe extract as a gel material, is nontoxic to human body and pollution-free to environment, and the problem of poor aloe gel permeability is solved by adding polyvinylpyrrolidone. Aiming at different corrosion conditions of gold plating copper modeling, the rust remover with different components is arranged, the combination of sodium glutamate and acetic acid can effectively remove green rust and blue rust corrosion, the combination of thiourea and citric acid can effectively remove red rust, and the combination of the 4 components can effectively remove mixed rust.
Drawings
Figure 1 is a graph of viscosity measurements of different aloe vera gels.
FIG. 2 shows the adsorption rate of patina reaction under different conditions of adding a permeation agent.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following more detailed description. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Example 1 extraction and viscosity measurement of Aloe gel
Taking aloe leaves, peeling off leaf skin, taking out internal gel, pulping, putting the pulp into 70% ethanol solution, carrying out ultrasonic extraction for 2 times at an initial temperature of 60 ℃ under the ultrasonic frequency of 25KHz for 25min each time, adding 0.6% activated carbon for decolorization, stirring for 30min at room temperature, filtering out the activated carbon, carrying out reduced pressure distillation to remove the ethanol solvent, and reducing the water content to the following gradient: 90%, 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%.
The viscosity of aloe gel with different water contents is measured by NDJ-8S rotational viscometer, the measurement result is shown in figure 1, the viscosity increases with the decrease of the water content of the aloe gel, and the measurement of the viscosity with the water content of 50% exceeds the measuring range of the tester and cannot be measured. The larger the viscosity of the aloe gel is, the better the shaping is kept, when the aloe gel is applied to removing rust from the golden copper image, the poorer the permeability of the rust remover is, the more the golden copper image can be protected, but the larger the viscosity is, the longer the time for the rust remover to exert the effect is, and the larger the viscosity is, the rust removal cannot be carried out.
The inventor finds that the rust remover sodium glutamate (1-6%) and acetic acid (1-6%) are added into the aloe gel, the moisture content of the aloe gel needs to reach more than 80% to achieve the rust removing effect, however, under the condition of the moisture content, the viscosity of the gel is too low, the shaping retention time is too short, the rust remover is easy to permeate to cause the gild layer to fall off, the moisture content of the aloe gel is about 70% to achieve a good shaping retention effect, and at the moment, the permeation effect is too poor to remove rust.
EXAMPLE 2 selection of penetrants
The repairing agent comprises the following components in parts by weight: 100 parts of aloe gel (water content is 70%), 6 parts of penetrant, 4 parts of sodium glutamate and 4 parts of acetic acid.
The penetrant is selected from the following substances: polyoxyethylene ether, polyvinylpyrrolidone, isooctanol polyoxyethylene ether phosphate, diisobutyl naphthalene sulfonate, dioctyl sodium sulfosuccinate, methyl methacrylate, butyl acrylate and polyvinyl alcohol.
The essence of the gold plating copper modeling green corrosion component is Cu 2 (OH) 2 CO 3 The main components of the malachite are the substances, the malachite is adopted as an experimental material to verify the repairing effect of the repairing agent, the malachite is pulverized into powder and sieved by a 100-mesh sieve, 20g of the malachite is taken in each experiment and compacted at 5X 5Cm 2 In the small square grids, 20g of the repairing agent is uniformly covered on the compacted malachite powder, the small square grids are kept stand for 4 hours, the gel is carefully taken out and weighed, the repairing effect of the repairing agent is calculated, the repairing effect takes the reaction adsorption rate of the malachite as an index, and the higher the index is, the better the repairing effect is proved.
Reaction adsorption rate (gel weight after repair-20)/20X 100%
The test result is shown in fig. 2 (the contrast is no permeation agent), the reaction adsorption rate is significantly higher after the polyvinylpyrrolidone is added than that of other groups, and the polyvinylpyrrolidone is proved to be capable of being used as the permeation agent in the repairing agent component.
Example 3 Complex Effect of Rust remover
Sodium glutamate and acetic acid can be used as rust remover of malachite, but the principle of rust removal is different, the sodium glutamate adopts the action principle of complexing divalent copper ions, and the acetic acid and the malachite generate acid-base reaction, so that the divalent copper ions are released and adsorbed by gel to remove rust, but the antagonism or synergism is not known in combination of the sodium glutamate and the acetic acid.
