Device and method for reinforcing rock cultural relics

Abstract

The present invention discloses a device and method for reinforcing rock cultural relics, relating to the field of cultural relic protection technology. The device comprises an electrochemical deposition cell, wherein a first buffer sponge, a first agar spacer, an AlCl3 patch material, a weathered stone storage chamber, a diammonium phosphate patch material, a second agar spacer, and a second buffer sponge are disposed between two electrodes in the electrochemical deposition cell; the first and second buffer sponges are impregnated with a phosphate buffer; the AlCl3 patch material is prepared from raw materials including a cellulose AlCl3 aqueous solution; and the diammonium phosphate patch material is prepared from raw materials including cellulose and a diammonium phosphate aqueous solution. The present invention can produce an aluminum phosphate precipitate protective layer on the surface and interior of weathered carbonate rock through electrochemical deposition. The protective layer is dense and has low porosity, thereby improving the acid resistance of the aluminum phosphate protective layer.

Description

Technical Field

[0001] The present invention relates to the technical field of cultural relics protection, and in particular to a device and method for reinforcing rock cultural relics. Background Art

[0002] The information disclosed in this background technology section is only intended to enhance understanding of the overall background of the invention and should not necessarily be regarded as an admission or any form of suggestion that the information constitutes the prior art already known to those skilled in the art.

[0003] Among rock-based cultural relics, carbonate-based cultural relics are extremely susceptible to corrosion and other diseases caused by water and acid in the preservation environment, resulting in cracking, discoloration and other problems, which seriously affect the historical and artistic value of carbonate-based cultural relics. In order to prevent carbonate-based cultural relics from being corroded, materials such as calcium oxalate, hydroxyapatite or aluminum phosphate are often used for reinforcement. However, studies have found that: calcium oxalate materials have low permeability due to their rapid reaction with calcium carbonate, and the thickness of the reinforcement layer formed is relatively thin, which cannot completely avoid problems such as falling off and cracking; hydroxyapatite materials have a moderate reaction time with calcium carbonate, but there is a lattice mismatch problem between hydroxyapatite and calcium carbonate crystals, which results in the coating's acid resistance not meeting expectations; aluminum phosphate materials have a more similar crystal form to calcium carbonate, and aluminum phosphate's acid resistance is much higher than that of calcium carbonate, so they can provide excellent reinforcement and protection.

[0004] Current aluminum phosphate reinforcement methods commonly use drip infiltration or capillary absorption. This involves adding a liquid containing the aluminum phosphate reinforcement material to weathered carbonate rock, allowing the aluminum phosphate component to penetrate the cracks in the carbonate rock under the influence of gravity or capillary forces, achieving reinforcement and protection. However, this method still causes coating cracking, resulting in limited improvement in acid resistance. Summary of the Invention

[0005] In response to the shortcomings of the existing technology, the purpose of the present invention is to provide a device and method for reinforcing rock cultural relics. The electrochemical deposition method is used to produce aluminum phosphate precipitation on the surface and inside of weathered carbonate rock to form an aluminum phosphate protective coating, which effectively prevents cracking of the protective layer and improves acid resistance.

[0006] In order to achieve the above object, the present invention is implemented through the following technical solutions:

[0007] A first aspect of the present invention provides a device for reinforcing rock cultural relics, comprising:

[0008] An electrochemical deposition cell, wherein one end of the electrochemical deposition cell is provided with an electrode connected to the positive pole of a power supply, and the other end thereof is provided with an electrode connected to the negative pole of the power supply;

[0009] The electrochemical deposition cell is provided with a first buffer sponge, a first agar septum, an AlCl3 application material, a weathered stone placement chamber, a (NH4)2HPO4 application material, a second agar septum, and a second buffer sponge, which are sequentially connected to form a conductive loop;

[0010] The first buffer sponge and the second buffer sponge are soaked in phosphate buffer;

[0011] The raw materials for preparing the Al Cl3 patch material include cellulose and an Al Cl3 aqueous solution with a concentration of 0.1 to 0.2 M, and the mass ratio of cellulose to the Al Cl3 aqueous solution is 1:2 to 3;

[0012] The raw materials for preparing the (NH4)2HPO4 patch material include cellulose and a (NH4)2HPO4 aqueous solution with a concentration of 0.1 to 0.2 M, and the mass ratio of cellulose to the (NH4)2HPO4 aqueous solution is 1:2 to 3;

[0013] The outer wall of the weathered stone placement chamber is made of porous material and is used for placing rock cultural relics to be reinforced.

