阅读说明：本技术 一种二氧化碳气氛下低温等离子体活化氢氧化钙加固风化石质文物的装置及方法 (Device and method for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in carbon dioxide atmosphere ) 是由 陈家昌 张良帅 贺思予 陈晓琳 唐静 闫海涛 王鑫光 迟铭 崔新战 刘欣 于 2019-12-17 设计创作，主要内容包括：本发明提供了一种二氧化碳气氛下低温等离子体活化氢氧化钙加固风化石质文物的的装置和方法,本发明从低温等离子体物理与文物保护学原理出发,将低温等离子体技术应用到文物保护领域,尤其是活化氢氧化钙加固风化石质文物领域。本发明使用通入二氧化碳气体的低温等离子体源对氢氧化钙进行活化加固,可在1min-2min内实现氢氧化钙的碳化、沉淀,并对风化石质文物起到加固作用,具有安全、高效、无损、无副作用的特点。(The invention provides a device and a method for strengthening weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in a carbon dioxide atmosphere. The invention uses the low-temperature plasma source which is introduced with carbon dioxide gas to activate and reinforce the calcium hydroxide, can realize the carbonization and the precipitation of the calcium hydroxide within 1-2 min, plays a role in reinforcing weathered stone cultural relics, and has the characteristics of safety, high efficiency, no damage and no side effect.)

1. The utility model provides a device that low temperature plasma activated calcium hydroxide consolidates morals and manners stone historical relic under carbon dioxide atmosphere which characterized in that: the device comprises a low-temperature plasma source, wherein a nozzle is arranged at the front end of the low-temperature plasma source, a carbon dioxide container is connected to the rear end of the low-temperature plasma source through a connecting pipe, and a pressure gauge is arranged on the carbon dioxide container.

2. The device for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma under carbon dioxide atmosphere according to claim 1, which is characterized in that: the carbon dioxide container is a carbon dioxide steel bottle.

3. The device for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma under carbon dioxide atmosphere according to claim 1, which is characterized in that: the rear end of the low-temperature plasma source is also connected with a power supply connecting wire and a grounding wire, the power supply connecting wire is connected with a power supply, and a switch is arranged on the power supply.

4. The device for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma under carbon dioxide atmosphere according to claim 1, which is characterized in that: a pressure gauge and a valve are arranged on the outlet of the carbon dioxide container.

5. A method for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in a carbon dioxide atmosphere is characterized by comprising the following steps: comprises the following steps of (a) carrying out,

(1) cleaning attachments on the surface of the stone cultural relic;

(2) dispersing calcium hydroxide into 5-5.5 vol% isopropanol water solution to obtain saturated solution with calcium hydroxide particle size smaller than 6.5 μm;

(3) spraying the reinforcing agent prepared in the step (2) on the weathered layer of the stone cultural relic;

(4) spraying the stone cultural relic sprayed with the reinforcing agent by the low-temperature plasma source nozzle introduced with carbon dioxide gas;

(5) repeating the step (3) and the step (4) for 10-15 times.

6. The method for strengthening weathered stone cultural relics by using the low-temperature plasma activated calcium hydroxide under the carbon dioxide atmosphere as claimed in claim 5, wherein the method comprises the following steps: in the step (4), the working voltage of the low-temperature plasma source is 110V-240V, the frequency is 50 Hz-60 Hz, and the maximum power is 30W; and (4) reinforcing once every time step (3) and step (4) are carried out, wherein the interval of reinforcing for each time is at least 20 min.

7. The method for reinforcing weathered stone cultural relics by using the device for reinforcing the weathered stone cultural relics by using the low-temperature plasma activated calcium hydroxide under the carbon dioxide atmosphere as claimed in claim 5, wherein the device comprises: in the step (4), the standard processing distance of the low-temperature plasma source is 2 mm-10mm, and the standard processing width is 5-20 mm.

8. The method for strengthening weathered stone cultural relics by using the low-temperature plasma activated calcium hydroxide under the carbon dioxide atmosphere as claimed in claim 5, wherein the method comprises the following steps: in the step (4), the low-temperature plasma source generates cold plasma with the temperature of less than 50 ℃.

