A mural reinforcing protective agent, a preparation method and application thereof
By loading Ba(OH)2 nanoparticles in situ onto a bacterial cellulose carrier, the problems of existing mural reinforcement materials being unable to deeply reinforce the underlying structure and surface whitening were solved, achieving deep penetration and uniform dispersion, thus improving the protection effect and the safety of cultural relics.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- SHAANXI PROVINCIAL INST OF CULTURAL RELICS PROTECTION
- Filing Date
- 2023-12-25
- Publication Date
- 2026-06-23
Smart Images
Figure CN117757308B_ABST
Abstract
Description
Technical Field
[0001] This application relates to the field of cultural relic restoration technology, and in particular to a mural reinforcement and protection agent, its preparation method, and its application. Background Technology
[0002] Ancient murals are a very ancient form of painting, dating back to prehistoric times. They are typically painted on hard materials such as walls, stone, and wood, and served multiple purposes including decoration, recording, and cultural transmission. Ancient murals possess extremely high artistic, historical, scientific, and cultural value, and are an important part of historical and cultural heritage.
[0003] Conservation of ancient murals is a crucial task because they are an important part of historical and cultural heritage, possessing extremely high artistic, historical, scientific, and cultural value. However, due to the effects of time, natural environment, and human factors, ancient murals often suffer damage and destruction, making their conservation particularly important.
[0004] Currently, traditional inorganic alkaline earth metal hydroxides, such as Ba(OH)2 and Ca(OH)2, are mainly used to protect ancient murals. However, these materials cannot penetrate deeply into the narrow pores of ancient murals, thus failing to reinforce the underlying structure and easily adhering to the surface, causing the surface pigments to turn white. Summary of the Invention
[0005] This application provides a mural reinforcement and protection agent, its preparation method, and its application, which solves the technical problem that existing mural reinforcement materials cannot penetrate deep into the lower structure of ancient murals and are prone to adhering to the surface of the mural, causing the surface pigments to turn white.
[0006] To achieve the above objectives, the technical solution of this invention is as follows:
[0007] In a first aspect, embodiments of the present invention provide a mural reinforcement and protection agent, comprising a bacterial cellulose carrier and Ba(OH)2 nanoparticles in situ loaded on the bacterial cellulose carrier.
[0008] Secondly, embodiments of the present invention provide a method for preparing the above-mentioned mural reinforcement and protection agent, comprising:
[0009] Bacterial cellulose dispersion and BaCl2 solution were prepared separately;
[0010] The bacterial cellulose dispersion was mixed with the BaCl2 solution to obtain a precursor solution.
[0011] An alkaline precipitant is added to the precursor solution to carry out the reaction, and then the mural reinforcement and protection agent is separated and collected from the product.
[0012] In conjunction with the second aspect, in one possible implementation, the mass concentration of the bacterial cellulose dispersion is 0.2% to 0.8%.
[0013] In conjunction with the second aspect, in one possible implementation, the mass concentration of the BaCl2 solution is 0.01–0.1%.
[0014] In conjunction with the second aspect, in one possible implementation, when the bacterial cellulose dispersion is mixed with the BaCl2 solution, the volume ratio of the bacterial cellulose dispersion to the BaCl2 solution is 0.025 to 0.1.
[0015] In conjunction with the second aspect, in one possible implementation, the alkaline precipitant comprises a solvent and NaOH, ammonia, and urea dissolved in the solvent.
[0016] In conjunction with the second aspect, in one possible implementation, the mass ratio of the NaOH, the ammonia, and the urea is 1:4:8 to 1:1:1.
[0017] In conjunction with the second aspect, in one possible implementation, the time for mixing and reacting the bacterial cellulose dispersion with the BaCl2 solution is 1 h to 3 h.
[0018] In conjunction with the second aspect, in one possible implementation, the reaction time for adding the alkaline precipitant to the precursor solution is 0.5 h to 1.5 h.
[0019] Thirdly, embodiments of the present invention provide an application of the above-mentioned mural reinforcement and protection agent in the restoration of cultural relics.
