CN-121992386-A - Strengthening and protecting treatment method for fragile iron cultural relics with rust

Abstract

The invention discloses a strengthening and protecting treatment method for rusted fragile iron cultural relics, and belongs to the technical field of metal cultural relic protection. The method comprises the steps of firstly carrying out permeation treatment on a rust layer by adopting reinforcing liquid, carrying out in-situ filling of a newly generated rust product and induced regrowth of the original rust product, cooperatively improving compactness of the rust layer and inter-particle bonding strength, and then introducing a polyhydroxy cooperative regulation strategy into hydrolysis-polycondensation dynamics and film forming behavior control of hexadecyl trimethoxy silane by using ethanol, glycol and 1, 2-propanediol compound alcohol as a solvent system, so as to carry out hydrophobic seal protection on the reinforced rust layer, and endow the surface with long-term stable corrosion resistance. The invention applies the in-situ reinforcement of the ferrous ion source and the organic silicon hydrophobic film forming technology regulated by the compound alcohol to the protection of rusty fragile iron cultural relics for the first time, has mild and controllable treatment process and no secondary damage, is highly in accordance with the cultural relic protection principle of 'old repair and original appearance', has simple and convenient process, low cost and strong universality, and can be widely applied to the reinforcement and protection treatment of various unearthed, discharged and inherited fragile rusty iron cultural relics.

Inventors

• JIN PUJUN
• CHENG ZILONG
• DU JING
• LI NAISHENG
• LIU BAOSHAN
• SHAO DONG
• SHEN SHUKUN

Assignees

• 陕西师范大学

Dates

Publication Date

20260508

Application Date

20260302

Claims (9)

1. 1. The strengthening and protecting treatment method for the fragile rust iron cultural relics is characterized by comprising the following steps of: Step 1, preparation and use of reinforcing liquid Adding L-ascorbic acid into a citric acid aqueous solution, stirring until the L-ascorbic acid is completely dissolved, adding FeCO 3 powder, continuously stirring until the system is uniformly light green, standing, taking supernatant fluid to obtain a strengthening solution with ferrous ion concentration of 0.1-0.4 mol/L, completely immersing the fragile iron cultural relics with rust into the strengthening solution, ensuring that no area of the cultural relics is exposed to air, fixing the cultural relics by a bracket at the same time, avoiding the cultural relics from directly contacting the container wall, taking out the iron cultural relics after immersing for 10-15 minutes, drying in a blast drying oven, completing primary immersing-drying treatment, and circulating the immersing-drying treatment until the weight of the iron cultural relics is no longer increased, thereby obtaining pretreated iron cultural relics; Step 2, preparing and using the compound alcohol hydrolysis liquid Fully stirring and uniformly mixing ethanol, ethylene glycol, 1, 2-propylene glycol and ultrapure water to obtain a compound alcohol solvent, wherein the volume ratio of the ethanol to the ethylene glycol to the 1, 2-propylene glycol is 3-7:1:0-1, dropwise adding hexadecyl trimethoxy silane into the compound alcohol solvent, adding citric acid to adjust the pH value to 4-6, stirring and hydrolyzing to obtain a hydrolysate, completely soaking the pretreated iron cultural relics in the obtained hydrolysate for 10-15 minutes, taking out the pretreated iron cultural relics, and naturally drying at room temperature to obtain the firmly protected iron cultural relics.
2. 2. The strengthening and protecting treatment method for the fragile rust-bearing iron cultural relics is characterized in that in the step 1, the concentration of citric acid in the citric acid aqueous solution is 0.1-0.2 mol/L.
3. 3. The method for strengthening and protecting the rusty fragile iron cultural relics according to claim 1, wherein in the step 1, the molar ratio of the citric acid to the L-ascorbic acid is 1:0.03-0.05.
4. 4. The method for strengthening and protecting a rusty fragile iron cultural relic according to claim 1, wherein in the step 1, the molar ratio of FeCO 3 to citric acid is 1:0.2-0.5.
5. 5. The method for reinforcing and protecting the rusty fragile iron cultural relics according to claim 1 is characterized in that in the step 1, an iron cultural relic sample is taken out and is placed in a blast drying oven to be dried for 6-10 hours at 20-40 ℃.
6. 6. The method for reinforcing and protecting the rusty fragile iron cultural relics according to claim 1 is characterized in that in the step 2, the volume ratio of ethanol, ethylene glycol and 1, 2-propylene glycol in the compound alcohol solvent is 5:1:1.
7. 7. The strengthening and protecting treatment method for the rusty fragile iron cultural relics is characterized in that in the step 2, the volume ratio of the total volume of ethanol, ethylene glycol and 1, 2-propylene glycol to ultrapure water is 4-9:1.
8. 8. The method for reinforcing and protecting the rusty fragile iron cultural relics according to claim 1 is characterized in that in the step 2, the volume ratio of hexadecyltrimethoxysilane to the compound alcohol solvent is 5-10:1.
9. 9. The method for reinforcing and protecting the rusty fragile iron cultural relics according to claim 1 is characterized in that in the step 2, the rusty fragile iron cultural relics are stirred and hydrolyzed for 4-6 hours at 35-50 ℃.