9. The method for strengthening weathered stone cultural relics by using the low-temperature plasma activated calcium hydroxide under the carbon dioxide atmosphere as claimed in claim 5, wherein the method comprises the following steps: and (4) scanning the position of the stone cultural relic sprayed with the reinforcing agent for 1-2 min by using plasma flame at the nozzle of the low-temperature plasma source.

10. The method for strengthening weathered stone cultural relics by using the low-temperature plasma activated calcium hydroxide under the carbon dioxide atmosphere as claimed in claim 5, wherein the method comprises the following steps: in the step (2), the preparation method of the reinforcing agent comprises the steps of dispersing nano calcium hydroxide or calcium hydroxide which is less than or equal to 6.5 microns and is produced by Shanghai Mecline company into an isopropanol water solution with the volume concentration of 5-5.5%, and continuously stirring for 2-3 hours by using a magnetic stirrer or vibrating for 2-3 hours by ultrasonic waves to prepare a saturated solution.

Technical Field

The invention relates to the field of cultural relic protection, in particular to a device and a method for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in a carbon dioxide atmosphere.

Background

The materials for reinforcing weathered stone cultural relics at present mainly comprise three types of inorganic materials, organic materials and organic-inorganic composite materials. Among them, although organic materials have a good short-term reinforcing effect, they become brittle and yellow after aging for a long time, and their mechanical properties are reduced. Meanwhile, the film formed in the cultural relic is airtight, and the surface of the cultural relic can be expanded, pulverized and even dropped. In general, such materials have poor compatibility. Inorganic materials typified by calcium hydroxide have been widely studied in recent years because of their good compatibility. The calcium hydroxide particles react with carbon dioxide in the air to generate calcium carbonate so as to be integrated with the stone cultural relics. However, the traditional method for reinforcing the stone cultural relics by using calcium hydroxide also has the defects of low carbonization speed, low efficiency and the like, so that the reinforcing method is greatly restricted.

Disclosure of Invention

In order to solve the problems, the invention provides a device and a method for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in a carbon dioxide atmosphere.

The object of the invention is achieved in the following way: the device for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in carbon dioxide atmosphere comprises a low-temperature plasma source, wherein a nozzle is arranged at the front end of the low-temperature plasma source, a carbon dioxide container is connected to the rear end of the low-temperature plasma source through a connecting pipe, and a pressure gauge is arranged on the carbon dioxide container.

The carbon dioxide container is a carbon dioxide steel bottle.

The rear end of the low-temperature plasma source 1 is also connected with a power supply connecting wire and a grounding wire, the power supply connecting wire is connected with a power supply, and a switch is arranged on the power supply.

A pressure gauge and a valve are arranged on the outlet of the carbon dioxide container.

A method for strengthening weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in a carbon dioxide atmosphere comprises the following steps,

(1) cleaning attachments on the surface of the stone cultural relic;

(2) dispersing calcium hydroxide into 5-5.5 vol% isopropanol water solution to obtain saturated solution with calcium hydroxide particle size smaller than 6.5 μm;

(3) spraying the reinforcing agent prepared in the step (2) on the weathered layer of the stone cultural relic;

(4) and (3) spraying the stone cultural relic sprayed with the reinforcing agent by the low-temperature plasma source nozzle introduced with the carbon dioxide gas.

(5) Repeating the step (3) and the step (4) for 10-15 times.

And (4) reinforcing once every time step (3) and step (4) are carried out, wherein the interval of reinforcing for each time is at least 20 min.

In the step (4), the working voltage of the low-temperature plasma source is 110V-240V, the frequency is 50 Hz-60 Hz, and the power is maximally 30W.

In the step (4), the standard processing distance of the low-temperature plasma source is 2 mm-10mm, and the standard processing width is 5-20 mm.

In the step (4), the low-temperature plasma source generates cold plasma with the temperature of less than 50 ℃.

And (4) scanning the position of the stone cultural relic sprayed with the reinforcing agent for 1-2 min by using plasma flame at the nozzle of the low-temperature plasma source.

