A composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, and its preparation method and application

Abstract

The present invention belongs to the technical field of reinforcing materials for wooden cultural relics unearthed in arid environments, and discloses a composite filling and reinforcing agent for decayed wooden cultural relics unearthed in arid environments, as well as its preparation method and application. The composite filling and reinforcing agent comprises a natural rosin solution, an ethyl cellulose solution and glycerol; the volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1; the volume of glycerol is 1% of the total volume of the composite filling and reinforcing agent. The ethyl cellulose used in the present invention can be used as a retarder and adhesive, and can form a tough film, which can make up for the shortcomings of rosin; using ethanol as a solvent can better bring rosin and ethyl cellulose into the cavities caused by decay in the wood, and the glycerol contained therein can also provide a moisturizing function for the wood. The composite filling and reinforcing agent of the present invention has good permeability and can be applied to wood with a high degree of decay, and the color difference is also within an acceptable range.

Description

Technical Field

[0001] The invention relates to the technical field of reinforcing materials for wooden cultural relics unearthed in arid environments, and in particular to a composite filling reinforcing agent for rotten wooden cultural relics unearthed in arid environments, and a preparation method and application thereof. Background Art

[0002] With the development and improvement of archaeological technology, more and more cultural relics are being discovered and excavated, and the materials and types of cultural relics are constantly enriched. Only by preserving the original appearance of the cultural relics can the historical value, artistic value and scientific value contained in the cultural relics be preserved. Therefore, cultural relic protection technology must also be constantly innovated, and the principles of cultural relic protection must be followed in the process of implementing protection, which in turn increases the difficulty of cultural relic protection.

[0003] "Wooden artifacts" primarily refer to historical relics made primarily of wood. As a renewable resource compared to other materials, wood has long attracted significant attention in the development of human society due to its many excellent properties. From primitive society to the present day, wood has played a vital role in human life. However, wood also has its own disadvantages, including: 1. Wood is an anisotropic, non-homogeneous material. Its uneven expansion and contraction exacerbates deformation, and the differences in strength in all directions can easily lead to cracking. 2. Wood is a hygroscopic material, naturally swelling and shrinking under wet conditions, affecting its dimensional stability and making it susceptible to deformation. 3. Wood is a naturally high-molecular-weight organic polymer, susceptible to insects and fungi (molds and wood-decaying fungi), which can degrade the wood and damage wooden products. 4. Wood is flammable. 5. Wood preserved (excavated) in dry areas has a lower moisture content, and the main problems it suffers include cracking, deformation, decay, and insect infestation. Severely decayed wood completely loses its strength, thus losing its cultural value. Water-saturated wood, on the other hand, has a very high moisture content and rapidly loses water in the air after excavation, causing cracking and deformation in the process. Therefore, dehydration is the primary consideration in protecting water-saturated lacquered wood. Due to the different characteristics of dry and water-saturated wood, different reinforcements are required to address these characteristics.

[0004] Research on reinforcing materials for wooden objects has always been a key and challenging aspect of cultural relic preservation. Besides inherent damage to wooden objects, changes in the burial environment after excavation can also cause secondary damage to precious cultural relics. Wooden objects are typically found in two different states upon excavation: saturated and dry. Due to economic development and other factors, current research focuses on the characterization and reinforcement of saturated wood. These methods generally involve dehydration followed by an initial step to increase the structural strength of the artifact. Reinforcement of dried wood primarily involves the following methods: In the 19th century, inorganic water glass (NaSiO₃) was used for wood reinforcement. Natural organic products such as natural glues, oils, waxes, resins, and sucrose have also been used to reinforce dried wood. Natural glues include hide glue, bone glue, fish glue, and soybean glue. Due to their shortcomings, such as resistance to fungi and insects and poor hygroscopicity, they have been widely replaced in recent years by synthetic resins. Tung oil, a major oil, is known for its high hardness and water repellency. However, its disadvantages are that it struggles to fully harden when cooled and can stain the wood surface. In the early 20th century, a method of soaking wood in a hot wax-resin mixture was reported. Adding fungicides and insecticides to the wax not only strengthened the wood but also provided corrosion and insect repellent properties. Impregnating wood with beeswax also provided moisture resistance, but its effectiveness was limited. Furthermore, beeswax had poor weather resistance and was prone to aging and brittleness. Beeswax, rosin, and rosin-gasoline solutions could be used directly as wood reinforcements, with the addition of appropriate insecticides enhancing their insect repellency. Rosin-reinforced wood was heat-resistant and water-repellent, but its reinforcement was poor, with poor corrosion resistance and brittleness. Sucrose was also used to reinforce wood, but its hygroscopicity made the treated wood unstable under environmental changes. Furthermore, the presence of sugar easily led to mold, decay, and insect infestation, making this treatment insufficient. A later approach was to displace the sucrose solution from the wood with an ethanol solution of phenolic resin, thereby fixing the phenolic resin in the wood. This treatment did not alter the shape of the wood.