[0020] One or more technical solutions provided in the embodiments of the present invention have at least the following technical effects or advantages:
[0021] The mural reinforcement and protection agent provided in this invention includes a bacterial cellulose carrier and Ba(OH)2 nanoparticles in situ loaded on the bacterial cellulose carrier. This mural reinforcement and protection agent, by loading Ba(OH)2 nanoparticles in situ onto the bacterial cellulose carrier, allows for a strong synergistic effect between the Ba(OH)2 nanoparticles and bacterial cellulose. On one hand, it imparts high permeability to BC-Ba(OH)2, enabling it to deeply penetrate into the tiny pores of the mural, effectively filling cracks and solidifying loose particles within the mural. This strengthens the underlying structure of the mural, achieving deep reinforcement of ancient murals, improving protection effectiveness, stability, and durability. Furthermore, because BC-Ba(OH)2 fully penetrates the underlying structure of the mural, it prevents whitening of the mural surface and also improves the utilization rate of the mural reinforcement and protection agent. On the other hand, in-situ loading of Ba(OH)₂ nanoparticles onto a bacterial cellulose carrier imparts a uniform and stable structural morphology to BC-Ba(OH)₂, preventing aggregation and greatly enhancing the protective effect of the mural reinforcement agent, providing more durable and effective protection. Furthermore, bacterial cellulose, as a low-cost, non-toxic, and biocompatible carrier, will not damage the murals, ensuring the safety and integrity of the cultural relics.
[0022] The method for preparing the mural reinforcement and protection agent provided in this invention first involves preparing a bacterial cellulose carrier dispersion and a BaCl2 solution. Then, the bacterial cellulose dispersion and the BaCl2 solution are mixed and reacted to obtain a precursor solution. Bacterial cellulose is used as a carrier, and the surface of the bacterial cellulose is rich in OH groups. - with Ba 2+ Electrostatic attraction occurs, causing Ba 2+ It is introduced onto the surface of bacterial cellulose. Finally, an alkaline precipitant is added to the precursor solution to allow for reaction, OH... - Anchoring points are provided to allow Ba(OH)2 nanoparticles to nucleate and grow in situ on the surface of bacterial cellulose, which is conducive to the uniform dispersion of nanoparticles. The mural reinforcement and protection agent is then separated and collected from the product. Due to the strong physical interaction between bacterial cellulose and Ba(OH)2 nanoparticles, the aggregation and migration of nanoparticles are prevented, thus making the mural reinforcement and protection agent effective for a long time. Attached Figure Description
[0023] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the description of the embodiments of the present invention will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.
[0024] Figure 1 TEM image of bacterial cellulose provided in the embodiments of this application;
[0025] Figure 2 TEM image of BC-Ba(OH)2 provided in the embodiments of this application;
[0026] Figure 3 TEM images of different ratios of BC and Ba(OH)2 in BC-Ba(OH)2 provided for embodiments of this application: (a) BC:Ba(OH)2 = 1:2; (b) BC:Ba(OH)2 = 5:1; (c) BC:Ba(OH)2 = 20:1;
[0027] Figure 4 This is a comparison chart of the penetration depth of BC-Ba(OH)2 in this application and existing commercial Ba(OH)2;
[0028] Figure 5 Color difference diagrams for (a) an unreinforced sample, (b) a sample reinforced with commercially available Ba(OH)2, and (c) a sample reinforced with BC-Ba(OH)2 of this application;
[0029] Figure 6 SEM images of the reaction time of the bacterial cellulose dispersion with BaCl2 solution provided in the embodiments of this application for (a) 0.5 h and (b) 3.5 h;
[0030] Figure 7 SEM images of BC-Ba(OH)2 obtained when the mass ratio of NaOH, ammonia and urea provided in the embodiments of this application is (a) 1:2:4 and (b) 1:1:2;
[0031] Figure 8 SEM images of BC-Ba(OH)2 obtained when an alkaline precipitant was added to the precursor solution provided in the embodiments of this application and the reaction time was (a) 10 min and (b) 2 h.
[0032] Figure 9 The XRD pattern of BC-Ba(OH)2 prepared using the method for preparing the mural reinforcement and protective agent provided in the embodiments of this application.
