A kind of gel cleaning agent and its preparation method and application in removing fragile bronze cultural relics corrosion

Abstract

The application discloses a kind of gel cleaning agent and its preparation method and application in removing fragile bronze cultural relics corrosion, belong to cultural relic protection technical field.The gel cleaning agent includes copper ion chelating agent 0.1-0.8%, film forming agent 2-10%, humectant 1-10%, weak acid 0.1-3%, thickening agent 2-8% by mass percentage, and the rest is water.The gel cleaning agent is transparent milky white, can flow, is composed of organic polymer and copper ion cleaning component, has good hydrophilicity, film forming property, adhesive force, non-toxicity and biocompatibility etc., can form film in rust part to remove copper rust, reduce the damage of cultural relics surface caused by multiple cleaning, reduce gel residue, green and safe, do not pollute and destroy cultural relics surface, suitable for fragile and flaky bronze, also suitable for difficult to remove rust gap cavity etc..

Description

Technical Field

[0001] This invention belongs to the field of cultural relic protection technology, specifically relating to a gel cleaning agent, its preparation method, and its application in removing rust from fragile bronze cultural relics. Background Technology

[0002] Ancient bronzes and ceramics, as precious legacies of human history and culture, frequently require restoration and preservation to extend their lifespan and showcase their historical value. Due to long-term burial and exposure to water, chlorides, and other factors, bronzes develop extensive patina on their surfaces, including both harmful and harmless patina. Harmless patina primarily consists of CuO and Cu2O. Under normal conditions, this type of patina will not further corrode the bronze and can even provide some protection. Harmful patina, however, accelerates the corrosion and perforation of bronze artifacts, ultimately leading to their pulverization and even complete destruction.

[0003] Common methods for cleaning bronze rust generally involve soaking or applying the rust to acidic or alkaline solutions with complexing properties. For example, disodium ethylenediaminetetraacetate, sodium hexametaphosphate, thiourea, citric acid, cysteine, and ammonia are used as cleaning agents, which can complex with monovalent or divalent copper compounds, dissolving or softening the rust. In addition, researchers have also attempted acid-base neutralization methods for rust removal, using strong acidic ion exchange resins to clean the rust. However, these methods can potentially damage the bronze substrate due to over-cleaning. For some fragile bronze artifacts with severe surface corrosion and mineralization, resulting in low substrate strength and fragility, conventional mechanical rust removal and chemical soaking treatments can easily lead to further deterioration and disintegration.

[0004] Therefore, it is necessary to develop hydrogel stripping rust removal technology, which can gently and efficiently remove copper rust from the surface of fragile bronze artifacts, in order to solve the problems of targeted rust removal of such fragile bronze artifacts and the problems existing in traditional methods. Summary of the Invention

[0005] In order to overcome the shortcomings of the prior art, the present invention aims to provide a gel cleaning agent and its preparation method and its application in removing rust from fragile bronze artifacts, so as to solve the technical problem that the existing methods for cleaning brittle and flaky bronze rust can damage the bronze substrate due to excessive cleaning.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] This invention discloses a gel cleaning agent, comprising, by weight percentage: 0.1%-0.8% copper ion chelating agent, 2%-10% film-forming agent, 1%-10% humectant, 0.1%-3% weak acid, 2%-8% thickener, and the remainder being water.

[0008] Preferably, the gel cleaning agent comprises, in percentage by mass: 0.3%-0.8% of copper ion chelating agent, 2%-8% of film forming agent, 5%-9% of humectant, 1%-3% of weak acid, 5%-8% of thickening agent, and the rest is water.

[0009] Preferably, the copper ion chelating agent is at least one of amino triacetic acid, diethylene triamine pentaacetic acid, ethylene diamine tetraacetic acid, citric acid, tartaric acid, gluconic acid and polyacrylic acid.

[0010] Preferably, the film forming agent is at least one of polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxypropyl methyl cellulose, pectin, polyurethane, trimethyl siloxy silicate, acrylic resin, dimethyl siloxane copolymer and acrylic copolymer emulsion.

[0011] Preferably, the humectant is at least one of glycerol, butylene glycol, caprylyl glycol, sorbitol, hyaluronic acid, sodium polyglutamate, betaine, lysine, arginine, xylitol, collagen and algal extract.

[0012] Preferably, the weak acid is at least one of formic acid, acetic acid, propionic acid, oxalic acid, hypochlorous acid and nitrous acid.

[0013] Preferably, the thickening agent is at least one of starch, gum arabic, pectin, agar, gelatin, algin, carrageenan, propylene glycol alginic acid ester, carbomer, methyl cellulose, starch sodium phosphate, sodium carboxymethyl cellulose, sodium alginic acid, casein and sodium polyacrylate.

[0014] Preferably, the gel cleaning agent has a tensile strength of 5-48 KPa, an elastic modulus of 4.54-38.90 KPa, an elongation of 62.3%-248.1%, and a viscosity of 36027-334230 mPa·s.

[0015] The application also discloses a preparation method of the gel cleaning agent.

[0016] Water is heated to 90-95 DEG C, the copper ion chelating agent is added, stirred until completely dissolved, the film forming agent is added, and a transparent solution is obtained after complete dissolution; the humectant and the weak acid are added during stirring, and the thickening agent is added after uniform stirring, and the gel cleaning agent is obtained after complete dissolution and cooling to room temperature.

