CN112609507A

CN112609507A - Deacidifying protection method for concave-convex structured rubbing

Info

Publication number: CN112609507A
Application number: CN202011443319.3A
Authority: CN
Inventors: 张溪文; 陈炳铨; 施文正; 徐绍艳
Original assignee: Hangzhou Magnumaterials Technology Co ltd
Current assignee: Hangzhou Magnumaterials Technology Co ltd
Priority date: 2020-12-08
Filing date: 2020-12-08
Publication date: 2021-04-06
Anticipated expiration: 2040-12-08
Also published as: CN112609507B

Abstract

The application provides a deacidification protection method of a concave-convex structural rubbing, which comprises the following steps: 1) activating the surface of the rubbing by using plasma gas flow, and removing the inert layer on the surface of the rubbing; the plasma gas flow activation is to take out plasma generated by gas plasma discharge in the reaction chamber through air to generate plasma gas flow to perform activation treatment on the rubbing; 2) and atomizing the deacidification agent, and then carrying out deacidification treatment on the infiltration rubbing. The method completes deacidification of the rubbing on the premise of not damaging the concave-convex structure of the rubbing surface and the surface dye and ink marks of the rubbing.

Description

Deacidifying protection method for concave-convex structured rubbing

Technical Field

The application relates to the field of cultural relic deacidification protection, in particular to a deacidification protection method of a concave-convex structural rubbing.

Background

Rubbing is a paper sheet which is formed by rubbing the shapes of the surfaces of utensils such as inscriptions on stone, nail bone bronze, coins and pictures, characters and patterns on the surface of the utensils, etc., and the paper sheet is attached to the hard surface of the utensils, and the characters and the patterns on the surfaces of the utensils are clearly copied onto the paper sheet by rubbing and combining dyes. The rubbing is one of important carriers for recording long history and culture of Chinese nationalities, is an ancient traditional technology of China, and is a plurality of lost and damaged inscriptions, bronze wares and other cultural relics, and the recording can be stored only due to the existence of the rubbing. Rubbing paper is mostly the rice paper of super absorbent nature, and ancient rubbing dyestuff adopts chinese ink more, and modern rubbing usually uses the pencil to replace, and its main component all is graphite.

The rubbing paper mainly comprises cellulose, and due to the characteristics of the rubbing and the particularity of the preservation time and the environment of the rubbing, the rubbing paper is easy to acidify (namely, the rubbing is wholly acidic), and under the acidic environment, the cellulose in the rubbing paper can be hydrolyzed under the catalytic action of hydrogen ions, so that the fiber molecular chains are broken, the concave-convex structure on the surface of the rubbing is influenced, and the overall strength is reduced. Meanwhile, printing and dyeing ink marks can fall off, so that characters, patterns and the like stored on the surface of the rubbing are damaged, and the information loss on the surface of the rubbing is caused. It is therefore necessary to deacidify the acidified rubbing paper in a timely manner.

Because the rubbing surface has unevenness structure, and because the rubbing retention time is longer, there is the inert layer on the surface, this deacidification that makes the rubbing is different from the deacidification of ordinary paper, needs special deacidification agent and deacidification method. The deacidification method adopted by the rubbing at present mainly comprises a soaking deacidification method and a spraying deacidification method, wherein the soaking deacidification method is to directly soak the rubbing in deacidification liquid, and because the organic solvent deacidification liquid can damage ink on the surface of the rubbing, the rubbing is soaked by a water-based deacidification liquid; the spraying deacidification method is to spray rubbing by using alkaline nano magnesium oxide and other micro solid particles suspended in an organic solvent to achieve the deacidification effect. However, in the two methods, the water content in the rubbing is too high due to direct soaking in the aqueous deacidification solution, so that the fibers of the rubbing are deformed, and the structure of the rubbing is damaged; micro solid particles in the organic solvent can generate scouring action on the rubbing in the spraying process, and damage is caused to the concave-convex shape structure on the surface of the rubbing. And the inert layer on the surface of the rubbing can not be removed by the two deacidification methods, so the deacidification effect is not ideal.