[0005] With the continuous enrichment of materials, various synthetic organic materials are also used for the impregnation reinforcement of dried wooden cultural relics and have achieved certain results, such as: polyvinyl butyral, styrene, methyl methacrylate, epoxy resin, etc.

[0006] In recent years, Southwest Forestry University has used reinforcing agents made from rosin and shellac to reinforce water-saturated wooden cultural relics; Nanjing Forestry University has developed reinforcing agents for water-saturated rotten wood using suberic acid and alcohols (methanol, n-butanol and propylene glycol) as raw materials; the Wood Industry Research Institute of the Chinese Academy of Forestry uses nanocellulose to preserve and reinforce wood. This process requires soaking and vacuuming the wood, which is not conducive to the protection of cultural relics; Foshan Renhe Chemical Coatings Co., Ltd. uses wood wax oil, hexamethyldisiloxane and other raw materials to reinforce water-saturated cultural relics. The above methods have all been used to reinforce water-saturated wooden artifacts, but there has been no research on the reinforcement of wooden artifacts unearthed in arid environments.

[0007] Therefore, in response to the above problems and the characteristics of diseases on wooden objects unearthed in arid environments, preparing a convenient and practical reinforcement material is a key issue that needs to be urgently addressed. Summary of the Invention

[0008] The purpose of the present invention is to provide a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, as well as a preparation method and application thereof, to solve the above-mentioned problems existing in existing reinforcing materials.

[0009] In order to achieve the above-mentioned object of the invention, the present invention provides the following technical solutions:

[0010] The present invention provides a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, comprising a natural rosin solution, an ethyl cellulose solution and glycerol;

[0011] The volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1;

[0012] The volume of the glycerol is 1% of the total volume of the composite filling and reinforcing agent.

[0013] Preferably, in the above-mentioned composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, the natural rosin solution is obtained by dissolving natural rosin in anhydrous ethanol;

[0014] The ethyl cellulose solution is obtained by dissolving ethyl cellulose in anhydrous ethanol.

[0015] Preferably, in the composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, the concentration of the natural rosin solution is 2-5%;

[0016] The concentration of the ethyl cellulose solution is 2-5%.

[0017] Preferably, in the above-mentioned composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, the natural rosin in the natural rosin solution is grade IV or grade V rosin.

[0018] The present invention also provides a method for preparing a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in an arid environment, comprising the following steps:

[0019] A natural rosin solution and an ethyl cellulose solution are mixed and then propylene glycol is added to obtain a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments.

[0020] The present invention also provides an application of a composite filling and reinforcing agent for reinforcing rotten wooden cultural relics unearthed in an arid environment.

[0021] Preferably, in the application of the composite filling and reinforcing agent for reinforcing rotten wooden cultural relics unearthed in arid environments in reinforcing wooden cultural relics, the method for reinforcing wooden cultural relics comprises the following steps:

[0022] Spraying the composite filling and reinforcing agent on the surface of the wooden cultural relics;

[0023] Or apply cotton gauze on the surface of wooden cultural relics and then spray composite filling and reinforcement agent;

[0024] Or soak the wooden artifacts in a composite filling and reinforcing agent.

[0025] Preferably, in the application of the composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments in reinforcing wooden cultural relics, the number of times the wooden cultural relics are reinforced is greater than or equal to 1.

[0026] It can be seen from the above technical solutions that compared with the prior art, the present invention has the following beneficial effects:

[0027] The present invention adopts natural rosin, ethyl cellulose and glycerol, carries out a series of proportion combinations, dissolves by ethanol, and combines into a composite filling reinforcement agent. If the wooden cultural relics reinforced with rosin alone are heat-resistant and water-repellent, the reinforcement effect is poor, the corrosion resistance is poor and it is easy to become brittle. The ethyl cellulose used in the present invention can be used as a retarder and adhesive, and can form a tough film, which can make up for the shortcomings of rosin; using ethanol as a solvent can better bring rosin and ethyl cellulose into the cavity caused by the decay of the wood. After the ethanol evaporates, the mixture composed of rosin and ethyl cellulose can achieve a better reinforcement effect; the glycerol contained therein can also provide a moisturizing function for the wood. The composite filling reinforcement agent of the present invention has good permeability and can be applied to wood with a large degree of decay, and the color difference is also within an acceptable range. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for describing the embodiments or the prior art.

