Method for reinforcing unearthed water-saturated rotten bone cutin cultural relics

Abstract

The invention relates to a method for reinforcing unearthed water-saturated decayed bone keratin cultural relics, in particular to a method for reinforcing unearthed water-saturated decayed bone keratin cultural relics by using three-dimensional net-shaped hydroxyapatite, which comprises the following steps: 1) dehydrating the bone keratin cultural relics in an environment with constant temperature and humidity; (2) adding a calcium source solution into the surface of the obtained dehydrated bone keratin cultural relic, and carrying out dehydration treatment in an environment with constant temperature and humidity; (3) a phosphorus source solution is added to the surface of the dehydrated bone keratin cultural relic obtained in the step (2), and dehydration treatment is conducted again in the environment with the constant temperature and humidity; and 4) repeating the steps 2) to 3) for multiple times. Compared with the prior art, the calcium source and the phosphorus source are used for reinforcing the bone keratin cultural relics, three-dimensional net-shaped hydroxyapatite is generated in cracks of the bone keratin cultural relics, the reinforcing effect is effectively improved, safe dehydration and reinforcing of the unearthed water-saturated rotten bone keratin cultural relics are achieved, and the risk that the cultural relics disintegrate due to excessive water loss or excessive water replenishing is avoided.

Description

Technical Field

[0001] The invention belongs to the technical field of cultural relic protection materials, and relates to a method for reinforcing unearthed water-saturated trough rotten bone keratin cultural relics, and specifically, relates to a method for reinforcing unearthed water-saturated trough rotten bone keratin cultural relics by using three-dimensional network hydroxyapatite. Background Art

[0002] Ancient human bones, animal bones, teeth and other bone artifacts are important physical evidence for studying the history of human development and the history of natural development. Although they have their own characteristics in structure, their compositions are similar, and they are all composed of organic and inorganic components. The inorganic component is mainly hydroxyapatite, which gives it excellent mechanical properties such as crack resistance, compression resistance and bending resistance; while the organic component is mainly composed of collagen, protein, etc., which plays an important role in the toughness of bone materials. These components are intertwined in three-dimensional space to form a composite material with a special structure.

[0003] In a long-term underground burial environment, the organic part of bone materials (such as protein, fat, etc.) is gradually replaced by minerals in the environment, such as calcium dioxide (SiO2) and calcium carbonate (CaCO3), resulting in the gradual mineralization of bones and the formation of relatively stable fossils. However, archaeological excavations often encounter a large number of unmineralized bone and horny cultural relics, such as ancient ivory unearthed from Sanxingdui, human bones unearthed from sites in the middle reaches of the Yangtze River such as the Qujialing culture and Shijiahe culture periods, human bones and animal bones unearthed from sites in southern China such as the Liangzhu site, and ivory carvings unearthed from tombs in northern China such as the Dawenkou culture site in Shandong and the Yinxu site. Due to the short burial time, these cultural relics have not yet been completely fossilized. They are easily affected by multiple factors such as their own composition, surrounding soil, changes in environmental temperature and humidity, water action, pH, soluble salts, mold, animals and plants, and are seriously decayed. The interior is extremely fragile and urgently needs protection and reinforcement.

[0004] At present, the reinforcement of unearthed water-saturated and rotten bone and keratin cultural relics is one of the internationally recognized problems. The core problem is the lack of reinforcement materials with high penetration depth, good compatibility and suitable bonding strength. The existing technology mainly relies on organic materials, such as shellac, polyethylene glycol (PEG), acrylic resin and silicone resin. However, these materials are not fully compatible with cultural relics, have poor permeability, and are prone to aging and discoloration. In addition, although some modified water glass hybrid materials can replace the moisture inside bone and keratin cultural relics and fill the pores, there are also problems of incompatibility and destruction of the authenticity of cultural relics.