Description

Strengthening and protecting treatment method for fragile iron cultural relics with rust Technical Field The invention belongs to the technical field of cultural relic protection, and particularly relates to a method for reinforcing fragile rusty cultural relics by utilizing an iron ion source reinforcing liquid to strengthen the fragile rusty cultural relics, optimizing the dispersion effect of a silane coupling agent and improving the stability of a film layer through compounding an alcohol solvent, and finally realizing the protection method for reinforcing the fragile rusty cultural relics. Background The iron device is used as an important component of Chinese historical cultural heritage, and has extremely high historical, artistic and scientific values. In fact, the body of the iron ware is rusted completely or seriously in the process of unearthing, water yielding or iron ware storing, for example, the iron ware of the sunk ship of the south China sea I is completely mineralized and only rusted, the iron ware of the haverse iron ware storing in the archaeological research institute of the tin-free city is rusted with crisp powder, the structure is endangered to disintegrate, and the surface layer of the iron part of the Weiyuan-small train is seriously mineralized and peeled in a layered manner. There has been great attention to how to rust protect such fragile ironware. The fragile iron cultural relics with rust generally have complex pore structures and multi-layer rust features that the outer layer is loose and easy to fall-off harmful rust, the middle layer often contains metastable transition rust products, the inner layer is commonly provided with 'powdery rust' with strong hygroscopicity and self-catalytic corrosion, and the powdery rust continuously permeates into a matrix, so that the cultural relics are crisp, perforated and even wholly dispersed. Meanwhile, the porous structure of the protective material makes the conventional protective material difficult to form complete coating, a single solvent system can only cover the surface and cannot penetrate into the pores, and corrosive medium still remains in the pores, and air and residual corrosive medium in the pores can prevent the formation of a protective film, so that the problems of discontinuous film layer, poor adhesive force, rapid failure of protective effect and the like are caused. In recent years, metal cultural relic protection technology has advanced to some extent. For example Wu Saimin and the like construct an organosilicon hydrophobic film on the surface of the simulated bronze by a sol-gel method, and reduce water erosion by using low surface energy substances, patent CN119735971A adopts organosilicon modified micro-nano silicon dioxide precursor liquid to realize corrosion inhibition and sealing of the surface of the metal cultural relics, and patent CN103694425A discloses a TiO 2 particle modified acrylate composite coating for enhancing the surface layer stability of the cultural relics. However, the method is mainly aimed at protecting the surface of a compact metal matrix, and has obvious limitations on fragile iron cultural relics which are seriously mineralized, loose and porous, (1) a protective material is difficult to penetrate deep in a pore, and can not effectively solidify and isolate a powdery rust area, (2) the protective material is easy to crack and fall off after film forming and has poor suitability with a mineralized interface, (3) the treatment process involves heating or a strong solvent, and is easy to cause secondary damage to the fragile body, and (4) the protective material lacks an in-situ reinforcing effect on the strength of the iron matrix. The basic principle of cultural relic protection is that the old and original appearance is maintained, so that development of a pretreatment technology which can effectively enhance the structural strength of fragile iron cultural relics and has a corrosion inhibition function, and the treatment process is mild and controllable is needed, and the existing protection bottleneck is broken through. Disclosure of Invention Aiming at the obvious defects of the prior art for protecting the fragile iron cultural relics with rust in the aspects of structural reinforcement and permeation sealing protection, the invention provides a mild, controllable, safe and efficient method for reinforcing and protecting the fragile iron cultural relics with rust. According to the method, the mineralized rust layer is subjected to in-situ strength reinforcement through the reinforcement liquid, the organic silicon film forming performance is optimized by combining the compound alcohol system, the structure reinforcement and corrosion protection of the iron cultural relics are synchronously realized, the problems of cracking, crisp powder, film falling and the like which are easy to cause in the traditional treatment process are effectively avoided, and an innovative protection