[0033] Figure 10 The following are examples of mural reinforcement using the mural reinforcement and protection agent provided in this application, wherein (a) is before reinforcement and (b) is after mural reinforcement using the mural reinforcement and protection agent of this application;
[0034] Figure 11 (a) Unprocessed, (b) Color difference diagram of the mural simulation sample after processing according to Example 1 of this application;
[0035] Figure 12(a) Unprocessed, (b) Color difference diagram of the simulated mural sample after processing according to Example 2 of this application;
[0036] Figure 13 (a) Unprocessed, (b) Color difference diagram of the mural simulation sample after processing according to Example 3 of this application. Detailed Implementation
[0037] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some, not all, of the embodiments of this application. All other embodiments obtained by those skilled in the art based on the embodiments of this application without creative effort are within the scope of protection of this application.
[0038] In the following description of this embodiment, the term "and / or" is used to describe the association relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, B existing alone, and A and B existing simultaneously. A and B can be singular or plural. The character " / " generally indicates that the preceding and following related objects have an "or" relationship.
[0039] In the following description of this embodiment, the term "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c", can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.
[0040] The terminology used in the embodiments of this application is for the purpose of describing particular embodiments only and is not intended to be limiting of this application. The singular forms "a" and "the" as used in the embodiments of this application and the appended claims are also intended to include the plural forms, unless the context clearly indicates otherwise.
[0041] Those skilled in the art should understand that, in the following description of the embodiments of this application, the sequence of numbers does not imply the order of execution. Some or all steps may be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the embodiments of this application.
[0042] Those skilled in the art will understand that the numerical ranges in the embodiments of this application should be understood to specifically disclose each intermediate value between the upper and lower limits of the range. Each smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included within the scope of this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.
[0043] Unless otherwise stated, the technical / scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains. While this application describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this application. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.
[0044] Firstly, the mural reinforcement and protection agent provided in this application includes a bacterial cellulose carrier and Ba(OH)2 nanoparticles in situ loaded on the bacterial cellulose carrier. This mural reinforcement and protection agent, by loading Ba(OH)2 nanoparticles in situ onto the bacterial cellulose carrier, allows for a strong synergistic effect between the Ba(OH)2 nanoparticles and bacterial cellulose. On one hand, it imparts high permeability to BC-Ba(OH)2, enabling it to deeply penetrate into the tiny pores of the mural, effectively filling cracks and solidifying loose particles, thereby reinforcing the underlying structure of the mural. This achieves deep reinforcement of ancient murals, improving the protective effect, stability, and durability. Furthermore, because BC-Ba(OH)2 fully penetrates into the underlying structure of the mural, it prevents whitening of the mural surface and also improves the utilization rate of the mural reinforcement and protection agent. On the other hand, as... Figure 1 As shown, bacterial cellulose possesses a three-dimensional network structure and high porosity. Ba(OH)₂ nanoparticles are in situ loaded onto a bacterial cellulose support, such as... Figure 2 As shown, Ba(OH)₂ nanoparticles can be uniformly dispersed on the bacterial cellulose carrier, giving BC-Ba(OH)₂ a uniform and stable structural morphology without aggregation. This greatly enhances the protective effect of the mural reinforcement agent on the mural and provides more durable and effective protection. Furthermore, bacterial cellulose, as a low-cost, non-toxic, and biocompatible carrier, will not damage the mural, ensuring the safety and integrity of the cultural relic.
[0045] Furthermore, the BC:Ba(OH)2 ratios in BC-Ba(OH)2 were selected to be 1:2, 5:1, and 20:1, respectively. TEM results of BC-Ba(OH)2 showed that... Figure 3(a) It can be seen that when BC:Ba(OH)2 = 1:2, Ba(OH)2 nanoparticles exhibit severe aggregation and agglomeration. From Figure 3 (b) It can be seen that when BC:Ba(OH)2 = 5:1, the Ba(OH)2 nanoparticles are uniformly dispersed and have consistent size. Figure 3 (c) It can be seen that when BC:Ba(OH)2 = 20:1, the content of Ba(OH)2 nanoparticles is extremely low. Therefore, a high proportion of Ba(OH)2 nanoparticles in BC-Ba(OH)2 will lead to an increase in the particle size of BC-Ba(OH)2 particles, affecting permeability and the utilization rate of the mural reinforcement and protection agent, thus affecting the reinforcement effect. A low proportion of Ba(OH)2 nanoparticles will result in a lower content of the effective components in the mural reinforcement and protection agent, affecting the reinforcement effect.