[0005] Hydroxyapatite (HAP) is an important inorganic component of many organisms and is also the main component of the matrix of bone and horny cultural relics. The introduction of hydroxyapatite into the matrix of bone and horny cultural relics can not only preserve the authenticity of the cultural relics, but also its chemical properties are very stable and its solubility is extremely low. In addition, hydroxyapatite has moderate mechanical strength and good bonding performance with the matrix, which has the natural advantage of becoming a protective material for bone and horny cultural relics. However, since the unearthed water-saturated and decayed bone and horny cultural relics are very fragile, excessive water loss or excessive water replenishment may cause the cultural relics to disintegrate. In addition, these cultural relics have a high water content, requiring the reinforcement material to be synthesized inside the bone and horny cultural relics while also achieving safe water replacement. Based on this, the synthesis of hydroxyapatite inside the cultural relics requires overcoming many process challenges, ensuring that the material has sufficient penetration depth and meets the specific requirements of the formed hydroxyapatite structure. Summary of the invention

[0006] The present invention aims to overcome the deficiencies of existing materials and processes, and provides a method for reinforcing rotten bone and keratin cultural relics unearthed in water-saturated troughs. Specifically, it relates to a method for using three-dimensional network hydroxyapatite to reinforce rotten bone and keratin cultural relics unearthed in water-saturated troughs. The three-dimensional network hydroxyapatite is an inorganic material with the characteristics of stable chemical properties, moderate mechanical strength and excellent cementing properties. The present invention proposes a "bone to bone" cycle process through multiple "safe water loss-application of reinforcing materials (rapid water replenishment)", which overcomes the limitations of the existing reinforcing materials that have insufficient penetration depth and only act on larger cracks on the surface of cultural relics and are difficult to penetrate into small cracks inside. The method effectively avoids the risk of cultural relics disintegrating due to excessive water loss or excessive water replenishment, and realizes the effective reinforcement and protection of rotten bone and keratin cultural relics unearthed in water-saturated troughs.

[0007] Since the unearthed water-saturated rotten bone keratin cultural relics have a high water content, the reinforcement material needs to achieve safe water replacement while being synthesized inside the cultural relics. Through appropriate raw materials and processes, hydroxyapatite with a three-dimensional network structure is formed in the matrix of the cultural relics, which can not only meet the needs of the cultural relics' air permeability, but also combine well with the matrix of the cultural relics, filling the internal pores of various sizes, thereby achieving safe dehydration and reinforcement of the cultural relics.

[0008] The purpose of the present invention can be achieved by the following technical solutions:

[0009] The present invention provides a method for reinforcing unearthed water-saturated and rotten bone and keratin cultural relics by using three-dimensional network hydroxyapatite, which specifically comprises the following steps:

[0010] (1) Dehydration treatment of unearthed water-saturated and rotten bone and keratin cultural relics in an environment with constant temperature and humidity;

[0011] (2) adding a calcium source solution to the surface of the unearthed water-saturated rotten bone horny cultural relics, and performing a dehydration treatment again in an environment of constant temperature and humidity;

[0012] (3) adding a phosphorus source solution to the surface of the unearthed water-saturated rotten bone keratin cultural relic obtained in step (2) and performing a dehydration treatment again in an environment of constant temperature and humidity;

[0013] (4) Repeat steps (2) to (3) multiple times.

[0014] Furthermore, the unearthed water-soaked and rotten bone and keratin cultural relics are unearthed water-soaked and rotten ivory.

[0015] Furthermore, when two calcium sources are used for reinforcement, the calcium sources include a first calcium source and a second calcium source. After step (1), the first calcium source is first used to perform steps (2) to (4), and then the second calcium source is used to replace the first calcium source to repeat steps (2) to (4), so that the unearthed water-saturated rotten bone and keratin cultural relics are reinforced with three-dimensional network hydroxyapatite.

[0016] Furthermore, when two calcium sources are used for reinforcement, the dehydration treatment time of the first calcium source and the second calcium source is equal. Preferably, the dehydration treatment time of the first calcium source and the second calcium source is 7 days.

[0017] Furthermore, the calcium source includes at least one of calcium formate, calcium acetate, calcium propionate, and nano calcium hydroxide, and the phosphorus source is diammonium hydrogen phosphate.

[0018] Furthermore, when the calcium source is calcium formate, calcium acetate, or calcium propionate, the solvent of the calcium source solution is water; when the calcium source is nano calcium hydroxide, the solvent of the calcium source solution is isopropanol; and the solvent of the phosphorus source solution is water.