Disclosure of Invention

Therefore, the technical problem of how to complete the effective deacidification of the rubbing under the condition of not damaging the concave-convex structure, the dye and the ink marks on the surface of the rubbing needs to be solved, and the deacidification protection method of the rubbing with the concave-convex structure is provided.

The technical scheme provided by the invention is as follows: a deacidification protection method of a concave-convex structural rubbing comprises the following steps:

1) activating the surface of the rubbing by using plasma gas flow, and removing the inert layer on the surface of the rubbing; the plasma gas flow activation is to take out plasma generated by gas plasma discharge in the reaction chamber through air to generate plasma gas flow to perform activation treatment on the rubbing;

2) and atomizing the deacidification agent, and then carrying out deacidification treatment on the infiltration rubbing.

Among the above-mentioned technical scheme, adopt the plasma air current to treat the deacidification rubbing and handle, can get rid of the inert layer on rubbing surface to introduce free radical and other active particles on rubbing surface, improve the reactivity on rubbing surface, increase rubbing surface deacidification agent's adsorption capacity, improve rubbing's deacidification effect. Secondly, the rubbing is activated by plasma, the rubbing is not activated directly in the plasma reaction chamber, but plasma generated by gas discharge in the reaction chamber is taken out through air, and the rubbing is activated by using plasma airflow. Because contain graphite in the dyestuff on rubbing surface, if directly handle it in plasma emergence room, the part of rubbing surface enrichment graphite can be lighted under the plasma electric field, finally leads to rubbing paper body, surface pattern and concave-convex structure to receive the destruction, consequently this technical scheme can accomplish the deacidification to the rubbing under the condition of not destroying rubbing surface concave-convex structure and dyestuff, ink mark, deacidification process easy operation, and deacidification effect is obvious.

Several alternatives are provided below, but not as an additional limitation to the above general solution, but merely as a further addition or preference, each alternative being combinable individually for the above general solution or among several alternatives without technical or logical contradictions.

Optionally, the plasma is a cold plasma. The cold plasma is composed of electrons, free radicals and positive and negative ions, has high reactivity, and the temperature of the electrons in the cold plasma is high, but the temperature of heavy particles such as ions is low, so that the whole gas flow of the cold plasma is in a low-temperature state, and the inert layer on the surface of the rubbing can be removed without damaging the paper body and the paper surface information.

Optionally, the plasma is generated by a gaseous dielectric barrier discharge, glow discharge or corona discharge. Gas dielectric barrier discharge, namely, a specific dielectric material is attached to the discharge electrodes, and gas between the electrodes is punctured to complete discharge; glow discharge means that positive ions bombard the surface of a cathode electrode under certain air pressure to generate secondary electrons to complete discharge; the corona discharge is completed by ionizing and exciting the gas by using a high-intensity local electric field near a tip electrode with a small curvature radius.

Preferably, the plasma is generated by a gas dielectric barrier discharge mode, the method can be completed under normal pressure, the gas discharge energy level is high, the distribution is uniform, and the rubbing of the concave-convex structure can be fully and uniformly activated.

Optionally, the plasma is generated by an electrical discharge of one or more of air, nitrogen or an inert gas. The inert gas includes helium, argon, and the like.

Optionally, the time of the activation treatment of the rubbing in the plasma airflow is 2-5 min. Because the surface of the rubbing has an inert layer formed by dirt such as dust and the like, and needs to be activated and removed by plasma airflow, the time for plasma airflow treatment cannot be too short, and correspondingly, the long-time plasma treatment can affect the concave-convex structure, the dye, the ink marks and the like on the surface of the rubbing. Further preferably, the time of the activation treatment of the rubbing in the plasma airflow is 3-4 min.

Optionally, the deacidification agent in the step 2) is an aqueous deacidification liquid. Since the solvent of the organic deacidification agent is an organic solution with good dissolution and permeability, the dye, ink and the like on the surface of the rubbing can be damaged.

Optionally, the aqueous deacidification agent is one or more of a calcium hydroxide solution, a magnesium hydroxide solution, a calcium bicarbonate solution or a magnesium bicarbonate solution.

Optionally, the deacidification agent is atomized by mechanical atomization, medium atomization or ultrasonic atomization.

