阅读说明：本技术 一种青铜器清洗剂及其制备方法 (Bronze ware cleaning agent and preparation method thereof ) 是由 马菁毓 候长旭 牛春梅 王若琳 于 2021-08-12 设计创作，主要内容包括：本发明涉及文物清洗技术领域,具体公开一种青铜器清洗剂及其制备方法。所述清洗剂,按照重量百分比计,包括以下组分：植物多糖：2％～2.4％、葡萄糖酸钠2％～4％和氨基酸1％～2％,其余为水,其中所述植物多糖为羟丙基瓜尔胶和海藻酸钠的混合物。本发明选择的植物多糖、葡萄糖酸钠和氨基酸安全温和,具有生物降解性,不含有任何有害成分,能够在青铜器表面的污垢上充分覆盖润湿成膜,使用方便,还能根据青铜器文物的纹理改变形成除锈膜,确保本申请提供的清洗剂与青铜器文物均匀接触,且在清洗过程中不会断裂和留下残留物,保证了清洗的定点、可控,避免了扩散造成二次污染情况的发生。(The invention relates to the technical field of cultural relic cleaning, and particularly discloses a bronze ware cleaning agent and a preparation method thereof. The cleaning agent comprises the following components in percentage by weight: plant polysaccharide: 2-2.4% of sodium gluconate, 1-2% of amino acid and the balance of water, wherein the plant polysaccharide is a mixture of hydroxypropyl guar gum and sodium alginate. The plant polysaccharide, the sodium gluconate and the amino acid selected by the cleaning agent are safe and mild, have biodegradability, do not contain any harmful component, can be fully covered and wetted to form a film on dirt on the surface of a bronze ware, are convenient to use, can form a rust removal film according to the change of the texture of the bronze ware cultural relic, ensure that the cleaning agent provided by the application is uniformly contacted with the bronze ware cultural relic, cannot break and leave residues in the cleaning process, ensure that the cleaning is fixed and controllable, and avoid the occurrence of secondary pollution caused by diffusion.)

1. A bronze ware cleaning agent is characterized in that: the paint comprises the following components in percentage by weight: plant polysaccharide: 2-2.4% of sodium gluconate, 1-2% of amino acid and the balance of water, wherein the plant polysaccharide is a mixture of hydroxypropyl guar gum and sodium alginate.

2. The bronze cleaning agent as set forth in claim 1, wherein: the mass ratio of the hydroxypropyl guar gum to the sodium alginate is 3-2: 2-1.

3. The bronze cleaning agent as set forth in claim 1, wherein: the molecular weight of the hydroxypropyl guar gum is 10-13 ten thousand daltons.

4. The bronze cleaning agent as set forth in claim 1, wherein: the hydroxypropyl guar gum has a hydroxypropyl degree of substitution of 1.2-1.7.

5. The bronze cleaning agent as set forth in claim 1, wherein: the amino acid is at least one of arginine, glutamic acid, glycine, threonine or alanine.

6. The bronze cleaning agent as claimed in any one of claims 1 to 5, wherein: the apparent viscosity of the cleaning agent is 12000mPa & s-16000 mPa & s.

7. A preparation method of a bronze ware cleaning agent is characterized by comprising the following steps: at least comprises the following steps:

weighing the components according to the raw material proportion of any one of claims 1 to 6;

step two, adding the plant polysaccharide into water under the stirring condition to obtain a glue solution;

and step three, respectively adding the sodium gluconate and the amino acid into the glue solution, and uniformly stirring to obtain the bronze ware cleaning agent.

8. The method for preparing a bronze ware cleaning agent according to claim 7, wherein the bronze ware cleaning agent comprises: in the second step, the stirring speed is 80-100 rpm, and the adding speed of the plant polysaccharide is 1-2 g/min.

Technical Field

The invention relates to the technical field of cultural relic cleaning, and particularly relates to a bronze ware cleaning agent and a preparation method thereof.

Background

The bronze ware mainly comprises copper, lead and zinc, is generally used for recording national events, and has great significance for historical witnesses. However, during long-term storage, various kinds of dirt and rust appear on the surface of the bronze ware, which not only affect the appearance, but also irreparably damage the bronze ware itself due to the presence of the patina component. Therefore, the removal of the patina on the surface of the bronze ware becomes an urgent problem to be solved in the protection of bronze ware cultural relics.