[0019] Furthermore, the molar ratio of the calcium source added in step (2) to the phosphorus source added in step (3) is (0.05-1):(0.2-0.8), preferably (0.34-1):0.6.

[0020] Furthermore, when the calcium source is calcium formate, calcium acetate, or calcium propionate, the molar ratio of the calcium source to the phosphorus source is 1:0.6; when the calcium source is nano calcium hydroxide, the molar ratio of the calcium source to the phosphorus source is 0.34:0.6. Calcium source solution and phosphorus source solution are used as precursor solutions for synthesizing hydroxyapatite in unearthed water-saturated rotten bone and keratin cultural relics. Calcium formate, calcium acetate, and calcium propionate are dissolved in water to form an organic calcium aqueous solution, which has high permeability and can react with the phosphorus source to generate hydroxyapatite in the fine cracks inside the unearthed water-saturated rotten bone and keratin cultural relics. Calcium hydroxide is a nano suspension, which can react with the phosphorus source to generate hydroxyapatite in the large cracks on the surface of the unearthed water-saturated rotten bone and keratin cultural relics.

[0021] Furthermore, in steps (1) to (3), the temperature in the constant temperature and humidity environment is 20-25°C and the humidity is 80-90%. Preferably, the temperature in the constant temperature and humidity environment is 25°C and the humidity is 85%. Since the burial environment of the unearthed water-saturated and rotten bone and keratin cultural relics is a high-humidity environment, they are stored in a high-humidity environment to prevent the cultural relics from being damaged due to excessive water loss.

[0022] Furthermore, in step (4), the process is repeated several times until the color difference ΔE of the unearthed water-saturated rotten bone and keratin cultural relics is less than 5. The repetition time is determined according to the amount of reinforcement material (calcium source solution and phosphorus source solution) applied and the state of the unearthed water-saturated rotten bone and keratin cultural relics themselves. Specifically, for unearthed water-saturated rotten ivory cultural relics, when the penetration rate of the reinforcement material slows down significantly, a colorimeter is used to measure the color difference ΔE of the unearthed water-saturated rotten ivory. When ΔE<5, the process can be stopped. The repetition time may be different for different cultural relics according to their specific conditions.

[0023] Furthermore, in steps (2) to (3), the dehydration treatment time is 10-20 hours; in step (4), after repeated treatments, the cumulative dehydration treatment time is 10-20 days. Preferably, in steps (2) to (3), the dehydration treatment time is 12 hours; in step (4), after repeated treatments, the cumulative dehydration treatment time is 14 days.

[0024] Furthermore, the mass addition amount of the calcium source solution and the phosphorus source solution is equal to the water loss amount of the water loss treatment before addition.

[0025] Compared with the prior art, the present invention has the following characteristics:

[0026] 1) The present invention provides a method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics, i.e., a "bone-to-bone" cycle process of "safe dehydration-application of reinforcing materials (rapid water replenishment)" for multiple times, which effectively realizes the safe dehydration and reinforcement of water-saturated rotten bone and keratin cultural relics, and avoids the risk of cultural relics disintegrating due to large-scale water loss or water replenishment;

[0027] 2) The present invention uses a calcium source solution and a phosphorus source solution as precursor solutions for synthesizing hydroxyapatite in unearthed water-saturated rotten bone and keratin cultural relics, and has a high penetration depth. When the organic calcium aqueous solution and the nano calcium hydroxide suspension are used as calcium sources at the same time and are used in steps with the phosphorus source to reinforce the unearthed water-saturated rotten bone and keratin cultural relics, the organic calcium aqueous solution has a high permeability and can generate a three-dimensional network hydroxyapatite with the phosphorus source inside, and the nano calcium hydroxide suspension can generate a three-dimensional network hydroxyapatite with the phosphorus source in larger cracks. The three-dimensional network hydroxyapatite has good compatibility with the cultural relic matrix material, can effectively combine with the cultural relic matrix, and has an excellent pore structure. At the same time, the three-dimensional network structure can meet the air permeability requirements of the bone and keratin cultural relics;