[0014] Optionally, the sponges in the first buffer sponge and the second buffer sponge are nano sponges.

[0015] Optionally, the phosphate buffer has a neutral pH value and includes potassium dihydrogen phosphate, sodium hydroxide and water.

[0016] Optionally, the concentration of potassium dihydrogen phosphate in the phosphate buffer is 0.04-0.06M.

[0017] Optionally, the raw materials for preparing the first agar spacer and the second agar spacer include agar and water in a mass ratio of (4-8):96.

[0018] Optionally, the porous material of the weathered stone placement room includes one or more of gauze, non-woven fabric and rice paper.

[0019] Optionally, the rock cultural relics to be reinforced are made of carbonate rock.

[0020] Optionally, the electrodes in the electrochemical deposition cell are connected to the power supply via wires.

[0021] In a second aspect, a method for reinforcing rock cultural relics using the above-mentioned device for reinforcing rock cultural relics comprises the steps of:

[0022] S1. Wrap the rock artifact to be reinforced with a porous material and saturate the porous material with a neutral phosphate buffer solution to obtain a weathered rock chamber.

[0023] S2. An AlCl3 patch material, a first agar septum, and a first buffer sponge are sequentially connected to one side of the weathered stone material placement chamber; and an (NH4)2HPO4 patch material, a second agar septum, and a second buffer sponge are sequentially connected to the other side of the weathered stone material placement chamber;

[0024] S3. Connect the first buffer sponge to the positive pole of the power supply, connect the second buffer sponge to the negative pole of the power supply, start the power supply and maintain the set time to complete the reinforcement of the rock cultural relics.

[0025] Optionally, start the power supply and set it to: current 30±5mA, voltage 120±10V, and power-on time 24±4h.

[0026] The beneficial effects of the present invention are as follows:

[0027] 1. The device and method of the present invention can produce aluminum phosphate precipitation on the surface and interior of weathered carbonate rock through electrochemical deposition. Aluminum ions and phosphate ions form a precipitated protective layer under the action of an applied electric field. The resulting protective layer is dense and has low porosity, effectively preventing cracking and improving the acid resistance of the aluminum phosphate protective layer.

[0028] 2. The present invention sets up a weathered stone placement chamber made of porous materials to avoid direct contact between the stone and the application material, prevent the reactants from gathering in a small area, and effectively improve the uniformity and density of the protective layer.

[0029] 3. The protective layer prepared by the present invention has a moderate thickness and good color protection ability. The color change of the sample is not obvious, which can effectively protect the artistic value of the cultural relics. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] The accompanying drawings, which constitute a part of the present invention, are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute improper limitations on the present invention.

[0031] In order to show the positions of various parts, the distances or sizes between them are exaggerated in the figure, and the schematic diagram is for reference only.

[0032] Figure 1 Schematic diagram of the structure of the device for reinforcing rock cultural relics in Example 1.

[0033] Among them, 1. simulated weathering sample; 2. gauze; 3. AlCl3 application material; 4. (NH4)2HPO4 application material; 5. first agar spacer; 6. second agar spacer; 7. first buffer sponge; 8. second buffer sponge; 10. electrode material; 11. power supply. DETAILED DESCRIPTION

[0034] It should be noted that the following detailed descriptions are exemplary and intended to provide further explanation of the present invention. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs.

[0035] It should be noted that the terms used herein are only for describing specific embodiments and are not intended to limit the exemplary embodiments according to the present invention. As used herein, unless the context clearly indicates otherwise, the singular form is intended to include the plural form. In addition, it should be understood that when the terms "comprise" and / or "include" are used in this specification, they indicate the presence of features, steps, operations, devices, components and / or combinations thereof.

[0036] A device for reinforcing rock cultural relics, comprising:

[0037] An electrochemical deposition cell, wherein one end of the electrochemical deposition cell is provided with an electrode connected to the positive pole of a power supply, and the other end thereof is provided with an electrode connected to the negative pole of the power supply;

[0038] The electrochemical deposition cell is provided with a first buffer sponge, a first agar septum, an AlCl3 application material, a weathered stone placement chamber, a (NH4)2HPO4 application material, a second agar septum, and a second buffer sponge, which are sequentially connected to form a conductive loop;

[0039] The first buffer sponge and the second buffer sponge are soaked with phosphate buffer;

[0040] The raw materials for preparing the Al Cl3 patch material include cellulose and a 0.1-0.2M Al Cl3 aqueous solution, and the mass ratio of cellulose to Al Cl3 aqueous solution is 1:2-3;

[0041] The raw materials for preparing the (NH4)2HPO4 patch material include cellulose and a (NH4)2HPO4 aqueous solution with a concentration of 0.1 to 0.2 M, and the mass ratio of cellulose to the (NH4)2HPO4 aqueous solution is 1:2 to 3;

[0042] The outer wall of the weathered stone storage room is made of porous material and is used to place rock artifacts to be reinforced.