[0017] The application also discloses application of the gel cleaning agent in removing rust on fragile bronze cultural relics, and the gel cleaning agent is thickly applied to a rust removal part of the bronze ware, and then is peeled off after film formation.

[0018] Compared with the prior art, the application has the following beneficial effects:

[0019] The present application discloses a kind of gel cleaning agent, comprising by mass percentage: copper ion chelating agent 0.1%-0.8%, film forming agent 2%-10%, humectant 1%-10%, weak acid 0.1%-3%, thickening agent 2%-8%, and the rest is water.Select reagent safety green, less harm to cultural relics and human body, copper ion chelating agent contains carboxyl and ethylenediamine group, both can participate in complexation reaction of copper ion, and copper rust is removed by chelation;The addition of thickening agent can make the gel cleaning agent have proper viscosity, so as to be more easily daubed and kept on the surface of cultural relics.This is very important for improving rust removal effect and reducing gel residue.The combination of film forming agent and thickening agent can form a stable protective film, which helps to form a film on the rust site to remove copper rust, while reducing damage to the surface of cultural relics caused by multiple cleaning.Humectant can keep the moisture of gel, prevent it from becoming dry after long time use, and help the gel to better adhere to the surface of cultural relics, improve the rust removal effect.Weak acid can react with copper rust to accelerate the removal of copper rust.Meanwhile, the addition of weak acid can also adjust the pH value of the gel cleaning agent, making it more suitable for cleaning the surface of cultural relics.The gel cleaning agent is transparent and milky white, and can flow, which is composed of organic macromolecules and copper ion cleaning components.It has good hydrophilicity, film forming property, adhesion, non-toxicity and biocompatibility, etc., and can form a film on the rust site to remove copper rust, reduce damage to the surface of cultural relics caused by multiple cleaning, reduce gel residue, green and safe, without polluting and damaging the surface of cultural relics, suitable for brittle and thin sheet bronze, also suitable for rust removal of gap and other parts.

[0020] Further, polyvinyl alcohol is used as film forming agent, and the main chain of polyvinyl alcohol molecule is carbon chain, and each repeating unit contains one hydroxyl group.Because the size of hydroxyl group is small, the polarity is strong, and hydrogen bond is easy to form, the hydrogen bond existing between polyvinyl alcohol molecules makes it have good chemical stability and thermal stability, and the large number of hydroxyl groups on its molecular chain makes it have strong hydrophilicity, film forming property, adhesion and emulsifying property, and it is non-toxic, biodegradable and biocompatible.

[0021] Further, carboxyvinyl polymer is used as thickening agent, the carboxyvinyl polymer molecule contains 56%-68% carboxylic acid group, in powder state, the carboxyvinyl polymer molecule chain is in crimped state, after being dispersed in water, part of the carboxylic acid group of the carboxyvinyl polymer molecule chain is free, hydration occurs, and the molecule chain gradually expands, at this time, the water dispersion is weakly acidic. The carboxyvinyl polymer does not support the growth of bacteria and mold, has good acid resistance, good gel thermal reversibility, high strength, no toxicity and no irritation, and the viscosity is not affected by temperature. The carboxyvinyl polymer has large thickening effect when the amount is small, therefore, when the carboxyvinyl polymer is used in combination with polyvinyl alcohol, if the content of the carboxyvinyl polymer is too high, the gel has poor fluidity and high viscosity, and the fragile cultural relics are easily damaged; if the content of the carboxyvinyl polymer is too low, the gel has too strong fluidity, is not easy to adhere to the surface of the cultural relics, the rust removal effect is weakened, and the cultural relics are secondarily damaged.

[0022] Further, ethylenediaminetetraacetic acid is used as copper ion chelating agent, the ethylenediaminetetraacetic acid can form stable water-soluble complex with alkali metals, rare earth elements and transition metals. In addition to sodium salt, there are ammonium salt and various salts of iron, magnesium, calcium, copper, manganese, zinc, cobalt and aluminum, the ethylenediaminetetraacetic acid is an excellent calcium and magnesium ion chelating agent, which is used as chelating agent for water for emulsion polymerization, and can remove Ca 2+ , Mg 2+ , Fe 2+ , Fe 3+ and other metal ions.

[0023] The application further discloses a preparation method of the gel cleaning agent, and the method comprises the following steps: heating water to 90-95 DEG C, ensuring that all ingredients can be uniformly and quickly mixed together, so as to prepare a uniform gel cleaning agent. Adding a copper ion chelating agent, stirring until completely dissolved, ensuring that the copper ion chelating agent is uniformly distributed in the whole solution system, providing sufficient active ingredients for subsequent copper rust removal. Adding a film-forming agent, until completely dissolved to obtain a transparent solution, forming a stable network structure in the solution system, providing a basis for the formation of the subsequent gel. Adding a humectant and a weak acid during stirring, the humectant can increase the moisture retention performance of the gel, and the weak acid can adjust the pH value of the solution, which is helpful for the removal of copper rust. After stirring uniformly, adding a thickening agent, stirring until completely dissolved, and cooling to room temperature to obtain the gel cleaning agent. The thickening agent is uniformly distributed in the solution system, which increases the viscosity and consistency of the solution, so that the required gel cleaning agent is obtained. The obtained gel cleaning agent can effectively remove the copper rust on the surface of cultural relics, and reduce the damage to the surface of cultural relics caused by multiple cleaning. The gel can form a film on the rusted part, improve the rust removal effect, and reduce the gel residue. The components in the formula are safe and green, meet the principles of “minimum intervention” and “not changing the appearance of cultural relics”. The gel preparation process is simple and easy to save, and is suitable for the parts such as gaps and cavities which are difficult to remove rust.