[0028] 3) The method for reinforcing unearthed water-saturated and decayed bone and horn cultural relics provided by the present invention can not only reinforce and protect the small cracks inside the bone and horn cultural relics, but also repair and protect the larger cracks inside the bone and horn cultural relics, thereby effectively improving the reinforcement effect;

[0029] 4) The three-dimensional network structure of hydroxyapatite prepared by the present invention has the advantages of high penetration depth, good compatibility and bonding with the bone keratin cultural relic matrix material, and excellent pore structure, and can effectively improve the reinforcement effect on bone keratin cultural relics. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a schematic diagram of the process flow of reinforcing unearthed water-saturated rotten bone and keratin cultural relics in the present invention;

[0031] Figure 2 The X-ray diffraction (XRD) pattern and scanning electron microscope (SEM) pattern of the hydroxyapatite prepared in Example 1;

[0032] Figure 3 The XRD spectrum and SEM spectrum of the hydroxyapatite prepared in Example 2;

[0033] Figure 4 The XRD spectrum and SEM spectrum of the hydroxyapatite prepared in Example 3;

[0034] Figure 5 The SEM images of the water-saturated and rotten ivory unearthed in Example 4 after reinforcement and the hardness and elastic modulus data before and after reinforcement;

[0035] Figure 6 The SEM images of the water-saturated and decayed ivory unearthed in Example 5 after reinforcement and the hardness and elastic modulus data before and after reinforcement;

[0036] Figure 7 The SEM images of the water-saturated and decayed ivory unearthed in Example 6 after reinforcement, as well as the hardness and elastic modulus data before and after reinforcement. DETAILED DESCRIPTION

[0037] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and provides a detailed implementation method and specific operation process, but the protection scope of the present invention is not limited to the following embodiments.

[0038] In the following examples, unless otherwise specified, raw materials, reagents or processing techniques are all conventional commercial products or conventional processing techniques in the art.

[0039] The nano calcium hydroxide used in the following examples is CaLoSil; the unearthed water-soaked rotten bone and keratin cultural relics used are water-soaked rotten ivory samples unearthed from the No. 3 sacrificial pit at the Sanxingdui site.

[0040] The embodiment provides a method for reinforcing unearthed water-saturated rotten bone and horny cultural relics, which specifically includes the following steps:

[0041] After the unearthed water-saturated and rotten bone and keratin artifacts are taken out, they are placed in an environment with constant temperature and humidity to dehydrate for 12 hours;

[0042] Add calcium acetate solution to the surface of the unearthed water-saturated rotten bone and keratin artifacts, and continue to place them in a constant temperature and humidity environment for dehydration treatment for 12 hours;

[0043] Add diammonium phosphate solution to the surface of the unearthed water-saturated rotten bone and keratin artifacts, and continue to place them in a constant temperature and humidity environment for dehydration treatment for 12 hours;

[0044] Add nano-calcium hydroxide suspension to the surface of the unearthed water-saturated rotten bone and keratin artifacts, and continue to place them in a constant temperature and humidity environment for dehydration treatment for 12 hours;

[0045] Add diammonium phosphate solution to the surface of the unearthed water-saturated rotten bone and keratin artifacts again, and continue to place them in a constant temperature and humidity environment for dehydration treatment for 12 hours;

[0046] The above process is repeated until the unearthed water-saturated rotten bone and keratin artifacts are reinforced with three-dimensional network hydroxyapatite.

[0047] In some specific embodiments, the unearthed water-soaked and decayed bone and keratin cultural relics are unearthed water-soaked and decayed ivory.

[0048] In some specific embodiments, the concentration of the calcium acetate solution is 1 mol / L.

[0049] In some specific embodiments, the concentration of the diammonium hydrogen phosphate solution is 0.6 mol / L.

[0050] In some specific embodiments, the concentration of the calcium hydroxide nanosuspension is 0.34 mol / L.

[0051] In some specific embodiments, calcium acetate solution and diammonium phosphate solution are alternately added to the surface of unearthed water-saturated and decayed ivory, and this process is repeated in an environment of constant temperature and humidity until the ivory is reinforced with a three-dimensional network of hydroxyapatite.