In the embodiment, malachite is used as an experimental material to verify the composite effect of the rust remover, and the formula of the repairing agent group 1 is as follows: 100 parts of aloe gel (with the water content of 70 percent), 6 parts of penetrant and 8 parts of sodium glutamate; the formula of group 2 is: 100 parts of aloe gel (the water content is 70%), 6 parts of penetrating agent and 8 parts of acetic acid; the formula of group 3 is: 100 parts of aloe gel (with the water content of 70 percent), 6 parts of penetrant, 4 parts of sodium glutamate and 4 parts of acetic acid;
pulverizing malachite into powder, sieving with 100 mesh sieve, collecting 20g of the powder for each experiment, and compacting at 5X 5Cm 2 In the small square grids, 20g of the repairing agents of groups 1 to 3 are taken respectively, evenly covered on the compacted malachite powder, kept stand for 4 hours, the gel is carefully taken out and weighed, and the repairing agents are calculatedThe repairing effect of the compound is characterized in that the reactive adsorption rate of the malachite is taken as an index, and the higher the index is, the better the repairing effect is proved to be.
The adsorption rate of the reaction is (weight of gel after repairing-20)/20X 100%
The results are shown in Table 1:
TABLE 1
Note: represents p <0.05 compared to group 3.
As can be seen from Table 1, the combination of sodium glutamate and acetic acid has a remarkable synergistic effect compared with the single dose.
Example 4 composite Effect of Red Rust remover
Thiourea and citric acid use alone all can get rid of red rust, and the essence of red rust is monovalent copper ion oxide, and this embodiment adopts cuprous oxide as the experimental materials, verifies the repairing effect of repairing agent, and repairing agent group 1 formula: 100 parts of aloe gel (water content is 70%), 6 parts of polyvinylpyrrolidone and 8 parts of thiourea; the repairing agent group 2 comprises the following formula: 100 parts of aloe gel (water content is 70%), 6 parts of polyvinylpyrrolidone and 8 parts of citric acid; the repairing agent group 3 comprises the following formula: 100 parts of aloe gel (with the water content of 70 percent), 6 parts of polyvinylpyrrolidone, 4 parts of thiourea and 4 parts of citric acid;
20g of cuprous oxide is taken in each experiment and compacted at 5X 5Cm 2 In the small square grids, 20g of the repairing agent is uniformly covered on the compacted malachite powder, the small square grids are kept stand for 4 hours, the gel is carefully taken out and weighed, the repairing effect of the repairing agent is calculated, the repairing effect takes the reaction adsorption rate of the malachite as an index, and the higher the index is, the better the repairing effect is proved.
The adsorption rate of the reaction is (weight of gel after repairing-20)/20X 100%
The results are shown in Table 2:
TABLE 2
Note: represents p <0.05 compared to group 3.
As can be seen from Table 2, the combination of thiourea and citric acid has a remarkable synergistic effect compared with the single dosage.
Example 5 removal of Mixed Rust
According to the results of examples 1-4, it is suggested that the mixed rust formulation is set up as follows: aloe gel (water content 70%), polyvinylpyrrolidone 6 parts, sodium glutamate 2 parts, acetic acid 2 parts, thiourea 2 parts, and citric acid 2 parts.
Taking 10g of malachite powder and 10g of cuprous oxide for each experiment, uniformly mixing, and compacting at 5X 5Cm 2 In the small square grids, 20g of the repairing agent is uniformly covered on the compacted malachite powder, the small square grids are kept stand for 4 hours, the gel is carefully taken out and weighed, the repairing effect of the repairing agent is calculated, the repairing effect takes the reaction adsorption rate of the malachite as an index, and the higher the index is, the better the repairing effect is proved.