[0024] The application also discloses application of the gel cleaning agent in rust removal of fragile bronze cultural relics, and the gel cleaning agent is applied on the rust removal part of the bronze ware, and then is removed after film formation. The rust removal by using the gel cleaning agent can effectively protect the surface of the bronze ware and reduce damage in the cleaning process. By the application mode, the gel cleaning agent can fully cover and penetrate into the rust removal part of the bronze ware. The application mode can ensure that the cleaning agent fully contacts with copper rust and improves the rust removal effect. After the cleaning agent fully reacts with the copper rust and forms a film, the copper rust can be easily removed by the removing mode. The operation mode is simple and convenient, and does not need complex equipment and steps. Meanwhile, since the cleaning agent has reacted with the copper rust in the film formation process, the copper rust can be effectively removed after the removing, and damage to the surface of the bronze ware in the cleaning process is reduced. In addition, the cleaning agent after film formation is easy to peel off from the surface of the bronze ware, reduces the residue of the cleaning agent, and is beneficial to protect the surface of the bronze ware. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 Schematic diagram of bronze ware test sample before and after rust removal in soil environment;

[0026] Figure 2 XRD analysis diagram of copper rust of test sample residual part in soil environment;

[0027] Figure 3 SEM analysis diagram of copper rust of test sample residual part in soil environment;

[0028] Figure 4 XRD analysis diagram of gel cleaning agent after rust removal;

[0029] Figure 5 SEM analysis diagram of gel cleaning agent after rust removal. DETAILED DESCRIPTION

[0030] In order to enable the personnel in the technical field to better understand the present application, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present application. Obviously, the described embodiments are only a part of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor should belong to the protection scope of the present application.

[0031] It is to be understood that the terminology "first", "second", and the like used in the specification and the claims of the application as well as the appended drawings is merely used for distinguishing between similar objects and does not necessarily imply a required or a particular order or sequence. It is to be understood that the data used herein can be interchanged, where appropriate, so that the embodiments of the application described herein can be carried out in other than the order described. Additionally, the terms "comprising", "having", "including" and "containing" are to be construed as open-ended terms (i.e., meaning "including, but not limited to") unless otherwise noted. It is intended that the application encompass each and every combination of features described herein.

[0032] The application will be further described in detail with reference to the drawings.

[0033] Referring to Figure 1 The schematic diagram of bronze test sample before and after rust removal in soil environment; it can be seen from the diagram that green rust layer is generated before rust removal and is relatively dense, and brown soil rust is mixed in the green rust product. The contrast effect of bronze test sample and residual piece before and after cleaning by the gel rust remover of Example 3 is obvious, which shows that the gel rust remover has good removal effect and can remove rust while restoring the original metal luster of the gold layer.

[0034] Figure 2 The XRD analysis diagram of copper rust of the test sample residual piece in soil environment; it can be seen from the diagram that in combination with the bronze test sample diagram, the green rust layer is mainly malachite [CuCO3·Cu(OH)2], and the brown and brick red rust products are mainly cuprite (Cu2O).

[0035] Figure 3 The SEM analysis diagram of copper rust of the test sample residual piece in soil environment; it can be seen from the diagram that the rust of the test sample residual piece shows a polymer morphology and completely covers the test sample residual piece.

[0036] Figure 4 The XRD analysis diagram of the gel cleaning agent after rust removal; it can be seen from the diagram that Cu 2+ and Cu + are detected in the gel film after rust removal, which indicates that the rust product reacts with the gel cleaning agent, and the rust product is stripped from the cultural relics after film formation.

[0037] Figure 5 The SEM analysis diagram of the gel cleaning agent after rust removal; it can be seen from the diagram that the surface of the gel film after rust removal has no obvious protrusions, which indicates that the cultural relics body is not damaged in the cleaning process.

[0038] The present application discloses a kind of gel cleaning agent, comprising: copper ion chelating agent 0.1%-0.8%, film forming agent 2%-10%, humectant 1%-10%, weak acid 0.1%-3%, thickening agent 2%-8%, the rest is water.

[0039] Wherein, copper ion chelating agent is at least one of amino triacetic acid, diethylene triamine pentaacetic acid, ethylenediamine tetraacetic acid, citric acid, tartaric acid, gluconic acid and polyacrylic acid, preferably ethylenediamine tetraacetic acid.

[0040] Film forming agent is at least one of polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxypropyl methyl cellulose, pectin, polyurethane, trimethyl siloxy silicate, acrylic resin, dimethyl siloxane copolymer and acrylic copolymer emulsion.

[0041] Humectant is at least one of glycerol, butanediol, octanediol, sorbitol, hyaluronic acid, polyglutamic acid sodium, betaine, lysine, arginine, xylitol, collagen and algal extract, preferably glycerol.

[0042] Weak acid is at least one of formic acid, acetic acid, propionic acid, oxalic acid, hypochlorous acid and nitrous acid, preferably propionic acid.

[0043] Thickening agent is at least one of starch, gum arabic, pectin, agar, gelatin, algin, carrageenan, propylene glycol alginate, carbomer, methyl cellulose, starch sodium phosphate, sodium carboxymethyl cellulose, sodium alginate, casein and polyacrylic acid sodium.