[0052] In some specific embodiments, nano calcium hydroxide suspension and diammonium phosphate solution are alternately dripped onto the surface of unearthed water-saturated and decayed ivory, and this process is repeated in an environment of constant temperature and humidity until the ivory is reinforced with a three-dimensional network of hydroxyapatite.

[0053] In some specific embodiments, calcium acetate solution, nano calcium hydroxide suspension and diammonium phosphate solution are dripped onto the surface of unearthed water-saturated and decayed ivory, and this process is repeated in an environment of constant temperature and humidity until the ivory is reinforced with three-dimensional network hydroxyapatite.

[0054] The three-dimensional network hydroxyapatite provided by the present invention is not only suitable for reinforcing unearthed decayed and water-saturated ivory, but can also be extended to be applied to reinforcing and protecting other unearthed decayed and water-saturated bone and keratin cultural relics.

[0055] It should be noted that the individual differences of bone and horn artifacts unearthed in waterlogged and decayed conditions are usually large, and this phenomenon also exists in bone and horn artifacts unearthed at the same excavation site. Due to the particularity of the structure, it is extremely difficult to obtain simulated (standard) samples of bone and horn artifacts. In addition, due to the heterogeneity of ancient ivory artifacts, there is still a lack of a complete characterization method for the physical properties of artifacts before and after reinforcement. Therefore, the ratio of various components used to form the three-dimensional network hydroxyapatite needs to be optimized according to the individual artifacts to be reinforced and protected.

[0056] The embodiment also provides a three-dimensional network hydroxyapatite and a synthesis method thereof:

[0057] In an alkaline environment, a calcium acetate solution, a diammonium hydrogen phosphate solution and a calcium hydroxide nano suspension are mixed in a certain proportion and sequence;

[0058] The mixed solution is placed in an environment with constant temperature and humidity;

[0059] Finally, a three-dimensional network structure of hydroxyapatite is obtained.

[0060] In some specific embodiments, in the alkaline environment, the pH value is 9.0.

[0061] In some specific embodiments, the concentration of the calcium acetate solution is 1 mol / L.

[0062] In some specific embodiments, the concentration of the diammonium hydrogen phosphate solution is 0.2 mol / L or 0.6 mol / L.

[0063] In some specific embodiments, the concentration of the calcium hydroxide nanosuspension is 0.34 mol / L.

[0064] In some specific embodiments, only calcium acetate solution and ammonium dihydrogen phosphate solution are mixed and placed in a curing box with constant temperature and humidity to obtain a three-dimensional network of hydroxyapatite.

[0065] In some specific embodiments, only the nano calcium hydroxide suspension and the ammonium dihydrogen phosphate solution are mixed and placed in a curing box at a constant temperature and humidity to obtain a three-dimensional network of hydroxyapatite.

[0066] In some specific embodiments, calcium acetate solution, nano calcium hydroxide suspension and ammonium dihydrogen phosphate solution are mixed simultaneously and placed in a curing box at a constant temperature and humidity to obtain three-dimensional network hydroxyapatite.

[0067] Embodiment 1:

[0068] A three-dimensional network hydroxyapatite, the synthesis method of which comprises:

[0069] Prepare 1 mol / L calcium acetate solution and 0.6 mol / L diammonium phosphate solution and add ammonia water to adjust the pH of the solution to 9 to make the solution weakly alkaline. Take 1 mL of calcium acetate solution and add it to a 5 mL beaker, then take 1 mL of diammonium phosphate solution and add it to the above beaker. After a brief stirring, place the beaker in a curing box with a constant temperature of 25°C and a constant humidity of 85%, and take it out after two weeks (14 days). Use XRD and SEM to observe the phase composition and microscopic morphology of the product (see Figure 2 ). The results showed that the product was hydroxyapatite, and its structure was lamellar stacking.

[0070] Embodiment 2:

[0071] The preparation method of this example is similar to that of Example 1, except that the calcium acetate solution (1 mol / L) is replaced by a nano calcium hydroxide suspension (0.34 mol / L, the solvent is isopropanol), and the concentration of the diammonium hydrogen phosphate solution is 0.2 mol / L. XRD and SEM are used to observe the phase composition and microscopic morphology of the product (see Figure 3 ). The results showed that the product was hydroxyapatite, which had a layered structure but a certain three-dimensional network structure.