[0043] Through the above setup, aluminum phosphate precipitates are produced on and within the weathered carbonate rock using electrochemical deposition. Under the influence of an applied electric field, aluminum and phosphate ions gradually diffuse into the porous material of the weathered rock chamber and onto the surfaces and crevices of the rocky artifacts within, forming a precipitated protective layer. The resulting protective layer is dense and has low porosity, effectively preventing cracking and, in turn, preventing acid from penetrating the crevices, thereby enhancing acid resistance.

[0044] Optionally, the sponges in the first buffer sponge and the second buffer sponge are nanosponges, which play the role of fixing the buffer.

[0045] Optionally, the pH value of the phosphate buffer is neutral, and it includes potassium dihydrogen phosphate, sodium hydroxide and water; the sodium hydroxide serves as a pH adjuster.

[0046] Optionally, the concentration of potassium dihydrogen phosphate is 0.04-0.06M, which serves to neutralize the acid generated by electrolyzed water.

[0047] Optionally, the raw materials for preparing the first agar spacer and the second agar spacer include agar and water in a mass ratio of (4-8):96; the agar gel acts as a barrier, provides conductivity and electrolyzes water, and can also reduce the precipitation formed by phosphate buffer and aluminum chloride.

[0048] Optionally, the porous material of the weathered stone placement room includes: one or more of gauze, non-woven fabric and rice paper; avoiding direct contact between the stone and the pasting material is conducive to the uniform diffusion of ions in the pasting material.

[0049] Optionally, the rock cultural relics to be reinforced are made of carbonate rock, specifically calcium carbonate rock material, which is more similar in crystal form to aluminum phosphate and can achieve better reinforcement and protection effects.

[0050] Optionally, the electrodes in the electrochemical deposition cell are connected to the power supply via wires to avoid forming a conductive loop outside the set conductive path, thereby preventing reduction in the generation effect of the protective layer.

[0051] A method for reinforcing rock cultural relics using the above-mentioned device for reinforcing rock cultural relics comprises the following steps:

[0052] S1. Wrap the rock artifacts to be reinforced with porous materials to create a weathered stone storage chamber;

[0053] S2. An AlCl3 patch material, a first agar septum, and a first buffer sponge are sequentially connected to one side of the weathered stone material placement chamber; and an (NH4)2HPO4 patch material, a second agar septum, and a second buffer sponge are sequentially connected to the other side of the weathered stone material placement chamber;

[0054] S3. Connect the first buffer sponge to the positive pole of the power supply, connect the second buffer sponge to the negative pole of the power supply, start the power supply and maintain the set time to complete the reinforcement of the rock cultural relics.

[0055] Through the above process, a relatively dense and uniform aluminum phosphate protective layer can be formed on the cultural relics, effectively improving the weathering and acid resistance of the cultural relics.

[0056] Optionally, the power supply is set to: current 30±5mA, voltage 120±10V; power-on time is 24±4h; it needs to be adjusted according to the thickness of the protective layer you want to generate and the size of the surface area of ​​the cultural relic.

[0057] Example 1

[0058] Preparation of AlCl3 patch material: First, add 1.33g of aluminum chloride to 100ml of deionized water to prepare a 0.1M AlCl3 aqueous solution, and mix them evenly at a ratio of AlCl3 aqueous solution: cellulose = 2:1 (w:w) to obtain a gel-like AlCl3 patch material.

[0059] Preparation of (NH4)2HPO4 patch material: First, add 1.32g of diammonium hydrogen phosphate to 100ml of deionized water to prepare a (NH4)2HPO4 aqueous solution with a concentration of 0.1M, and mix the obtained (NH4)2HPO4 aqueous solution: cellulose at a ratio of 2:1 (w:w) to obtain a gel-like (NH4)2HPO4 patch material.

[0060] Preparation of agar septa: Place 4 g of agar powder in a beaker, add 96 g of deionized water, heat in a water bath (set the water bath temperature to 92°C), and stir continuously to mix evenly. After about 30 minutes, remove from the water bath, pour into a plastic box, and cool to room temperature to obtain a nearly transparent gel solid, i.e., the agar septa. The agar material is from HEOWNS and is of biological grade purity. It is divided into a first agar pad and a second agar septa by segmentation.