The rust removal of the bronze ware is realized by removing rust on the surface of the bronze ware through a physical method or a chemical method, and the physical rust removal method is quite direct, but has higher process requirement, immature technology, difficult rust removal work on a larger area, easy damage to a bronze ware matrix and incapability of completely removing powdery harmful rust (cuprous chloride). The chemical rust removal method can remove some rust materials in a targeted and thorough manner, but the chemical reagent has the problems of residue, easy flowing, incapability of well controlling the working range of the rust remover, easy volatilization and the like, not only can corrode or otherwise damage the bronze ware matrix, but also can reduce the working efficiency of rust removal.

Disclosure of Invention

In view of the above, the invention provides a bronze ware cleaning agent and a preparation method thereof, which have biodegradability, no residue and no flow phenomenon, excellent cleaning effect and can thoroughly remove harmful rust.

In order to achieve the purpose of the invention, the embodiment of the invention adopts the following technical scheme:

the bronze ware cleaning agent comprises the following components in percentage by weight: plant polysaccharide: 2-2.4% of sodium gluconate, 1-2% of amino acid and the balance of water, wherein the plant polysaccharide is a mixture of hydroxypropyl guar gum and sodium alginate.

Compared with the prior art, the bronze ware cleaning agent provided by the application has the following advantages:

the application takes sodium gluconate and amino acid as metal chelating agents, the sodium gluconate has strong complexing ability to metal ions such as calcium, magnesium, iron, copper and the like on the surface of a bronze ware, then the copper ions are removed in the cleaning process, the amino acid and the monovalent copper ions on the surface of the bronze ware form coordinate bonds to obtain a chelate of the monovalent copper ions, so that the cleaning agent can also remove the harmful rust cuprous chloride in the patina in the cleaning process, hydroxypropyl guar gum with a large number of hydrogen bonds and sodium alginate containing carboxyl and sugar rings are taken as macromolecular polysaccharide skeletons, the molecules and the intermolecular can form strong hydrogen bonds and are associated with each other to be physically entangled to form gel with reasonable viscosity, the cleaning agent can avoid the phenomenon of flowing when the viscosity is too low in the cleaning process, and can also avoid the phenomenon that sodium gluconate and amino acid in gel can not be chelated with metal ions on the surface of a bronze ware due to the fact that the cleaning agent has too high viscosity and can not permeate into the texture of the bronze ware.

Preferred plant polysaccharide, sodium gluconate and amino acid are safe mild, have the biodegradability, do not contain any harmful component, can fully cover moist membrane of forming on the dirt on bronze ware surface, high durability and convenient use, can also change the formation rust removal membrane according to the texture of bronze ware historical relic, ensure that the cleaner that this application provided and bronze ware historical relic even contact, and can not fracture and leave the residue in the cleaning process, guaranteed abluent fixed point, controllable, avoided the diffusion to cause the emergence of secondary pollution condition. The cleaning agent provided by the application can realize in-situ, efficient and controllable derusting, and has great potential application value in cultural relic repair and protection.

Preferably, the mass ratio of the hydroxypropyl guar gum to the sodium alginate is 3-2: 2-1.

The preferable proportion of the hydroxypropyl guar gum and the sodium alginate ensures that the cleaning agent forms a dense three-dimensional network structure and has a specific viscosity, so that the cleaning agent can be adhered to the surface of the bronze ware, cannot flow, and cannot be easily remained or damage the surface of the bronze ware due to excessive viscosity.

Preferably, the molecular weight of the hydroxypropyl guar gum is 10-13 ten thousand daltons.

The preferred molecular weight is such that the hydroxypropyl guar gum and sodium alginate form plant polysaccharide macromolecules of a specific viscosity, such that the cleaning agent has a specific viscosity.

Preferably, the hydroxypropyl guar has a hydroxypropyl degree of substitution of 1.2 to 1.7.

Preferably, the amino acid is at least one of arginine, glutamic acid, glycine, threonine, or alanine.

Preferred amino acids contain-COOH and-NH in the molecule₂And the oxygen on the carboxyl group, the nitrogen on the amino group and the monovalent copper ions form coordinate bonds, so that the amino acid and the monovalent copper ions are chelated, and the harmful rust cuprous chloride in bronze rust is removed in the cleaning process.

Preferably, the apparent viscosity of the cleaning agent is 12000 mPas-16000 mPas.