The adsorption rate of the reaction is (weight of gel after repairing-20)/20X 100%
The reaction adsorption rate of the repairing agent is calculated by experiments to be 32.8%, and the repairing agent has a good effect of removing mixed rust.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is specific and detailed, but not to be understood as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (4)
1. A gilded copper image surface repairing method is characterized by comprising the following steps:
(1) judging the type of corrosion on the imaging surface of the gilded copper, selecting a repairing agent, and if blue rust and/or green rust account for more than 70% of the corrosion area, adopting a No. 1 repairing agent; if the red rust accounts for more than 70% of the rust area, a No. 2 repairing agent is adopted; if the rust has blue rust and/or green rust and red rust, and the rust areas respectively account for more than 30 percent, a No. 3 repairing agent is adopted;
(2) applying a repairing agent on the rusted surface of the golden copper statue, keeping for 2-6h, wiping off a large repairing agent by using a cotton swab, and wiping off a small repairing agent remained on the surface by using cotton;
(3) cleaning repairing agent residues attached to the surface of the golden copper image with ethanol, and naturally drying at room temperature;
(4) sealing and protecting the gilded copper statue after rust removal by using acrylic resin solution;
the No. 1 repairing agent comprises the following components in parts by weight: 80-120 parts of aloe gel, 3-10 parts of polyvinylpyrrolidone, 2-8 parts of sodium glutamate and 2-8 parts of acetic acid;
the No. 2 repairing agent comprises the following components in parts by weight: 80-120 parts of aloe gel, 3-10 parts of polyvinylpyrrolidone, 2-8 parts of thiourea and 2-8 parts of citric acid;
the No. 3 repairing agent comprises the following components in parts by weight: 80-120 parts of aloe gel, 3-10 parts of polyvinylpyrrolidone, 1-4 parts of sodium glutamate, 1-4 parts of acetic acid, 1-4 parts of thiourea and 1-4 parts of citric acid.
2. The method for repairing the surface of gilded copper figuration according to claim 1, wherein the acrylic resin is Paraloid B-72.
3. The method for repairing the surface of the gilded copper image according to claim 1, wherein the sealing and protecting method in step (4) is as follows: dipping 2% acrylic resin solution with a brush, uniformly brushing in one direction for 3-5 times, standing for 18-30h, drying and curing.
4. The method for repairing the surface of the gilded copper image according to claim 1, wherein the method for extracting the aloe gel comprises the following steps: taking aloe leaves, peeling off leaf skin, taking out internal gel, pulping, putting the pulp into 70% ethanol solution, performing ultrasonic extraction for 2 times at an initial temperature of 60 ℃ and an ultrasonic frequency of 25KHz for 25min each time, adding 0.6% activated carbon for decolorization, stirring at room temperature for 30min, filtering off the activated carbon, performing reduced pressure distillation to remove the ethanol solvent, and reducing the water content to be less than 75% to obtain gel, thus obtaining the aloe leaf juice.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996035645A1 (en) * | 1995-05-12 | 1996-11-14 | Chem Pro Laboratory, Inc. | Corrosion products removal methods and compositions for use therein |
| CN104357861A (en) * | 2014-10-31 | 2015-02-18 | 陕西师范大学 | Gel rust remover for aerugo of gilding layer |
| CN108842155A (en) * | 2018-06-21 | 2018-11-20 | 上海理工大学 | A kind of copper and copper alloy environment-friendly rust remover and its derusting method |
| CN109135945A (en) * | 2018-09-06 | 2019-01-04 | 维希艾防锈新材料(上海)有限公司 | Environmentally friendly neutrality rust remover |
| CN110724961A (en) * | 2019-10-30 | 2020-01-24 | 电子科技大学 | Corrosion inhibitor and application thereof in copper metal pickling solution and chemical polishing solution |
-
2021
- 2021-01-12 CN CN202110036561.7A patent/CN112877701B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996035645A1 (en) * | 1995-05-12 | 1996-11-14 | Chem Pro Laboratory, Inc. | Corrosion products removal methods and compositions for use therein |
| CN104357861A (en) * | 2014-10-31 | 2015-02-18 | 陕西师范大学 | Gel rust remover for aerugo of gilding layer |
| CN108842155A (en) * | 2018-06-21 | 2018-11-20 | 上海理工大学 | A kind of copper and copper alloy environment-friendly rust remover and its derusting method |
| CN109135945A (en) * | 2018-09-06 | 2019-01-04 | 维希艾防锈新材料(上海)有限公司 | Environmentally friendly neutrality rust remover |
| CN110724961A (en) * | 2019-10-30 | 2020-01-24 | 电子科技大学 | Corrosion inhibitor and application thereof in copper metal pickling solution and chemical polishing solution |
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Denomination of invention: A Surface Repair Method and Repair Agent for Gilded Copper Statues Effective date of registration: 20230711 Granted publication date: 20220913 Pledgee: Hubei Daye Rural Commercial Bank Co.,Ltd. Pledgor: Hubei juechen Technology Co.,Ltd. Registration number: Y2023420000298 |