[0044] Preferably, the mass percentage composition of the gel cleaning agent is: polyvinyl alcohol 2%-8%, carbomer 2%-8%, copper ion chelating agent 0.1%-0.8%, glycerol 1%-10%, weak acid 0.1%-3%, the rest is water.

[0045] Preferably, the mass percentage composition of the gel cleaning agent is: polyvinyl alcohol 2%-8%, carbomer 2%-4%, copper ion chelating agent 0.3%-0.8%, glycerol 5%-9%, weak acid 1%-3%, the rest is water.

[0046] The preparation method of the gel cleaning agent of the present application: heat ultrapure water to 90-95℃, add ethylenediamine tetraacetic acid, stir until ethylenediamine tetraacetic acid is completely dissolved, add polyvinyl alcohol, until polyvinyl alcohol is completely dissolved to obtain a transparent solution, add glycerol and propionic acid during stirring, after stirring for a period of time, add carbomer in small amounts and multiple times, observe a small amount of carbomer agglomerates during stirring, continue to stir until carbomer is completely dissolved, cool to room temperature to obtain the gel cleaning agent.

[0047] The application method of the gel cleaning agent in the application of rust removal of fragile bronze ware is as follows: the gel cleaning agent is thickly applied to the rust removal part, and after the film is formed, the gel film is gently removed, and the operation is repeated until the copper rust is completely removed.

[0048] The application adopts polyvinyl alcohol as a film forming agent, carbomer as a thickening agent, and a carrier of weak acid and copper ion chelating agent, adds glycerol as a humectant, and selects a reagent safe green, which is less harmful to cultural relics and human bodies.

[0049] The application adopts polyvinyl alcohol as a film forming agent, carbomer as a thickening agent, and a carrier of weak acid and copper ion chelating agent, adds glycerol as a humectant, and selects a reagent safe green, which is less harmful to cultural relics and human bodies.

[0050] The application adopts ethylenediaminetetraacetic acid as a copper ion chelating agent, and ethylenediaminetetraacetic acid can form stable water-soluble complexes with alkali metals, rare earth elements and transition metals. In addition to sodium salt, there are ammonium salt and various salts of iron, magnesium, calcium, copper, manganese, zinc, cobalt and aluminum, and these salts have different uses. Ethylenediaminetetraacetic acid is an excellent calcium and magnesium ion chelating agent, which is used as a chelating agent for water used in emulsion polymerization to remove Ca 2+ , Mg 2+ , Fe 2+ , Fe 3+ and other metal ions.

[0051] The gel cleaning method adopted in the application is transparent and milky white, and is flowable, and is composed of organic polymer and copper ion cleaning components. The gel has good hydrophilicity, film forming property, adhesion, non-toxicity and biocompatibility, and can form a film on the rust site to remove copper rust, reduce the damage to the surface of cultural relics caused by multiple cleaning, reduce the gel residue, is green and safe, does not pollute and damage the surface of cultural relics, is suitable for rust removal of brittle and thin sheet bronze cultural relics, and is also suitable for rust removal of gap and hollow sites.

[0052] The application utilizes the characteristics of gel film forming and copper ion chelating agent to clean the copper rust of the gap site of cultural relics. The gel preparation process is simple and easy to preserve, and meets the principles of "minimum intervention" and "not changing the appearance of cultural relics". The gel has slow release and adhesion, and can realize the controlled release of the cleaning components in the gel. The composition is simple, the selected reagents are safe and green, the harm to cultural relics and human body is small, the operation is easy, the gel can be easily removed, and the gel does not damage the surface of cultural relics. The gel is suitable for brittle and thin sheet bronze, and is also suitable for rust removal of gap and hollow sites.

[0053] Example 1

[0054] A preparation method of a gel cleaning agent, comprising:

[0055] 25g of ultrapure water is heated to 90℃, 0.15g of ethylenediaminetetraacetic acid is added, and stirring is continued until complete dissolution. Then, 0.5g of polyvinyl alcohol 1799 is added until the polyvinyl alcohol is completely dissolved to obtain a transparent aqueous solution. Under stirring, 1.5mL of glycerol and 0.5mL of propionic acid are added, and stirring is continued for a period of time. Then, 1.5g of carbomer 940 is added to the solution in small amounts and multiple times, and stirring is continued. After the carbomer 940 is completely dissolved, a milky white solution is obtained. The solution is cooled to room temperature to obtain a copper rust gel cleaning agent. The viscosity of the gel cleaning agent is 47074mPa·s as determined by a viscometer.

[0056] Example 2

[0057] A preparation method of a gel cleaning agent, comprising:

[0058] 25g of ultrapure water is heated to 90℃, 0.15g of ethylenediaminetetraacetic acid is added, and stirring is continued until complete dissolution. Then, 0.5g of polyvinyl alcohol 1799 is added until the polyvinyl alcohol is completely dissolved to obtain a transparent aqueous solution. Under stirring, 1.5mL of glycerol and 0.5mL of propionic acid are added, and stirring is continued for a period of time. Then, 1.5g of carbomer 940 is added to the solution in small amounts and multiple times, and stirring is continued. After the carbomer 940 is completely dissolved, a milky white solution is obtained. The solution is cooled to room temperature to obtain a copper rust gel cleaning agent. The viscosity of the gel cleaning agent is 47074mPa·s as determined by a viscometer.