[0072] Embodiment 3:

[0073] The preparation method of this embodiment refers to that of embodiment 1, except that 1 mL of calcium acetate solution (1 mol / L), 1 mL of diammonium hydrogen phosphate solution (0.6 mol / L), 1 mL of nano calcium hydroxide suspension (0.34 mol / L, the solvent is isopropanol) and 1 mL of diammonium hydrogen phosphate solution (0.2 mol / L) are used to react at the same time. XRD and SEM are used to observe the phase composition and microscopic morphology of the product (see Figure 4 ). The results showed that the product was hydroxyapatite, and its structure was an ideal three-dimensional network structure.

[0074] Embodiment 4:

[0075] Figure 1The present invention is a process flow diagram for reinforcing water-saturated rotten bone and keratin cultural relics. The specific process is as follows: take a piece of water-saturated rotten ivory unearthed by archaeology, wipe the surface clay with a cotton swab, and weigh it with a balance: 1) place it in a curing box with a constant temperature of 25°C and a constant humidity of 85% for dehydration treatment for 12 hours, then take it out, weigh it and calculate the dehydration mass M1; 2) drip a calcium acetate solution (1 mol / L) of the same mass as the above-mentioned dehydration mass M1 on the surface of the ivory, continue to place the ivory in a curing box with a constant temperature of 25°C and a constant humidity of 85% for dehydration treatment for 12 hours, then take it out, weigh it and calculate the dehydration mass M2; 3) drip a diammonium hydrogen phosphate solution (0.6 mol / L) of the same mass as the above-mentioned dehydration mass M2 on the surface of the ivory, continue to place the ivory in a curing box with a constant temperature of 25°C and a constant humidity of 85% for dehydration treatment for 12 hours, then take it out, weigh it and calculate the dehydration mass M3. After repeating the steps 2) and 3) for 14 days, ivory reinforced with hydroxyapatite was obtained. At this time, the penetration rate of the reinforcing materials (calcium acetate solution and diammonium hydrogen phosphate solution) on the ivory surface slowed down significantly, less than 50% of the first day. At the same time, the color difference ΔE of the ivory measured by the colorimeter was less than 5, and the process was stopped. The microstructure of the reinforced ivory was observed by SEM, and nanoindentation tests were performed on the ivory before and after reinforcement to evaluate the changes in its mechanical properties (see Figure 5 ). The results showed that a hydroxyapatite structure similar to that of the ivory matrix was generated in the cracks of the ivory. The nanoindentation technique measured that the average hardness of the ivory before reinforcement was 0.086 GPa and the average elastic modulus was 2.83 GPa; the average hardness of the ivory after reinforcement was 0.153 GPa and the average elastic modulus was 5.08 GPa.

[0076] Embodiment 5:

[0077] The preparation method of this example is similar to that of Example 4, except that the calcium acetate solution (1 mol / L) is replaced by a nano calcium hydroxide suspension (0.34 mol / L, the solvent is isopropanol). The microstructure of the reinforced ivory was observed by SEM, and nanoindentation tests were performed on the ivory before and after reinforcement to evaluate the changes in mechanical properties (see Figure 6 ). The results showed that the hydroxyapatite structure in the ivory cracks was similar to that in the ivory matrix and had a three-dimensional network structure. The nanoindentation technique measured that the average hardness of the ivory before reinforcement was 0.11 GPa and the average elastic modulus was 2.53 GPa; the average hardness of the ivory after reinforcement was 0.17 GPa and the average elastic modulus was 5.74 GPa.

[0078] Embodiment 6:

[0079] The preparation method of this example is similar to that of Example 4, except that the calcium acetate solution (1 mol / L) was replaced with a nano calcium hydroxide suspension (0.34 mol / L, the solvent is isopropanol) after repeating the operation of the example for one week (7 days). The microstructure of the reinforced ivory was observed by SEM, and nanoindentation tests were performed on the ivory before and after reinforcement to evaluate the changes in its mechanical properties (see Figure 7 ). The results showed that a large number of reticular hydroxyapatite structures were generated in the cracks of the ivory. The nanoindentation technique measured that the average hardness of the ivory before reinforcement was 0.175 GPa and the average elastic modulus was 4.73 GPa; the average hardness of the ivory after reinforcement was 0.259 GPa and the average elastic modulus was 10.37 GPa.