The invention has the following beneficial effects:

(1) the method provided by the invention can complete deacidification of the rubbing on the premise of not damaging the concave-convex structure of the rubbing surface and the surface dye and ink marks of the rubbing.

(2) The plasma gas flow treatment adopted by the invention is non-contact dry operation, the requirements on equipment and environment are low, the inert layer on the surface of the rubbing can be removed, the wettability of the aqueous deacidification agent on the paper surface can be improved, and the subsequent deacidification effect can be improved.

(3) The atomization deacidification process provided by the invention is simple in process flow, the distribution of the deacidification agent after atomization on the rubbing is uniform, the deacidification process is mild, the surface structure of the rubbing cannot be damaged, and the deacidification effect is obvious.

Drawings

FIG. 1 is a picture of the acidification topology of example 1 before and after deacidification treatment;

FIG. 2 is a photograph of the acidified topology of comparative example 1 after direct treatment in a plasma reaction chamber.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

For a better description and illustration of embodiments of the application, reference may be made to one or more of the drawings, but additional details or examples used in describing the drawings should not be construed as limiting the scope of any of the inventive concepts of the present application, the presently described embodiments, or the preferred versions.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

Example 1

Select the rubbing of acidizing (rice paper material), adopt direct current high voltage power supply to produce plasma through dielectric barrier discharge's mode in the plasma reaction chamber, gaseous helium that adopts, reaction voltage is 60V, and the electric current is 0.3A, let in the plasma that gas discharge produced in with the reaction chamber in the air and take out, produce the plasma air current, when the stable pulse current filament appears in treating the reaction chamber, the time that starts the timing, the rubbing is handled to the plasma air current is 3min, after plasma handles the completion, the power is closed, take out the rubbing and put into deacidification room for use.

Firstly, carrying out ultrasonic atomization on a calcium hydroxide solution with the concentration of 4 wt%, introducing an atomized deacidification agent into a deacidification chamber, taking out the rubbing after the rubbing surface is infiltrated by the atomized deacidification agent, and naturally drying the rubbing in the air to finish the deacidification process of the rubbing.

And (3) performance testing:

a picture of the deacidified treated topology of example 1 and the same topology without any treatment is shown in FIG. 1, from which it can be seen that the relief structure and the dyes, ink marks, etc. of the surface of the topology after deacidification by plasma gas flow activation did not change significantly and remained substantially the same as the original topology.

The same untreated fabric of example 1 and the fabric of example 1 that had been subjected to plasma gas flow activation and deacidification were tested for pH and the results are shown in table 1. It can be seen from the table that when not deacidifying, the rubbing presents obvious acidity, after plasma air current processing and deacidification agent are handled, the pH value on rubbing surface obviously improves, and the deacidification effect is obvious, and the rubbing is weak alkaline after the deacidification, can play continuous guard action to the rubbing.

Table 1: pH value before and after deacidification of acidification rubbing (rice paper material)

Number of measurements	Original	After deacidification
			1	5.3	8.1
2	5.7	8.3
			3	5.8	7.8
Average	5.6	8.1

Comparative example 1

The rubbing (rice paper material) of selecting acidizing is directly put into the plasma reacting chamber, adopts direct current high voltage power supply, and the gas discharge mode is dielectric barrier discharge, and gas adopts the helium, opens the power, and adjustment reaction voltage is 60V, and the electric current is 0.3A, when treating that stable pulse current filament appears in rubbing surface in the reacting chamber, begins the timing, and the time of rubbing processing is 3min in the plasma reacting chamber, handles 3min after, takes out the rubbing.

Looking at the surface of the rubbing, as shown in FIG. 2, it was found that a portion of the surface of the rubbing directly processed in the plasma reaction chamber was damaged. This is because the dye and ink on the surface of the rubbing contain graphite, and the graphite-rich areas can be ignited by the high voltage electric field in the plasma reaction chamber, thereby damaging the surface pattern and structure of the rubbing.

Comparative example 2

Selecting an acidified rubbing (rice paper material), treating for 3min by using a general gas flow without cold plasma, taking out the rubbing after 3min treatment, and putting the rubbing into an acid removal chamber for later use.