[0059] Example 3

[0060] A method for preparing a gel cleaning agent, comprising:

[0061] Heat 25 g of ultrapure water to 90℃, add 0.15 g of ethylenediaminetetraacetic acid, continue stirring until completely dissolved, then add 1.5 g of polyvinyl alcohol type 1799, until the polyvinyl alcohol is completely dissolved to obtain a transparent aqueous solution, under stirring, add 1.5 mL of glycerol, 0.5 mL of propionic acid, after stirring for a period of time, add 1.5 g of carbomer 940 to the solution in small amounts and multiple times, continue stirring, and after the carbomer 940 is completely dissolved, a milky white solution is obtained, cool to room temperature to obtain a bronze gel cleaning agent. The viscosity is 260210 mPa·s as determined by a viscometer.

[0062] Example 4

[0063] A method for preparing a gel cleaning agent, comprising:

[0064] Heat 25 g of ultrapure water to 90℃, add 0.15 g of ethylenediaminetetraacetic acid, continue stirring until completely dissolved, then add 2 g of polyvinyl alcohol type 1799, until the polyvinyl alcohol is completely dissolved to obtain a transparent aqueous solution, under stirring, add 1.5 mL of glycerol, 0.5 mL of propionic acid, after stirring for a period of time, add 1.5 g of carbomer 940 to the solution in small amounts and multiple times, continue stirring, and after the carbomer 940 is completely dissolved, a milky white solution is obtained, cool to room temperature to obtain a bronze gel cleaning agent. The viscosity is 334230 mPa·s as determined by a viscometer.

[0065] Example 5

[0066] A method for preparing a gel cleaning agent, comprising:

[0067] Heat 25 g of ultrapure water to 90℃, add 0.2 g of amino triacetic acid, continue stirring until completely dissolved, then add 1.5 g of polyvinylpyrrolidone, until the polyvinylpyrrolidone is completely dissolved to obtain a transparent aqueous solution, under stirring, add 1.25 mL of glycerol, 0.25 mL of formic acid, after stirring for a period of time, add 2 g of starch to the solution in small amounts and multiple times, continue stirring, and after the starch is completely dissolved, a milky white solution is obtained, cool to room temperature to obtain a bronze gel cleaning agent. The viscosity is 36027 mPa·s as determined by a viscometer.

[0068] Example 6

[0069] A method for preparing a gel cleaning agent, comprising:

[0070] The 25 g of ultrapure water is heated to 90 °C, 0.075 g of citric acid is added, and stirred until completely dissolved. Then 1.5 g of hydroxypropyl methyl cellulose is added, and stirred until the hydroxypropyl methyl cellulose is completely dissolved to obtain a transparent aqueous solution. Under stirring, 1.25 g of octisols, 0.25 mL of oxalic acid is added, and stirred for a period of time. Then 2 g of pectin is added to the solution in small amounts and multiple times, and continues to stir. After the pectin is completely dissolved, a milky white solution is obtained. After cooling to room temperature, a bronze gel cleaner is obtained. The viscosity is 76923 mPa·s measured by a viscometer.

[0071] Example 7

[0072] A method for preparing a gel cleaner, comprising:

[0073] The 25 g of ultrapure water is heated to 90 °C, 0.075 g of citric acid is added, and stirred until completely dissolved. Then 1.5 g of hydroxypropyl methyl cellulose is added, and stirred until the hydroxypropyl methyl cellulose is completely dissolved to obtain a transparent aqueous solution. Under stirring, 1.25 g of octisols, 0.25 mL of oxalic acid is added, and stirred for a period of time. Then 2 g of pectin is added to the solution in small amounts and multiple times, and continues to stir. After the pectin is completely dissolved, a milky white solution is obtained. After cooling to room temperature, a bronze gel cleaner is obtained. The viscosity is 76923 mPa·s measured by a viscometer.

[0074] Example 8

[0075] A method for preparing a gel cleaner, comprising:

[0076] The 25 g of ultrapure water is heated to 90 °C, 0.075 g of citric acid is added, and stirred until completely dissolved. Then 1.5 g of hydroxypropyl methyl cellulose is added, and stirred until the hydroxypropyl methyl cellulose is completely dissolved to obtain a transparent aqueous solution. Under stirring, 1.25 g of octisols, 0.25 mL of oxalic acid is added, and stirred for a period of time. Then 2 g of pectin is added to the solution in small amounts and multiple times, and continues to stir. After the pectin is completely dissolved, a milky white solution is obtained. After cooling to room temperature, a bronze gel cleaner is obtained. The viscosity is 76923 mPa·s measured by a viscometer.

[0077] Example 9

[0078] A method for preparing a gel cleaner, comprising:

[0079] Heat 20 g of ultrapure water to 95℃, add 0.1 g of glucose acid, stir until completely dissolved, then add 0.4 g of polyurethane, stir until the polyurethane is completely dissolved to obtain a transparent aqueous solution, add 0.2 g of hyaluronic acid, 0.02 mL of nitrous acid under stirring, stir for a period of time, then add 0.4 g of gelatin to the solution in small quantities, continue to stir, and after the gelatin is completely dissolved, a milky white solution is obtained. Cool to room temperature to obtain a bronze gel cleanser. The viscosity is 42387 mPa·s as determined by a viscometer.