[0029] Figure 1 Schematic diagram of the penetration depth of the composite filling and reinforcing agent of Example 1;

[0030] Figure 2 Schematic diagram of the penetration depth of the composite filling and reinforcing agent of Example 2;

[0031] Figure 3 Schematic diagram of the penetration depth of the composite filling and reinforcing agent of Example 3;

[0032] Figure 4 The compressive strength test results of the cultural relics samples before reinforcement;

[0033] Figure 5 These are the compressive strength test results of the cultural relics samples after reinforcement. DETAILED DESCRIPTION

[0034] The present invention provides a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, comprising a natural rosin solution, an ethyl cellulose solution and glycerol;

[0035] The volume ratio of the natural rosin solution to the ethyl cellulose solution is preferably 1:1;

[0036] The volume of the glycerol is preferably 1% of the total volume of the composite filling and reinforcing agent.

[0037] In the present invention, the natural rosin solution is preferably obtained by dissolving natural rosin in anhydrous ethanol;

[0038] The ethyl cellulose solution is preferably obtained by dissolving ethyl cellulose in anhydrous ethanol.

[0039] In the present invention, the concentration of the natural rosin solution is preferably 2-5%, more preferably 2, 3, 4 or 5%, and more preferably 3%;

[0040] The concentration of the ethyl cellulose solution is preferably 2-5%, more preferably 2, 3, 4 or 5%, and even more preferably 4%.

[0041] In the present invention, the natural rosin in the natural rosin solution is preferably grade 4 or grade 5 rosin, more preferably grade 5 rosin. The natural rosin used in the subsequent examples of the present invention is commercially available Qinbao violin-specific rosin No. 602#.

[0042] The present invention also provides a method for preparing a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in an arid environment, comprising the following steps:

[0043] A natural rosin solution and an ethyl cellulose solution are mixed and then propylene glycol is added to obtain a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments.

[0044] The present invention also provides an application of a composite filling and reinforcing agent for reinforcing rotten wooden cultural relics unearthed in an arid environment.

[0045] In the present invention, the method for reinforcing wooden cultural relics comprises the following steps:

[0046] Spraying the composite filling and reinforcing agent on the surface of the wooden cultural relics;

[0047] Or apply cotton gauze on the surface of wooden cultural relics and then spray composite filling and reinforcement agent;

[0048] Or soak the wooden artifacts in a composite filling and reinforcing agent.

[0049] In the present invention, the number of times the wooden cultural relic is reinforced is preferably greater than or equal to 1 time, more preferably 3 to 10 times, and even more preferably 7 times.

[0050] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0051] Example 1

[0052] This embodiment provides a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, comprising a 3% natural rosin solution (obtained by dissolving natural rosin in anhydrous ethanol), a 3% ethyl cellulose solution (obtained by dissolving ethyl cellulose in anhydrous ethanol), and 1% glycerol, accounting for the total volume of the composite filling and reinforcing agent. The volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1.

[0053] The preparation method of the composite filling and reinforcing agent comprises the following steps:

[0054] After the natural rosin solution and the ethyl cellulose solution are evenly mixed, glycerol is added and mixed evenly to obtain a composite filling and reinforcing agent.

[0055] Example 2

[0056] This embodiment provides a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, comprising a 4% natural rosin solution (obtained by dissolving natural rosin in anhydrous ethanol), a 4% ethyl cellulose solution (obtained by dissolving ethyl cellulose in anhydrous ethanol), and 1% glycerol, accounting for the total volume of the composite filling and reinforcing agent. The volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1.

[0057] The preparation method of the composite filling and reinforcing agent comprises the following steps:

[0058] After the natural rosin solution and the ethyl cellulose solution are evenly mixed, glycerol is added and mixed evenly to obtain a composite filling and reinforcing agent.

[0059] Example 3

[0060] This embodiment provides a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, comprising a 5% natural rosin solution (obtained by dissolving natural rosin in anhydrous ethanol), a 5% ethyl cellulose solution (obtained by dissolving ethyl cellulose in anhydrous ethanol), and 1% glycerol, accounting for the total volume of the composite filling and reinforcing agent. The volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1.

[0061] The preparation method of the composite filling and reinforcing agent comprises the following steps:

[0062] After the natural rosin solution and the ethyl cellulose solution are evenly mixed, glycerol is added and mixed evenly to obtain a composite filling and reinforcing agent.

[0063] Performance testing:

[0064] Permeability test: Take wood samples with a specification of 10*0.2*0.8cm, and put them into the composite filling and reinforcement agent with a depth of 5mm in Examples 1 to 3 respectively, and place them for 30 minutes. Then take them out and place them at room temperature and dry them in the shade; then put them into an iodine cylinder for 10 minutes and take them out. The penetration depth is measured (when the penetration depth reaches more than 10mm, it meets the requirements). The results are as follows Figures 1 to 3 As shown. Figures 1 to 3 It can be seen that the penetration depth of the wood sample in the composite filling and reinforcing agent of Example 1 is about 4 cm, the penetration depth of the wood sample in the composite filling and reinforcing agent of Example 2 is about 3 cm, and the penetration depth of the wood sample in the composite filling and reinforcing agent of Example 3 is about 5 cm.