The method for testing the apparent viscosity specifically comprises the following steps: standing the cleaning agent prepared by the method until bubbles disappear stably, and testing the apparent viscosity of the cleaning agent by using a DV3T type BROOKFIELD rheometer under the test conditions of 25 ℃ and 62 ℃ as a rotor^#。

The preferable apparent viscosity enables the cleaning agent to be adhered to the surface of the bronze ware to form a three-dimensional network structure, and the cleaning agent does not flow, and the release of sodium gluconate and amino acid in the cleaning agent cannot be influenced due to overlarge viscosity.

Further, the invention also provides a preparation method of the bronze ware cleaning agent, which at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

step two, adding the plant polysaccharide into water under the stirring condition to obtain a glue solution;

and step three, respectively adding the sodium gluconate and the amino acid into the glue solution, and uniformly stirring to obtain the bronze ware cleaning agent.

The preparation method provided by the application is simple to operate, low in production cost, high in safety and environment-friendly, and is beneficial to realizing industrial production of the bronze ware cleaning agent.

Preferably, in the second step, the stirring speed is 80-100 rpm, and the adding speed of the plant polysaccharide is 1-2 g/min.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.

FIG. 1 is a diagram showing the rust removing effect provided in embodiments 1 to 6 of the present invention;

FIG. 2 is a diagram showing the rust removing effect provided in comparative examples 1 to 2 of the present invention;

FIG. 3 is an infrared spectrum of the bronze ware cleaning agent provided in example 1 of the present invention;

FIG. 4 is a scanning electron micrograph of a bronze ware cleaning agent provided in example 1 of the present invention;

FIG. 5 is a scanning electron micrograph of a bronze ware cleaning agent according to comparative example 1 of the present invention;

FIG. 6 is a scanning electron micrograph of a bronze ware cleaning agent according to comparative example 2 of the present invention.

Detailed Description

In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

The following examples are provided to better illustrate the embodiments of the present invention.

Example 1

The embodiment provides a bronze ware cleaning agent which comprises the following components in percentage by weight: hydroxypropyl guar gum: 1.6 percent of sodium alginate, 0.8 percent of sodium alginate, 2 percent of sodium gluconate and 1.5 percent of arginine, and the balance of water.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

slowly adding the hydroxypropyl guar gum and the sodium alginate into water at a speed of 1g/min under the stirring condition, and stirring at a speed of 100rpm until the mixture is uniform to obtain transparent gum solution;

and step three, respectively adding the sodium gluconate and the arginine into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

Example 2

The embodiment provides a bronze ware cleaning agent which comprises the following components in percentage by weight: hydroxypropyl guar gum: 1.2 percent of sodium alginate, 0.8 percent of sodium alginate, 4 percent of sodium gluconate and 1 percent of glutamic acid, and the balance of water.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

slowly adding the hydroxypropyl guar gum and the sodium alginate into water at a speed of 2g/min under the stirring condition, and stirring uniformly at a speed of 80rpm to obtain a transparent gum solution;

and step three, respectively adding the sodium gluconate and the glutamic acid into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

Example 3

The embodiment provides a bronze ware cleaning agent which comprises the following components in percentage by weight: hydroxypropyl guar gum: 1.2 percent of sodium alginate, 1.2 percent of sodium gluconate, 3 percent of glycine and the balance of water.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

step two, slowly adding the hydroxypropyl guar gum and the sodium alginate into water at a speed of 1.5g/min under the stirring condition, and stirring uniformly at a speed of 90rpm to obtain transparent gum solution;

and step three, respectively adding the sodium gluconate and the glycine into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

Example 4

The embodiment provides a bronze ware cleaning agent which comprises the following components in percentage by weight: hydroxypropyl guar gum: 1.5 percent of sodium alginate, 0.5 percent of sodium gluconate, 2.5 percent of threonine and the balance of water.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

step two, slowly adding the hydroxypropyl guar gum and the sodium alginate into water at a speed of 1.8g/min under the stirring condition, and stirring uniformly at a speed of 100rpm to obtain transparent gum solution;

and step three, respectively adding the sodium gluconate and the threonine into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

Example 5

The embodiment provides a bronze ware cleaning agent which comprises the following components in percentage by weight: hydroxypropyl guar gum: 1.8 percent of sodium alginate, 0.6 percent of sodium alginate, 2 percent of sodium gluconate and 1 percent of alanine, and the balance of water.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

slowly adding the hydroxypropyl guar gum and the sodium alginate into water at a speed of 2g/min under the stirring condition, and stirring uniformly at a speed of 95rpm to obtain a transparent gum solution;

and step three, respectively adding the sodium gluconate and the alanine into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

Example 6

The embodiment provides a bronze ware cleaning agent which comprises the following components in percentage by weight: hydroxypropyl guar gum: 1 percent of sodium alginate, 1 percent of sodium gluconate, 4 percent of glutamic acid and the balance of water.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

slowly adding the hydroxypropyl guar gum and the sodium alginate into water at a speed of 1g/min under the stirring condition, and stirring at a speed of 80rpm until the mixture is uniform to obtain a transparent gum solution;

and step three, respectively adding the sodium gluconate and the glutamic acid into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

In order to better illustrate the technical solution of the present invention, further comparison is made below by means of a comparative example and an example of the present invention.