And (3) performance testing:

the same rubbings without any treatment in comparative example 2 and the rubbings treated with the deacidification agent in comparative example 2 were taken for pH value test, and the test results are shown in Table 2. As can be seen from the table, when deacidification is not carried out, the rubbing is obviously acidic, after deacidification treatment, the pH value of the rubbing surface is improved, but the deacidification effect is poor, the rubbing is still weakly acidic after deacidification, and the phenomenon of acid reversion is easy to occur.

Table 2: pH value before and after acidification rubbing direct deacidification

Number of measurements	Original	After deacidification
			1	5.5	6.7
2	5.4	7.1
			3	5.7	6.8
Average	5.5	6.9

Example 2

The deacidification agent in example 1 was adjusted to a 3 wt% magnesium hydroxide solution, and the procedure was the same as in example 1. The final deacidification effect was substantially the same as in example 1.

Example 3

The deacidification agent in example 1 was adjusted to 8 wt% calcium hydrogen carbonate solution, and the procedure was otherwise the same as in example 1. The final deacidification effect was substantially the same as in example 1.

Example 4

The deacidification agent in example 1 was adjusted to a 5 wt% magnesium bicarbonate solution, and the procedure was otherwise the same as in example 1. The final deacidification effect was substantially the same as in example 1.

Example 5

The operation procedure of example 1 was otherwise the same as that of example 1 except that the deacidification agent atomization method in example 1 was changed to medium atomization and the medium was compressed air. The final deacidification effect was substantially the same as in example 1.

Example 6

The operation procedure of example 1 was otherwise the same as that of example 1 except that the deacidification agent atomization method in example 1 was changed to mechanical atomization. The final deacidification effect was substantially the same as in example 1.

Example 7

Select the rubbing of acidizing (coarse paper material), adopt direct current high voltage power supply to produce plasma through dielectric barrier discharge's mode in the plasma reaction chamber, gaseous nitrogen gas that adopts, reaction voltage is 50V, and the electric current is 0.2A, let in the plasma that gas discharge produced in with the reaction chamber of air, produce the plasma air current, when treating stable impulse current filament to appear in the reaction chamber, begin the timing, the time that the rubbing was handled to the plasma air current is 4min, after plasma handles the completion, the power is closed, take out the rubbing and put into deacidification room for use.

And (3) performance testing:

the same untreated rubbing of example 7 and the rubbing of example 7 treated with plasma gas flow and deacidifying agent were tested for pH, and the results are shown in Table 3. It can be seen from the table that when not deacidifying, the rubbing presents obvious acidity, after plasma air current processing and deacidification agent are handled, the pH value on rubbing surface obviously improves, and the deacidification effect is obvious, and the rubbing is weak alkaline after the deacidification, can play continuous guard action to the rubbing.

Table 3: pH value before and after deacidification of acidified rubbing (coarse paper material)

Number of measurements	Original	After deacidification
			1	5.3	7.7
2	5.1	7.9
			3	5.7	8.0
Average	5.4	7.9

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed 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 concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. A deacidification protection method of a concave-convex structural rubbing is characterized by comprising the following steps:

2. A process for deacidification and protection of a relief structure topology according to claim 1, wherein said plasma is a cold plasma.

3. A method for deacidification protection according to an attapulgite topology according to claim 1, wherein said plasma is generated by a gaseous dielectric barrier discharge, glow discharge or corona discharge.

4. A method for deacidification protection according to an abrasive relief structure according to claim 1, wherein said plasma is generated by one or more of electric discharge of air, nitrogen or inert gas.

5. A deacidification protection method according to an uneven structure type rubbing according to claim 1, characterized in that the time of activating treatment of said rubbing in plasma gas flow is 2-5 min.

6. A process for deacidification protection according to an embossing topology according to claim 1, wherein said deacidification agent in step 2) is an aqueous deacidification liquid.

7. A process for deacidification protection according to an attapulgite topology according to claim 6, wherein said aqueous deacidification agent is one or more of calcium hydroxide solution, magnesium hydroxide solution, calcium bicarbonate solution or magnesium bicarbonate solution.

8. A process for deacidification protection according to an embossing topology as recited in claim 1 wherein said deacidification agent is atomized by means including mechanical atomization, media atomization or ultrasonic atomization.