[0046] In practice, bacterial cellulose has no effect on the penetration depth. Figure 4 A comparison diagram of the penetration depth of BC-Ba(OH)2 from this application and existing commercial Ba(OH)2 nanoparticles is provided. (The penetration depth measurement steps are as follows: (a) Prepare a 1 cm square mural simulation sample. (b) Add BC-Ba(OH)2 from this application and existing commercial Ba(OH)2 nanoparticles to the center of the surfaces of the two mural simulation samples respectively. (c) Place the two mural simulation samples in a room temperature, ventilated environment to allow them to dry naturally. (d) Embed the two mural simulation samples in resin (with the cross-section facing outwards), polish the cross-section of the mural to make it flat, and use a micro-infrared microscope to collect infrared spectra from the edge of the mural simulation sample inwards, recording the distance moved during the process, and finally converting it into penetration depth. (e) Analyze the infrared absorption characteristics of Ba(OH)2 at different depths of the nano-reinforcement material to explore its penetration depth.) Figure 4 As shown, the BC-Ba(OH)2 of this application has a better penetration depth, which is nearly three times that of existing commercial Ba(OH)2 nanoparticles.
[0047] Figure 5 Color difference diagrams for (a) unreinforced samples, (b) samples reinforced with commercially available Ba(OH)2 nanoparticles, and (c) samples reinforced with BC-Ba(OH)2 as described in this application (Color difference test: tested using an X-rite VS450 colorimeter. The colorimetric standard is the CIE L*, a*, b* colorimetric system to evaluate the color change of the paint applied to the painting. L value represents the brightness of the color; the larger the value, the brighter the color, and the smaller the value, the darker the color. a represents the color index of red and green; when a is greater than 0, the color is more red, and when a is less than 0, the color is more green. b represents the color index of yellow and blue; when b is greater than 0, the pigment is more yellow, and when b is less than 0, the color is more blue. Color formulas are used to determine the color difference. This characterizes the degree of color change in the pigment layer when a coating is applied to a simulated sample. Here, ΔL, Δa, and Δb represent the differences in L, a, and b before and after the coating application, respectively, and ΔE is the color difference value. In cultural relic conservation, the degree of color change is assessed by monitoring changes in ΔE. Figure 5 It is known that samples reinforced with existing commercial Ba(OH)2 nanoparticles are significantly whiter than unreinforced samples, while samples reinforced with BC-Ba(OH)2 of this application are no different from unreinforced samples.
[0048] Secondly, another embodiment of the present invention provides a method for preparing the above-mentioned mural reinforcement and protection agent, comprising steps 101 to 103:
[0049] Step 101: Prepare bacterial cellulose dispersion and BaCl2 solution respectively.
[0050] The bacterial cellulose dispersion has a mass concentration of 0.2% to 0.8%, such as 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, and 0.8%. A mass concentration of 0.2% to 0.8% effectively ensures uniform dispersion of bacterial cellulose on the carrier, which is beneficial for Ba(OH)₂ loading and reduces the amount of bacterial cellulose carrier dispersion used, thus lowering costs. Too low a concentration may lead to uneven cellulose dispersion, affecting loading performance. Too high a concentration may result in excessively large cellulose particles. The BaCl₂ solution has a mass concentration of 0.01% to 0.1%, such as 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, and 0.1%. A BaCl2 solution with a mass concentration of 0.01–0.1% can effectively react with OH- in the bacterial cellulose carrier dispersion. - Ions combine to form an insoluble Ba(OH)₂ precipitate. Too low a concentration may result in insignificant precipitation, while too high a concentration may lead to excessive precipitation, affecting subsequent operations.
[0051] Specifically, the bacterial cellulose is first washed and filtered for later use, and then dissolved in a solvent, such as water, to obtain a bacterial cellulose carrier dispersion with a mass concentration of 0.2% to 0.8%.
[0052] BaCl2 is dissolved in a solvent, such as water, to obtain a BaCl2 solution with a mass concentration of 0.01–0.1%.
[0053] Step 102: Mix the bacterial cellulose dispersion with BaCl2 solution to obtain the precursor solution.
[0054] When the bacterial cellulose dispersion and BaCl2 solution are mixed and reacted, the volume ratio of the bacterial cellulose dispersion to the BaCl2 solution is 0.025 to 0.1, which can be 0.025, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, and 0.1, thereby ensuring that the mass ratio of the bacterial cellulose dispersion to the BaCl2 solution is 0.5:1 to 20:1.