[0080] The three-dimensional network structure hydroxyapatite prepared in the embodiment of the present invention has a good pore structure and is highly compatible with the base material of bone keratin ivory, thereby effectively improving the reinforcement effect. In addition, the method for reinforcing unearthed water-saturated rotten bone keratin ivory provided in this embodiment uses two calcium sources, an organic calcium aqueous solution and a nano calcium hydroxide suspension, in steps to repair the small cracks and larger cracks inside the unearthed water-saturated rotten ivory respectively. As precursor solutions, they have a high penetration depth and can generate a stable three-dimensional network structure in the internal cracks of the unearthed water-saturated rotten ivory. This method achieves the safe dehydration and reinforcement of the unearthed water-saturated rotten ivory, and avoids the disintegration of ivory due to large-scale water loss or water replenishment.

[0081] The description of the above embodiments is intended to help those skilled in the art understand and apply the present invention. Based on the disclosure of the present invention, the skilled person can make various modifications and adjustments to these embodiments, and apply the general principles described herein to other embodiments without the need for creative work. Therefore, the present invention is not limited to the above embodiments, and improvements and modifications made by those skilled in the art without departing from the scope of the present invention should be within the scope of protection of the present invention.

Claims

1. A method for reinforcing unearthed water-saturated rotten bone and horny cultural relics, It is characterized in that The three-dimensional hydroxyapatite network is used to reinforce the unearthed water-saturated and decayed bone and keratin artifacts, including the following steps: (1) Dehydration treatment of unearthed water-saturated and rotten bone and keratin cultural relics in an environment with constant temperature and humidity; (2) adding a calcium source solution to the surface of the unearthed water-saturated rotten bone horny cultural relics, and performing a dehydration treatment again in an environment of constant temperature and humidity; (3) adding a phosphorus source solution to the surface of the unearthed water-saturated rotten bone keratin cultural relic obtained in step (2) and performing a dehydration treatment again in an environment of constant temperature and humidity; (4) Repeat steps (2) to (3) multiple times.

2. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 1, It is characterized in that When two calcium sources are used for reinforcement, the calcium sources include a first calcium source and a second calcium source. After step (1), the first calcium source is first used to perform steps (2) to (4), and then the second calcium source is used to replace the first calcium source to repeat steps (2) to (4), so that the unearthed water-saturated rotten bone and keratin cultural relics are reinforced with three-dimensional network hydroxyapatite.

3. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 2, It is characterized in that When two calcium sources are used for reinforcement, the dehydration treatment time of the first calcium source and the second calcium source is equal.

4. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 1, It is characterized in that The calcium source includes at least one of calcium formate, calcium acetate, calcium propionate or nano calcium hydroxide, and the phosphorus source is diammonium hydrogen phosphate.

5. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 4, It is characterized in that When the calcium source is calcium formate, calcium acetate or calcium propionate, the solvent of the calcium source solution is water; when the calcium source is nano calcium hydroxide, the solvent of the calcium source solution is isopropanol; and the solvent of the phosphorus source solution is water.

6. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 1, It is characterized in that The molar ratio of the calcium source added in step (2) to the phosphorus source added in step (3) is (0.05-1):(0.2-0.8).

7. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 1, It is characterized in that In steps (1) to (3), the constant temperature and humidity environment has a temperature of 20-25° C. and a humidity of 80-90%.

8. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 1, It is characterized in that In step (4), the process is repeated several times until the color difference of the unearthed water-saturated rotten bone keratin cultural relics ΔE is less than 5.

9. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 1, It is characterized in that In steps (2) to (3), the dehydration treatment time is 10-20 hours; in step (4), after repeated treatments, the cumulative dehydration treatment time is 10-20 days.

10. The method for reinforcing unearthed water-saturated rotten bone and keratin cultural relics according to claim 1, It is characterized in that The mass addition amount of the calcium source solution and the phosphorus source solution is equal to the water loss amount in the water loss treatment before addition.

Images