[0080] Example 10

[0081] A method for preparing a gel cleanser, comprising:

[0082] Heat 20 g of ultrapure water to 95℃, add 0.1 g of polyacrylic acid, stir until completely dissolved, then add 0.4 g of trimethylsiloxy silicate, stir until the trimethylsiloxy silicate is completely dissolved to obtain a transparent aqueous solution, add 0.8 g of sodium polyglutamate, 0.01 mL of propionic acid and 0.01 mL of formic acid under stirring, stir for a period of time, then add 0.4 g of alginic acid to the solution in small quantities, continue to stir, and after the alginic acid is completely dissolved, a milky white solution is obtained. Cool to room temperature to obtain a bronze gel cleanser. The viscosity is 68513 mPa·s as determined by a viscometer.

[0083] Example 11

[0084] A method for preparing a gel cleanser, comprising:

[0085] Heat 20 g of ultrapure water to 90℃, add 0.1 g of ethylenediaminetetraacetic acid, stir until completely dissolved, then add 0.4 g of acrylic acid resin, stir until the acrylic acid resin is completely dissolved to obtain a transparent aqueous solution, add 1.4 g of betaine, 0.02 mL of propionic acid under stirring, stir for a period of time, then add 0.4 g of carrageenan to the solution in small quantities, continue to stir, and after the carrageenan is completely dissolved, a milky white solution is obtained. Cool to room temperature to obtain a bronze gel cleanser. The viscosity is 95470 mPa·s as determined by a viscometer.

[0086] Example 12

[0087] A method for preparing a gel cleanser, comprising:

[0088] Take 20 g of ultrapure water to 90℃, add 0.1 g of ethylenediaminetetraacetic acid, stir until completely dissolved, then add 0.4 g of dimethyl silicone copolymer, until the dimethyl silicone copolymer is completely dissolved to obtain a transparent aqueous solution, add 2 g of lysine, 0.02 mL of propionic acid under stirring, stir for a period of time, then add 0.4 g of propylene glycol alginate to the solution in small quantities, continue to stir, and after the propylene glycol alginate is completely dissolved, a milky white solution is obtained. Cool to room temperature to obtain a bronze gel cleaner. The viscosity is 86539 mPa·s measured by a viscometer.

[0089] Example 13

[0090] A method for preparing a gel cleaner, comprising:

[0091] Take 25 g of ultrapure water to 90℃, add 0.05 g of ethylenediaminetetraacetic acid, stir until completely dissolved, then add 2.25 g of acrylic acid copolymer emulsion, until the acrylic acid copolymer emulsion is completely dissolved to obtain a transparent aqueous solution, add 0.5 g of arginine, 0.125 mL of propionic acid under stirring, stir for a period of time, then add 1.25 g of methyl cellulose to the solution in small quantities, continue to stir, and after the methyl cellulose is completely dissolved, a milky white solution is obtained. Cool to room temperature to obtain a bronze gel cleaner. The viscosity is 78521 mPa·s measured by a viscometer.

[0092] Example 14

[0093] A method for preparing a gel cleaner, comprising:

[0094] Take 25 g of ultrapure water to 90℃, add 0.05 g of ethylenediaminetetraacetic acid, stir until completely dissolved, then add 2 g of polyvinyl alcohol and 0.25 g of polyvinylpyrrolidone, until the polyvinyl alcohol and polyvinylpyrrolidone are completely dissolved to obtain a transparent aqueous solution, add 0.5 g of xylitol, 0.2 mL of propionic acid under stirring, stir for a period of time, then add 1.25 g of starch sodium phosphate to the solution in small quantities, continue to stir, and after the starch sodium phosphate is completely dissolved, a milky white solution is obtained. Cool to room temperature to obtain a bronze gel cleaner. The viscosity is 86041 mPa·s measured by a viscometer.

[0095] Example 15

[0096] A method for preparing a gel cleaner, comprising:

[0097] Heat 25 g of ultrapure water to 90℃, add 0.05 g of ethylenediaminetetraacetic acid, continue to stir until completely dissolved, then add 2.25 g of polyvinyl alcohol type 1799, until the polyvinyl alcohol is completely dissolved to obtain a transparent aqueous solution, under stirring, add 0.5 g of collagen, 0.375 mL of propionic acid, stir for a period of time, then add 1.25 g of sodium carboxymethyl cellulose to the solution in small amounts and multiple times, continue to stir, and after the sodium carboxymethyl cellulose is completely dissolved, a milky white solution is obtained, cool to room temperature to obtain a bronze gel cleanser. The viscosity is 90572 mPa·s as determined by a viscometer.

[0098] Example 16

[0099] A method for preparing a gel cleanser, comprising:

[0100] Heat 25 g of ultrapure water to 95℃, add 0.05 g of ethylenediaminetetraacetic acid, continue to stir until completely dissolved, then add 2.25 g of polyvinyl alcohol type 1799, until the polyvinyl alcohol is completely dissolved to obtain a transparent aqueous solution, under stirring, add 0.5 g of algal extract, 0.75 mL of propionic acid, stir for a period of time, then add 1.25 g of sodium alginic acid to the solution in small amounts and multiple times, continue to stir, and after the sodium alginic acid is completely dissolved, a milky white solution is obtained, cool to room temperature to obtain a bronze gel cleanser. The viscosity is 85409 mPa·s as determined by a viscometer.

[0101] Example 17

[0102] A method for preparing a gel cleanser, comprising:

[0103] Heat 20 g of ultrapure water to 95℃, add 0.08 g of ethylenediaminetetraacetic acid, continue to stir until completely dissolved, then add 1.2 g of polyvinyl alcohol type 1799, until the polyvinyl alcohol is completely dissolved to obtain a transparent aqueous solution, under stirring, add 1 mL of glycerol, 0.4 mL of propionic acid, stir for a period of time, then add 0.6 g of casein to the solution in small amounts and multiple times, continue to stir, and after the casein is completely dissolved, a milky white solution is obtained, cool to room temperature to obtain a bronze gel cleanser. The viscosity is 77946 mPa·s as determined by a viscometer.