[0061] Prepare phosphate buffer: Take 0.68 g of potassium dihydrogen phosphate, add 29.1 ml of 0.1 mol / L sodium hydroxide solution, and dilute to 100 ml with water. Both potassium dihydrogen phosphate and sodium hydroxide are produced by Sinopharm Group and are of analytical grade without purification.

[0062] like Figure 1As shown, a simulated weathering sample 1 (calcium carbonate stone) is wrapped with gauze 2 to form a weathered stone placement chamber to prevent the simulated weathering sample 1 from directly contacting the application material; an AlCl3 application material 3 is applied to the anode of the weathered stone placement chamber, and a (NH4)2HPO4 application material 4 is applied to the cathode side of the weathered stone placement chamber. A first agar spacer 5 and a second agar spacer 6 are respectively arranged on the outside of the two application materials. Nanosponges with 5 ml of phosphate buffer added are placed on the outside of the two agar spacers, serving as a first buffer sponge 7 and a second buffer sponge 8 to neutralize the acid generated by electrolyzed water. The first buffer sponge 7 and the second buffer sponge 8 are respectively connected to an electrode material 10, and the electrode material 10 is respectively connected to a power supply 11, thereby obtaining a device for reinforcing rock cultural relics for placing rock cultural relics to be reinforced.

[0063] In this embodiment, the electrode material 10 is graphite. Along the current conduction direction, that is, from left to right in the figure, the thickness of the first buffer sponge 7 is 10 mm, the thickness of the first agar spacer 5 is 5 mm, the thickness of the AlCl3 applying material 3 is 2.5±0.5 mm, the thickness of the gauze 2 is 1.5±0.5 mm, the thickness of the (NH4)2HPO4 applying material 4 is 2.5±0.5 mm, the thickness of the second agar spacer 6 is 5 mm, the thickness of the second buffer sponge 8 is 10 mm, and the size of the simulated weathering sample 1 wrapped in gauze 2 is 20*20*10 mm.

[0064] During reinforcement, power supply 11 was started and set to: current 30 mA, voltage 120 V; after the entire device was powered on for 24 hours, the rock artifacts wrapped in gauze 2 were taken out, and the reinforced samples were rinsed with deionized water and placed in a 55°C oven for 7 hours.

[0065] Comparative Example 1

[0066] A sample with the same source and the same degree of dissolution as the simulated weathering sample in Example 1 was selected without treatment as Comparative Example 1.

[0067] Comparative Example 2

[0068] Samples with the same source and the same degree of dissolution as the simulated weathering specimens in Example 1 were selected, and an aqueous solution of diammonium hydrogen phosphate with a concentration of (0.1 to 0.2 M) and an aqueous solution of aluminum chloride with a concentration of (0.1 to 0.2 M) were added sequentially to the surface of the weathered carbonate rock cultural relics by the drip infiltration method for repair.

[0069] Performance testing

[0070] The color difference test process involves measuring and recording the L, a, and b values ​​of the sample surface using a portable colorimeter. The CI E1976 color difference formula and its CI ELAB color rendering system are used to measure the color space of an object. The color difference ΔE between two colors is the geometric distance between two locations in the CI E1976 (L, a, b) color space and is calculated using the formula.

[0071] ΔE=[(ΔL) 2 +(Δa) 2 +(Δb) 2 ] 1 / 2 (1)

[0072] Where, △L = L sample - L standard; △a = a sample - a standard; △b = b sample - b standard.

[0073] Color difference is generally evaluated using ΔE. Smaller ΔE values ​​indicate smaller color differences. During the experiment, five points were randomly selected from the sample for testing, and the average value was taken for analysis. The results are shown in Table 1.

[0074] Table 1

[0075]

[0076] Related research shows that after reinforcement, when ΔE* is less than 3, the color change is imperceptible to the human eye; when ΔE* is between 3 and 5, the color difference between materials is slightly different and within the generally acceptable range; and when ΔE* is greater than 5, it is considered aesthetically incompatible. In Example 1 of the present invention, the color difference values ​​of the reinforced sample were all less than 3, indicating that the color change of the sample reinforced by electrochemical methods was within the acceptable range, with a color difference of 2.00.

[0077] The porosity testing process included testing the porosity of the hardened mortar using a MicroActive AutoPoreV 9600 mercury intrusion porosimeter according to ISO 15901 Part 1. The results are shown in Table 2.

[0078] Table 2

[0079]

[0080] It can be seen that the porosity is reduced by 50.79% after reinforcement, indicating that the pores inside the sample are filled after reinforcement.