[0055] The bacterial cellulose dispersion is mixed with BaCl2 solution for 1 to 3 hours. For example, the reaction time can be 1 hour, 1.5 hours, 2 hours, 2.5 hours, or 3 hours, etc., to allow BaCl2 to react. 2+ Ba is adsorbed onto the surface of bacterial cellulose. If the stirring time is less than 1 hour, the bacterial cellulose surface cannot fully adsorb Ba. 2+ ,like Figure 6 As shown in (a). If the reaction time exceeds 3 hours, it can easily cause Ba... 2+ The phenomenon of reunification occurs, such as Figure 6 As shown in (b), the permeability of the final obtained BC-Ba(OH)2 is affected.
[0056] Step 103: Add an alkaline precipitant to the precursor solution to react, and then separate and collect the mural strengthening and protective agent BC-Ba(OH)2 from the product. Specifically, filter and wash the product, and dry it to obtain the mural strengthening and protective agent BC-Ba(OH)2. Add an alkaline precipitant to the precursor solution to react; the volume ratio of the precursor solution to the alkaline precipitant is 15:1 to 20:1, which can be 15:1, 16:1, 17:1, 18:1, 19:1, or 20:1. If the amount of alkaline precipitant is insufficient, Ba... 2+ Complete precipitation results in an excessively low loading. Excessive alkaline precipitant will lead to an overly alkaline system, which will damage the mural itself.
[0057] The alkaline precipitant includes a solvent and NaOH, ammonia, and urea dissolved in the solvent. The mass ratio of NaOH, ammonia, and urea is 1:4:8 to 1:1:1, and can be 1:4:8, 1:2:4, or 1:1:1, etc. Water is generally used as the solvent. In practice, NaOH, ammonia, and urea have different alkalinities, and the OH- ions produced... - The content and growth rate of particles differ. If the alkaline precipitant is only NaOH, the nucleation rate of Ba(OH)₂ in situ nucleation into nanoparticles is faster, resulting in larger BC-Ba(OH)₂ particles. If the alkaline precipitant is only ammonia or urea, the OH content in the alkaline precipitant will affect the growth rate. -The concentration was too low to induce Ba(OH)2 crystal growth. A mixture of NaOH, ammonia, and urea with different alkalinity gradients was used as an alkaline precipitant to grow high-performance Ba(OH)2 nanoparticles in situ on bacterial cellulose. Figure 7 The SEM images of BC-Ba(OH)2 obtained when the mass ratio of NaOH, ammonia, and urea provided in the embodiments of this application is (a) 1:2:4 and (b) 1:1:2. In (a), the NaOH concentration is higher, and it is obvious that the BC-Ba(OH)2 particles are larger. In (b), the urea concentration is higher, and it is impossible to induce the growth of Ba(OH)2 crystal nuclei.
[0058] The reaction time for adding an alkaline precipitant to the precursor solution is 0.5 h to 1.5 h. For example, the reaction time can be 0.5 h, 0.6 h, 0.7 h, 0.8 h, 0.9 h, 1.0 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, etc. The alkaline precipitant and Ba... 2+ The reaction allows Ba(OH)₂ to nucleate and grow into nanoparticles in situ. If the stirring time is less than 0.5 h, the alkaline precipitant cannot fully react with Ba. 2+ Reactions, such as Figure 8 (a) shows a SEM image of BC-Ba(OH)₂ obtained after reacting with an alkaline precipitant in the precursor solution for 10 min. If the stirring time exceeds 1.5 h, it is easy for Ba to... 2+ Agglomeration occurs, affecting the permeability of the final obtained BC-Ba(OH)2, such as... Figure 8 (b) shows a SEM image of BC-Ba(OH)2 obtained by reacting an alkaline precipitant in the precursor solution for 2 hours. Large agglomerates are visible in the image.
[0059] like Figure 9 The XRD pattern of BC-Ba(OH)2 prepared using the method for preparing the mural reinforcement and protective agent provided in the embodiments of this application is shown. Figure 9 It can be seen that the bacterial cellulose is indeed loaded with Ba(OH)2 nanoparticles.