[0104] Example 18

[0105] A method for preparing a gel cleanser, comprising:

[0106] 20g of ultrapure water was heated to 95℃, 0.08g of ethylenediaminetetraacetic acid was added, and stirred until completely dissolved, then 1.2g of polyvinyl alcohol type 1799 was added until the polyvinyl alcohol was completely dissolved to obtain a transparent aqueous solution, 1mL of glycerol, 0.4mL of propionic acid was added under stirring, after stirring for a period of time, 0.8g of sodium polyacrylate was added to the solution in small amounts, continue to stir, after the sodium polyacrylate was completely dissolved, a milky white solution was obtained, cooled to room temperature to obtain a bronze gel cleaner. The viscosity was determined by a viscometer, and the viscosity was 84209mPa·s.

[0107] Example 19

[0108] A method for preparing a gel cleaner, comprising:

[0109] 20g of ultrapure water was heated to 90℃, 0.08g of ethylenediaminetetraacetic acid was added, and stirred until completely dissolved, then 1.2g of polyvinyl alcohol type 1799 was added until the polyvinyl alcohol was completely dissolved to obtain a transparent aqueous solution, 1mL of glycerol, 0.4mL of propionic acid was added under stirring, after stirring for a period of time, 1g of carbomer 940 and 0.2g of methyl cellulose were added to the solution in small amounts, continue to stir, after the carbomer 940 and methyl cellulose were completely dissolved, a milky white solution was obtained, cooled to room temperature to obtain a bronze gel cleaner. The viscosity was determined by a viscometer, and the viscosity was 90687mPa·s.

[0110] Example 20

[0111] A method for preparing a gel cleaner, comprising:

[0112] 20g of ultrapure water was heated to 90℃, 0.08g of ethylenediaminetetraacetic acid was added, and stirred until completely dissolved, then 1.2g of polyvinyl alcohol type 1799 was added until the polyvinyl alcohol was completely dissolved to obtain a transparent aqueous solution, 1mL of glycerol, 0.4mL of propionic acid was added under stirring, after stirring for a period of time, 1.4g of methyl cellulose was added to the solution in small amounts, continue to stir, after the carbomer 940 and methyl cellulose were completely dissolved, a milky white solution was obtained, cooled to room temperature to obtain a bronze gel cleaner. The viscosity was determined by a viscometer, and the viscosity was 90687mPa·s.

[0113] Comparative Example 1

[0114] 50g distilled water was heated to 85℃, 1.0g polyvinyl alcohol 1799 was added and stirred until the polyvinyl alcohol 1799 was completely dissolved, heating was stopped and the solution temperature was cooled to 55℃, 4.0g carbomer 940 was added in small amounts, after the addition of carbomer 940, a small amount of carbomer was observed to be agglomerated, continued stirring until the aqueous solution became transparent, then 0.05g triethanolamine, 0.01g borax, 0.01g formic acid, 0.01g cysteine were added under stirring, cooled to room temperature, and distilled water was added to 100g, thus obtaining the golden layer copper rust gel rust remover.

[0115] Comparative Example 2

[0116] 0.8g hydroxypropyl guar gum and 0.4g sodium alginate were slowly added to 50g water under stirring at a speed of 1g / min, stirred until uniform, a transparent glue solution was obtained, then 1g sodium gluconate and 0.75g arginine were added to the glue solution respectively, stirred until uniform, and the bubbles disappeared after standing, thus obtaining the bronze cleaning agent.

[0117] Comparative Example 3

[0118] 0.6g hydroxypropyl guar gum and 0.4g sodium alginate were slowly added to 50g water under stirring at a speed of 2g / min, stirred until uniform, a transparent glue solution was obtained, then 2g sodium gluconate and 0.5g glutamic acid were added to the glue solution respectively, stirred until uniform, and the bubbles disappeared after standing, thus obtaining the bronze cleaning agent.

[0119] Comparative Example 4

[0120] 15g chitosan was added to 50g water under stirring, then 1g PVA was added to 25g water, and transparent aqueous solutions were obtained respectively, then the two aqueous solutions were mixed in a volume ratio of 2:1, stirred until uniform, 2mL of 0.1M silver nitrate aqueous solution was added, and stirred until uniform, thus obtaining a homogeneous solution.

[0121] Referring to Table 1, the components of the gel cleaning agents disclosed in Examples 1-20 and Comparative Examples 1-4 are compared; as can be seen from the table, the same multiple magnification or reduction of raw materials will not affect the properties of the finally obtained gel. The comparative examples in Table 1 do not contain a humectant component, and the addition of a humectant can prolong the service life of the gel rust remover. In order to reduce the influence of chemicals on bronze cultural relics and effectively remove copper rust, the pH value of the gel is adjusted by using only a weak acid, and the combination of carbomer and polyvinyl alcohol makes the gel rust remover have good film-forming property and viscoelasticity, so no crosslinking agent is added.

[0122] The results of the performance tests of the gel cleaning agents prepared in Examples 1-8 are compared in Table 2. The gel cleaning agents prepared in Examples are subjected to detailed mechanical property tests using an ultra-depth microscope and a universal testing machine. Good tensile properties can ensure the integrity of the film after film formation, and the gel will not be difficult to peel off due to excessive viscosity or directly damage the fragile cultural relics. Proper viscosity can make the gel stay on the surface of the cultural relics.