[0081] The acid resistance test process involves drying the sample at 55°C to constant weight and weighing it. An acidic solution with a pH of 3.5 is prepared using a 1:1 molar ratio of concentrated sulfuric acid and concentrated nitric acid. The specific ratio is 5.43 μL of 98% concentrated sulfuric acid and 6.25 μL of 70% concentrated nitric acid, both produced by Sinopharm Group, added to 1 L of deionized water. The sample is then placed in the acidic solution and subjected to a 40 kHz ultrasonic cleaning machine for 5 hours. The sample is then removed, rinsed with ultrapure water, dried at 55°C for 18 hours, and weighed. This constitutes one cycle. The results after ten acid resistance cycles are shown in Table 3.

[0082] Table 3

[0083]

[0084] It can be seen from Table 3 that the mass loss rate of comparative example 1 after ten acid-resistant cycles is 2.10%, and the mass loss rate of embodiment 1 after ten acid-resistant cycles after electrochemical reinforcement is 0.12%. Compared with comparative example 1, the mass loss inhibition rate is as high as 94.28%. It can be seen that the acid-resistant effect is greatly improved after reinforcement.

[0085] The above description is merely a preferred embodiment of the present application and is not intended to limit the present application. Various modifications and variations are possible for those skilled in the art. Any modifications, equivalent substitutions, or improvements made within the spirit and principles of the present application shall be included within the scope of protection of the present application.

Claims

1. A device for reinforcing rock cultural relics, characterized in that: include: The electrochemical deposition cell comprises an electrode connected to the positive electrode of a power supply at one end and an electrode connected to the negative electrode of the power supply at the other end; The electrochemical deposition cell is provided with a first buffer sponge, a first agar septum, an AlCl3 application material, a weathered stone placement chamber, a (NH4)2HPO4 application material, a second agar septum, and a second buffer sponge, which are sequentially connected to form a conductive loop; The first buffer sponge and the second buffer sponge are soaked in phosphate buffer; The raw materials for preparing the AlCl3 patch material include cellulose and an AlCl3 aqueous solution with a concentration of 0.1-0.2 M, and the mass ratio of cellulose to the AlCl3 aqueous solution is 1:2-3; The raw materials for preparing the (NH4)2HPO4 patch material include cellulose and a (NH4)2HPO4 aqueous solution with a concentration of 0.1-0.2 M, and the mass ratio of cellulose to the (NH4)2HPO4 aqueous solution is 1:2-3; The outer wall of the weathered stone storage chamber is a porous material soaked in phosphate buffer, which is used to place the rock artifacts to be reinforced; The phosphate buffer has a neutral pH value and includes potassium dihydrogen phosphate, sodium hydroxide and water; The porous material of the weathered stone placement room includes: one or more of gauze, non-woven fabric and rice paper; The rock cultural relics to be reinforced are made of carbonate rock.

2. The device for reinforcing rock cultural relics according to claim 1, characterized in that: The sponges in the first buffer sponge and the second buffer sponge are nano sponges.

3. The device for reinforcing rock cultural relics according to claim 1, characterized in that: In phosphate buffer, the concentration of potassium dihydrogen phosphate is 0.04~0.06 M.

4. The device for reinforcing rock cultural relics according to claim 1, characterized in that: The raw materials for preparing the first agar spacer and the second agar spacer include agar and water in a mass ratio of (4-8):

96.

5. The device for reinforcing rock cultural relics according to claim 1, characterized in that: The electrodes in the electrochemical deposition cell are connected to the power supply via wires.

6. A method for reinforcing rock cultural relics using the device for reinforcing rock cultural relics according to any one of claims 1 to 5, characterized in that: Including steps: S1. Wrap the rock artifact to be reinforced with a porous material and saturate the porous material with a neutral phosphate buffer solution to obtain a weathered rock chamber. S2. An AlCl3 patch material, a first agar septum, and a first buffer sponge are sequentially connected to one side of the weathered stone placement chamber; and an (NH4)2HPO4 patch material, a second agar septum, and a second buffer sponge are sequentially connected to the other side of the weathered stone placement chamber; S3. Connect the first buffer sponge to the positive pole of the power supply, connect the second buffer sponge to the negative pole of the power supply, start the power supply and maintain the set time to complete the reinforcement of the rock cultural relics.

7. The method for reinforcing rock cultural relics according to claim 6, characterized in that: In S3, the power supply settings are: current 30±5mA, voltage 120±10V; power-on time is 24±4h.

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