[0060] The method for preparing the mural reinforcement and protection agent provided in this invention first involves preparing a bacterial cellulose carrier dispersion and a BaCl2 solution. Then, the bacterial cellulose dispersion and the BaCl2 solution are mixed and reacted to obtain a precursor solution. Bacterial cellulose is used as a carrier, and the surface of the bacterial cellulose is rich in OH groups. - with Ba 2+ Electrostatic attraction occurs, causing Ba 2+ It is introduced onto the surface of bacterial cellulose. Finally, an alkaline precipitant is added to the precursor solution to allow for reaction, OH... -Anchoring points are provided to allow Ba(OH)2 nanoparticles to nucleate and grow in situ on the surface of bacterial cellulose, which is conducive to the uniform dispersion of nanoparticles. The mural reinforcement and protection agent is then separated and collected from the product. Due to the strong physical interaction between bacterial cellulose and Ba(OH)2 nanoparticles, the aggregation and migration of nanoparticles are prevented, thus making the mural reinforcement and protection agent effective for a long time.
[0061] Thirdly, another embodiment of the present invention provides an application of the above-mentioned mural reinforcement and protection agent in the restoration of cultural relics. Figure 10 The figures show examples of mural reinforcement and protection agents provided in this application for mural reinforcement. (a) shows the mural before reinforcement, and (b) shows the mural after reinforcement using the mural reinforcement and protection agent provided in this application. As can be seen from the figures, the mural reinforcement and protection agent provided in this application can effectively reinforce the mural.
[0062] Specific embodiments of the preparation method of the mural reinforcement and protection agent of this application are provided herein.
[0063] Example 1
[0064] A bacterial cellulose carrier dispersion with a mass concentration of 0.2% and a BaCl2 solution with a mass concentration of 0.01% were prepared, respectively.
[0065] The bacterial cellulose dispersion and BaCl2 solution (volume ratio of 0.025) were mixed and reacted at room temperature for 1 hour to obtain the precursor solution.
[0066] An alkaline precipitant consisting of NaOH, ammonia, and urea in a mass ratio of 1:4:8 was slowly added to the precursor solution and stirred at room temperature for 0.5 h to carry out the reaction. The mural reinforcement and protection agent was then separated and collected from the product.
[0067] The mural reinforcing agent obtained in Example 1 of this application has a penetration depth of 210 μm and a color difference ΔE = 1.89. Figure 11 As shown, this mural strengthening agent was used to strengthen the mural, and the strengthened mural was able to maintain its color well.
[0068] Example 2
[0069] A bacterial cellulose carrier dispersion with a mass concentration of 0.5% and a BaCl2 solution with a mass concentration of 0.055% were prepared, respectively.
[0070] The bacterial cellulose dispersion and BaCl2 solution (volume ratio of 0.05) were mixed and reacted at room temperature for 2 hours to obtain the precursor solution.
[0071] An alkaline precipitant consisting of NaOH, ammonia, and urea in a mass ratio of 1:2:4 was slowly added to the precursor solution and stirred at room temperature for 1 hour to allow the reaction to proceed. The mural reinforcement and protection agent was then separated and collected from the product.
[0072] The mural reinforcing agent obtained in Example 2 of this application has a penetration depth of 310 μm and a color difference ΔE = 1.31. Figure 12 As shown, this mural strengthening agent was used to strengthen the mural, and the strengthened mural was able to maintain its color well.
[0073] Example 3
[0074] A bacterial cellulose carrier dispersion with a mass concentration of 0.8% and a BaCl2 solution with a mass concentration of 0.1% were prepared, respectively.
[0075] The bacterial cellulose dispersion and BaCl2 solution (volume ratio of 0.1) were mixed and reacted at room temperature for 3 hours to obtain the precursor solution.
[0076] An alkaline precipitant consisting of NaOH, ammonia, and urea in a mass ratio of 1:1:1 was slowly added to the precursor solution and stirred at room temperature for 1.5 hours to allow the reaction to proceed. The resulting mural reinforcement and protection agent was then separated and collected from the product.
[0077] The mural reinforcing agent obtained in Example 3 of this application has a penetration depth of 260 μm and a color difference of ΔE = 1.78. Figure 13 As shown, this mural strengthening agent was used to strengthen the mural, and the strengthened mural was able to maintain its color well.