In the step (2), the preparation method of the reinforcing agent comprises the steps of dispersing nano calcium hydroxide or calcium hydroxide which is less than or equal to 6.5 microns and is produced by Shanghai Mecline company into an isopropanol water solution with the volume concentration of 5-5.5%, and continuously stirring for 2-3 hours by using a magnetic stirrer or vibrating for 2-3 hours by ultrasonic waves to prepare a saturated solution.

Has the advantages that: the invention provides a device and a method for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in a carbon dioxide atmosphere.

The calcium hydroxide is bombarded by abundant high-energy and high-activity particles in the low-temperature plasma, so that the calcium hydroxide is etched and coarsened, the surface solubility of the calcium hydroxide is increased, more active sites are provided, the calcium hydroxide is easy to react with activated carbon dioxide, and the nucleation and growth of the calcium carbonate are facilitated. The low-temperature plasma can activate the surface energy and promote the tight combination of weathered rock phase and calcium carbonate. Carbon dioxide gas is introduced into the integrated low-temperature plasma source and is used as ionized gas on one hand, and on the other hand, the activated carbon dioxide gas reacts with the activated calcium hydroxide to promote the orderly carbonization of the calcium hydroxide, so that the calcium carbonate is converted into calcite-type calcium carbonate with a reinforcing effect in an accelerating manner, and further the strength and the weathering resistance of the stone cultural relic are improved.

The invention uses the low-temperature plasma source which is introduced with carbon dioxide gas to activate and reinforce the calcium hydroxide, can realize the carbonization and the precipitation of the calcium hydroxide within 1-2 min, plays a role in reinforcing weathered stone cultural relics, and has the characteristics of safety, high efficiency, no damage and no side effect.

Drawings

FIG. 1 is a schematic diagram of the structure of the device of the present invention.

FIG. 2 is a first schematic diagram of the dropwise addition of a reinforcing agent.

FIG. 3 is a second schematic diagram of the dropwise addition of a reinforcing agent.

FIG. 4 is a first schematic diagram of a low temperature plasma source process.

FIG. 5 is a second schematic of the low temperature plasma source process.

Fig. 6 is a view of the surface of the weathered stone cultural relic, which is observed after the surface attachments of the weathered stone cultural relic are cleaned and magnified 1000 times.

Fig. 7 is a view of the surface of the weathered stone cultural relic, which is reinforced 5 times and enlarged 1000 times.

Fig. 8 is a view of the surface of the weathered stone cultural relic, which is enlarged 1000 times after 10 times of reinforcement.

Fig. 9 is a view of the surface of the weathered stone cultural relic, which is enlarged 1000 times after 15 times of reinforcement.

Detailed Description

As shown in figure 1, the device for reinforcing weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in carbon dioxide atmosphere comprises a low-temperature plasma source 1, wherein a nozzle 2 is arranged at the front end of the low-temperature plasma source 1, the rear end of the low-temperature plasma source is connected with an outlet of a carbon dioxide container 4 through a connecting pipe 3, the rear end of the low-temperature plasma source 1 is also connected with a power supply connecting wire 6 and a grounding wire 7, the power supply connecting wire 6 is connected with a power supply 5, a switch is arranged on the power supply, and a pressure gauge 40 and a valve 41 are arranged on the outlet of. The connecting pipes 3 are provided with a plurality of joints 30, and the joints 30 are arranged among the connecting pipes 30.

The carbon dioxide container is a carbon dioxide steel bottle.

The method for strengthening weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in carbon dioxide atmosphere comprises the following steps,

(1) cleaning attachments on the surface of the stone cultural relic;

(2) dispersing calcium hydroxide into 5-5.5 vol% isopropanol water solution to obtain saturated solution with calcium hydroxide particle size smaller than 6.5 μm;

(3) spraying the reinforcing agent prepared in the step (2) on the weathered layer of the stone cultural relic;

(4) and (3) spraying the stone cultural relic 8 sprayed with the reinforcing agent by the low-temperature plasma source nozzle introduced with carbon dioxide gas.