Comparative example 1

The comparative example provides a bronze ware cleaning agent which comprises the following components in percentage by weight: guar gum: 1.6 percent of sodium alginate, 0.8 percent of sodium alginate, 2 percent of sodium gluconate and 1.5 percent of arginine, and the balance of water.

The molecular weight of the guar gum is 10-13 ten thousand daltons.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

slowly adding the guar gum and the sodium alginate into water at a speed of 1g/min under the stirring condition, and stirring at a speed of 100rpm until the guar gum and the sodium alginate are uniform to obtain transparent gum liquid;

and step three, respectively adding the sodium gluconate and the arginine into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

Comparative example 2

The comparative example provides a bronze ware cleaning agent which comprises the following components in percentage by weight: hydroxypropyl guar gum: 1.6 percent of hydroxypropyl methylcellulose, 0.8 percent of sodium gluconate, 1.5 percent of arginine and the balance of water.

The preparation method of the bronze ware cleaning agent at least comprises the following steps:

step one, weighing the components according to the raw material ratio;

step two, slowly adding the hydroxypropyl guar gum and the hydroxypropyl methyl cellulose into water at the speed of 1g/min under the stirring condition, and stirring uniformly at the speed of 100rpm to obtain transparent gum solution;

and step three, respectively adding the sodium gluconate and the arginine into the glue solution, stirring uniformly, standing until bubbles disappear, and obtaining the bronze ware cleaning agent.

Test example 1

The bronze ware cleaning agent prepared in examples 1 to 6 and comparative examples 1 to 2 was used to remove rust on the surface of a bronze ware. Taking 8 copper sheet rust samples with similar surface rust adhesion conditions, drawing rust removal areas with the same or similar areas on the copper sheets, respectively taking 0.7g of the bronze ware cleaning agent prepared in examples 1-6 and comparative examples 1-2, respectively and uniformly spreading cleaning agent gel on the surfaces of the rust removal areas by using tweezers, naturally drying the coated bronze ware cleaning agent gel in the air for 20 minutes, removing the gel film by using tools such as the tweezers after the rust removal components fully react with the copper sheet surface rust and are dried to form a film, and observing the rust removal effect. The gel films revealed in examples 1 to 6 are shown in FIG. 1 (examples 1 to 6 correspond to 1 to 6 in FIG. 1, respectively), and the gel films revealed in comparative examples 1 to 2 are shown in FIG. 2 (comparative examples 1 to 2 correspond to 1 to 2 in FIG. 2, respectively).

As is obvious from figure 1, the gel film after rust removal by the cleaning agent prepared by the method is full of copper rust, and the rust removal effect is excellent. The amount of the patina in the gel film uncovered in the figure 2 is very little and far lower than that in the figure 1, namely the rust remover prepared in the comparative examples 1-2 has poor rust removing effect and cannot meet the requirement of rust removal of the bronze ware.

Test example 2

The bronze ware cleaning agent prepared in example 1 was subjected to infrared spectrogram analysis, and the result is shown in fig. 3, from which it can be seen that the-OH peak was blue-shifted, indicating that intermolecular entanglement and crosslinking were generated due to the formation of hydrogen bonds in the bronze ware cleaning agent prepared in the present application.

The infrared spectra of the bronze ware cleaning agents prepared in examples 2 to 5 were consistent with the results of example 1.

Test example 3

Scanning electron microscope analysis was performed on the bronze ware cleaning agents prepared in example 1 and comparative examples 1 to 2, and the results are shown in fig. 4 to 6, respectively. The three-dimensional net structure of the cleaning agent prepared by the method can be visually seen from fig. 4, and the cleaning agent also has a porous structure.

The scanning photographs of the bronze ware cleaning agents prepared in examples 2 to 5 were in agreement with the results of example 1.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents or improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.