[0078] Example 4
[0079] A bacterial cellulose carrier dispersion with a mass concentration of 0.3% and a BaCl2 solution with a mass concentration of 0.025% were prepared, respectively.
[0080] The bacterial cellulose dispersion and BaCl2 solution (volume ratio of 0.03) were mixed and reacted at room temperature for 1.4 h to obtain the precursor solution.
[0081] An alkaline precipitant consisting of NaOH, ammonia, and urea in a mass ratio of 1:4:8 was slowly added to the precursor solution and stirred at room temperature for 0.65 h to carry out the reaction. The mural reinforcement and protection agent was then separated and collected from the product.
[0082] Example 5
[0083] A bacterial cellulose carrier dispersion with a mass concentration of 0.4% and a BaCl2 solution with a mass concentration of 0.04% were prepared, respectively.
[0084] The bacterial cellulose dispersion and BaCl2 solution (volume ratio of 0.04) were mixed and reacted at room temperature for 1.75 h to obtain the precursor solution.
[0085] An alkaline precipitant consisting of NaOH, ammonia, and urea in a mass ratio of 1:2:4 was slowly added to the precursor solution and stirred at room temperature for 0.8 h to carry out the reaction. The mural reinforcement and protection agent was then separated and collected from the product.
[0086] Example 6
[0087] A bacterial cellulose carrier dispersion with a mass concentration of 0.6% and a BaCl2 solution with a mass concentration of 0.075% were prepared, respectively.
[0088] The bacterial cellulose dispersion and BaCl2 solution (volume ratio of 0.07) were mixed and reacted at room temperature for 2.4 h to obtain the precursor solution.
[0089] An alkaline precipitant consisting of NaOH, ammonia, and urea in a mass ratio of 1:2:4 was slowly added to the precursor solution and stirred at room temperature for 1.15 h to carry out the reaction. The mural reinforcement and protection agent was then separated and collected from the product.
[0090] Example 7
[0091] A bacterial cellulose carrier dispersion with a mass concentration of 0.7% and a BaCl2 solution with a mass concentration of 0.085% were prepared, respectively.
[0092] The bacterial cellulose dispersion and BaCl2 solution (volume ratio of 0.085) were mixed and reacted at room temperature for 2.75 h to obtain the precursor solution.
[0093] An alkaline precipitant consisting of NaOH, ammonia, and urea in a mass ratio of 1:1:1 was slowly added to the precursor solution and stirred at room temperature for 1.3 hours to allow the reaction to proceed. The resulting mural reinforcement and protection agent was then separated and collected from the product.
[0094] The relevant experimental data of embodiments four to seven of this application will not be listed one by one.
[0095] The various embodiments in this specification are described in a progressive manner. For the same or similar parts between the various embodiments, please refer to each other. Each embodiment focuses on describing the differences from other embodiments.
[0096] The above embodiments are only used to illustrate the technical solutions of this application, and are not intended to limit this application. Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features therein. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of this application.
Claims
1. A mural reinforcement and protection agent, characterized in that, Includes a bacterial cellulose carrier and Ba(OH)₂ nanoparticles in situ loaded on the bacterial cellulose carrier; The method for preparing the mural reinforcement and protective agent includes: Bacterial cellulose dispersion and BaCl2 solution were prepared separately; The bacterial cellulose dispersion was mixed with the BaCl2 solution to obtain a precursor solution. An alkaline precipitant was added to the precursor solution to carry out the reaction, and then the mural strengthening and protective agent was separated and collected from the product. The bacterial cellulose dispersion has a mass concentration of 0.2% to 0.8%. The mass concentration of the BaCl2 solution is 0.01–0.1%. When the bacterial cellulose dispersion is mixed with the BaCl2 solution, the volume ratio of the bacterial cellulose dispersion to the BaCl2 solution is 0.025 to 0.
1. The alkaline precipitant includes a solvent and NaOH, ammonia, and urea dissolved in the solvent; The mass ratio of NaOH, ammonia water and urea is 1:4:8 to 1:1:1; The reaction time for mixing the bacterial cellulose dispersion with the BaCl2 solution is 1 h to 3 h; The reaction time for adding the alkaline precipitant to the precursor solution is 0.5 h to 1.5 h.
2. The application of the mural reinforcement and protection agent according to claim 1 in the restoration of cultural relics.