(5) And (4) repeating the step (3) and the step (4) for 10-15 times, wherein the step (3) and the step (4) are carried out once, namely, the reinforcement is carried out once. The reinforcement is carried out at intervals of at least 20 min: after each treatment, the stone has 1 ℃ temperature change, and the time interval after each reinforcement can ensure sufficient carbonization, so that the residual calcium hydroxide can react with carbon dioxide in the air for carbonization. And if a plasma source is continuously used for long-term continuous work, when gas in the carbon dioxide steel cylinder is continuously released, the interface between the gas pipe and the steel cylinder is frozen due to temperature reduction after a long time (about half an hour), and the interval time of each reinforcement is at least 20 min.

In the step (4), the working voltage of the low-temperature plasma source is 110V-240V, the frequency is 50 Hz-60 Hz, and the power is maximally 30W.

In the step (4), the standard processing distance of the low-temperature plasma source is 2 mm-10mm, and the standard processing width is 5-20 mm.

In the step (4), the low-temperature plasma source generates cold plasma with the temperature of less than 50 ℃.

In the step (4), the plasma flame at the nozzle of the low-temperature plasma source is used for scanning the position of the stone cultural relic 8 after the reinforcing agent is sprayed for 1min-2 min.

In the step (2), the preparation method of the reinforcing agent comprises the steps of dispersing nano calcium hydroxide or calcium hydroxide which is less than or equal to 6.5 microns and is produced by Shanghai Mecline company into an isopropanol water solution with the volume concentration of 5-5.5%, and continuously stirring for 2-3 hours by using a magnetic stirrer or vibrating for 2-3 hours by ultrasonic waves to prepare a saturated solution.

Test verification:

the method for strengthening weathered stone cultural relics by activating calcium hydroxide through low-temperature plasma in carbon dioxide atmosphere comprises the following steps,

(1) cleaning attachments on the surface of the weathered stone cultural relic; observing the surface condition of the weathered stone cultural relic under the condition of 1000 times of magnification, wherein a specific observation image is shown in figure 6;

(2) dispersing calcium hydroxide in 5 vol% concentration isopropanol water solution to obtain saturated solution with calcium hydroxide particle size smaller than 6.5 micron;

(3) spraying the reinforcing agent prepared in the step (2) on the weathered layer of the stone cultural relic; the spraying test is shown in fig. 2 and fig. 3, as the test area of the stone cultural relic is small, a dropper is used for dripping;

(4) spraying the stone cultural relic sprayed with the reinforcing agent for 1min by the low-temperature plasma source nozzle introduced with the carbon dioxide gas, as shown in fig. 4 and 5; the working voltage of the low-temperature plasma source is 110V, the frequency is 50 Hz, and the power is 25W at most.

(5) Repeating the step (3) and the step (4), wherein the step (3) and the step (4) are carried out once, namely, the reinforcement is carried out once; and (3) repeating the steps (3) and (4) for 5 times, 10 times and 15 times, namely reinforcing for 5 times, 10 times and 15 times respectively, and observing the surface condition of the stone cultural relic under the condition of 1000 times magnification, wherein the specific observation images are respectively shown in fig. 7, fig. 8 and fig. 9.

Compare fig. 6, fig. 7, fig. 8, fig. 9. FIG. 6: before reinforcing, the surface of the stone cultural relic is seriously degraded, uneven and loose particles; FIG. 7: after the method is used for reinforcing for 5 times, calcium carbonate crystals are formed on the surface of the sample, calcium carbonate is filled in gaps of the particles, the calcium carbonate crystals are distributed more dispersedly, and the surface roughness of the stone is improved; FIG. 8: after 10 times of reinforcement, the calcium carbonate crystals are increased, the filling is more sufficient, the calcium carbonate crystal layers are continuously and uniformly distributed, an effective reinforcing layer is formed, the surface roughness of the stone is obviously improved, the surface strength is enhanced, and the color is not obviously changed; FIG. 9: after 15 times of reinforcement, the crystal quantity of the calcium carbonate is increased, the filling is complete, the crystal layers of the calcium carbonate are distributed continuously and uniformly, an effective reinforcing layer is formed, the surface of the deteriorated stone is flat, the surface is obviously strengthened, and the color is slightly whitened.

The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various changes and modifications can be made without departing from the overall concept of the present invention, and these should also be considered as the protection scope of the present invention.