[0123] The method for removing rust from bronze artifacts using the gel cleaning agents disclosed in Examples 1-8 and Comparative Examples 1-4 is shown in Table 3. The gel is applied to the surface of the copper rust by different methods in the present application. The formed gel can be peeled off from the surface of the cultural relics, and has a certain toughness to reduce residue. The gel rust remover cannot form a film after rust removal, and it is difficult to remove the chemical components, which causes new damage to the cultural relics protection work. Compared with the pouring method in the comparative examples, the present application has appropriate viscoelasticity, viscosity and toughness, which can make the gel stay on the surface of the cultural relics without flowing, ensure the integrity of the film after film formation, and will not be difficult to peel off due to excessive viscosity or directly damage the fragile cultural relics. It is suitable for fragile bronze and thin sheet-shaped fragile bronze, and is also suitable for parts such as gaps and cavities that are difficult to remove rust.

[0124] Table 1 Comparison of components of gel cleaning agents disclosed in Examples 1-20 and Comparative Examples 1-4

[0125]

[0126]

[0127] Table 2 Comparison of performance test results of gel cleaning agents prepared in Examples 1-8

[0128]

[0129] Table 3 Method for removing rust from bronze artifacts using gel cleaning agents disclosed in Examples 1-8 and Comparative Examples 1-4

[0130]

[0131] The method for cleaning the copper rust of fragile bronze artifacts prepared in the present application uses a variety of organic polymer film formers with biocompatibility, including polyvinyl alcohol, which causes less damage to cultural relics and has no corrosion effect on metals. The prepared gel cleaning agent is a coating type cleaning agent, and the effective substances in it can be more fully utilized. This gel cleaning agent has good film forming property and short film forming time, and also has certain functions such as moisturizing, antibacterial and acid resistance. The coating method can better contact with cultural relics, and due to its excellent toughness, the residue of the gel is greatly reduced after rust removal.

[0132] In order to prove the effect of the present application, the inventors cleaned the surface layer of the bronze relic fragment by using Example 3, and the photos before and after cleaning are shown in Figure 4 As can be seen from the figure, the present application can effectively remove the copper rust on the surface of the bronze relic fragment, and the golden color of the surface of the relic fragment is clearly exposed. According to element analysis, the gel film obtained after cleaning contains Cu and other elements in the copper rust, but does not contain Sn, Pt and other essential elements of bronze, which indicates that the present application can effectively remove the copper rust without damaging the cultural relics.

[0133] The above content only illustrates the technical idea of the present application, and cannot limit the protection scope of the present application. Any modification made according to the technical idea of the present application on the basis of the technical scheme falls within the protection scope of the claims of the present application.

Claims

1. A gel cleaner characterized by, The gel cleaning agent comprises, in mass percentage: 0.1%-0.8% of a copper ion chelating agent, 2%-10% of a film forming agent, 1%-10% of a humectant, 0.1%-3% of a weak acid, 2%-8% of a thickening agent, and the rest is water; the gel cleaning agent has a tensile strength of 5-48 KPa, an elastic modulus of 4.54-38.90 KPa, an elongation of 62.3%-248.1%, and a viscosity of 36027-334230 mPa·s; The copper ion chelating agent is at least one of amino triacetic acid, diethylene triamine pentaacetic acid, ethylene diamine tetraacetic acid, citric acid, tartaric acid, gluconic acid, and polyacrylic acid; The film forming agent is at least one of polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, hydroxypropyl methyl cellulose, pectin, polyurethane, trimethyl siloxy silicate, acrylic resin, dimethyl siloxane copolymer, and acrylic copolymer emulsion; The weak acid is at least one of formic acid, acetic acid, propionic acid, oxalic acid, hypochlorous acid, and nitrous acid; The thickening agent is at least one of starch, gum arabic, pectin, agar, gelatin, alginin, carrageenan, propylene glycol alginic acid ester, carbomer, methyl cellulose, starch sodium phosphate, sodium carboxymethyl cellulose, sodium alginic acid, casein, and sodium polyacrylate.

2. The gel cleaner of claim 1, wherein, The gel cleaning agent comprises, in mass percentage: 0.3%-0.8% of a copper ion chelating agent, 2%-8% of a film forming agent, 5%-9% of a humectant, 1%-3% of a weak acid, 5%-8% of a thickening agent, and the rest is water.

3. The gel cleaner of claim 1, wherein, The humectant is at least one of glycerol, butylene glycol, caprylyl glycol, sorbitol, hyaluronic acid, sodium polyglutamate, betaine, lysine, arginine, xylitol, collagen, and algal extract.

4. Process for the preparation of a gel cleaner according to any one of claims 1 to 3, characterized in that, The gel cleaning agent comprises: Water is heated to 90-95 ℃, the copper ion chelating agent is added and stirred until completely dissolved, the film forming agent is added until completely dissolved to obtain a transparent solution, the humectant and the weak acid are added during stirring, the thickening agent is added after stirring uniformly, and the gel cleaning agent is obtained after cooling to room temperature.

5. Use of the gel cleaning agent according to any one of claims 1 to 3 for the removal of corrosion from delicate bronze artefacts, characterized in that, The gel cleaning agent is thickly applied to the rust removal part of the bronze ware, and is removed after film formation.

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