[0065] Color difference analysis: A wood sample was placed on a colorimeter and its initial value was recorded. The composite filling and reinforcing agents prepared in Examples 1 to 3 were then applied to the sample surface, placed at room temperature, and dried in the shade. The values were measured again and the color difference was calculated. The composite filling and reinforcing agent was repeatedly applied and measured again. The statistical color difference values are shown in Tables 1 to 3.

[0066] Table 1 Color difference statistics of the composite filling and reinforcing agent of coating Example 1

[0067]

[0068] Table 2 Statistical results of color difference of the composite filling and reinforcing agent of coating Example 2

[0069]

[0070] Table 3 Color difference statistics of the composite filling and reinforcing agent of coating Example 3

[0071]

[0072]

[0073] It can be seen from Tables 1 to 3 that the average color difference of the composite filling reinforcement agent of Example 1 is 0.48, the average color difference of the composite filling reinforcement agent of Example 2 is 0.82, and the average color difference of the composite filling reinforcement agent of Example 3 is 0.65. The change in the color of the wood after reinforcement is slight or slight (the corresponding relationship between the ΔE value and the color change is shown in Table 4).

[0074] Table 4 Correspondence between △E value and color change

[0075]

[0076] Solvent permeability: Wood samples were reinforced with the composite filler reinforcements from Examples 1-3 and dried in the shade at room temperature. Purified water, ethanol, acetone, and ethyl acetate were then dripped onto the sample surfaces to observe their permeability and determine the reversibility of the composite filler reinforcements. The results showed that pure water, when dripped onto the surfaces of the reinforced samples at the three concentrations from Examples 1-3, failed to penetrate, remaining in a droplet-like form after half an hour, with slight penetration (wetting) at the edges. Ethanol, acetone, and ethyl acetate, when dripped onto the surfaces of the reinforced samples at the three concentrations from Examples 1-3, quickly penetrated, spread evenly across the sample, and dried quickly.

[0077] Reinforcement of cultural relics samples: The composite filling reinforcement agent of Example 3 was used to reinforce the unearthed tomb door. The specific experimental content was: relatively straight wooden strips were selected from the tomb door residue, and the composite filling reinforcement agent was lightly applied to the wood surface with a hook pen. According to the degree of decay of the wood, two reinforcements were performed; after reinforcement, its compressive strength was measured; the test results before and after reinforcement are shown as follows: Figures 4-5 As shown. Figures 4-5 It can be seen from the experimental data that the cultural relic samples have almost no compressive strength before reinforcement, and the samples will turn into powder after a little pressure is applied; after reinforcement, the cultural relic samples can withstand a pressure of up to 28N, which illustrates the effectiveness of the composite filling reinforcement agent.

[0078] The above is only a preferred embodiment of the present invention. It should be pointed out that for ordinary technicians in this technical field, several improvements and modifications can be made without departing from the principles of the present invention. These improvements and modifications should also be regarded as within the scope of protection of the present invention.

Claims

1. A composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments, characterized in that: including natural rosin solution, ethyl cellulose solution and glycerol; The volume ratio of the natural rosin solution to the ethyl cellulose solution is 1:1; The volume of the glycerol is 1% of the total volume of the composite filling and reinforcing agent; The natural rosin solution is obtained by dissolving natural rosin in anhydrous ethanol; The ethyl cellulose solution is obtained by dissolving ethyl cellulose in anhydrous ethanol; The concentration of the natural rosin solution is 2-5%; The concentration of the ethyl cellulose solution is 2-5%.

2. The composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments according to claim 1, characterized in that: The natural rosin in the natural rosin solution is grade 4 or grade 5 rosin.

3. The method for preparing a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments according to claim 1 or 2, characterized in that: The following steps are involved: A natural rosin solution and an ethyl cellulose solution are mixed and then propylene glycol is added to obtain a composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments.

4. Use of the composite filling and reinforcing agent for rotten wooden cultural relics unearthed in arid environments as claimed in claim 1 or 2 in reinforcing wooden cultural relics.

5. The use of a composite filling and reinforcing agent for reinforcing rotten wooden cultural relics unearthed in arid environments according to claim 4, characterized in that: The method for reinforcing wooden cultural relics comprises the following steps: Spraying the composite filling and reinforcing agent on the surface of the wooden cultural relics; Or apply cotton gauze on the surface of wooden cultural relics and then spray composite filling and reinforcement agent; Or soak the wooden artifacts in a composite filling and reinforcing agent.

6. Use of the composite filling and reinforcing agent for reinforcing rotten wooden cultural relics unearthed in arid environments according to claim 4 or 5, characterized in that: The number of reinforcements of the wooden cultural relics is greater than or equal to 1 time.

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