Inorganic structure reinforcing agent, preparation method and application thereof

Abstract

The application discloses an inorganic structure reinforcing agent and a preparation method and application thereof. The reinforcing agent comprises inorganic cations, anions, a molecular mediation agent and silicon / aluminum molecular precursors. The application is based on the concept of homogenous reinforcement, and utilizes the molecular mediation agent to integrate different components into a stable fluid, realizes deep penetration and avoids premature solidification. After the fluid fully penetrates and the molecular mediation agent is removed, the components in the system are solidified to form a reinforced structure which is highly matched with the original structure in physical properties. The homology between the materials ensures the maximum compatibility of the reinforced phase and the original structure in the properties such as the thermal expansion coefficient and the elastic modulus, overcomes the defects such as the easy yellowing and aging of organic materials and the large difference in thermal expansion, solves the drawbacks such as poor permeability and easy generation of microcracks of traditional inorganic reinforcing agents, improves the mechanical strength and weather resistance of the structure, and realizes good compatibility and stable reinforcement of the materials.

Description

Technical Field

[0001] This invention relates to the fields of reinforcement materials, cultural heritage protection, and specialty chemicals, and particularly to an inorganic structural reinforcement agent, its preparation method, and its application. Background Technology

[0002] Structures composed of inorganic porous materials such as stone, adobe, and ceramics are widely found in cultural relics, historical buildings, modern infrastructure, and various industrial facilities. During long-term service, these structures are continuously eroded by various factors, including wind, rain, temperature changes, salt crystallization, mechanical loads, and chemical corrosion, severely threatening their structural integrity. Common forms of degradation include surface powdering, particle spalling, flaking, crack propagation, and even a decrease in structural load-bearing capacity. To slow down these degradation processes and repair damaged structures, developing efficient, stable, and compatible reinforcement materials and technologies has become a critical scientific and engineering problem that urgently needs to be solved in building maintenance, cultural relic protection, and extending the lifespan of industrial facilities. Among current protection concepts, the "homogeneous reinforcement" concept is gradually gaining acceptance. This involves using materials with the same or similar chemical composition as the base material for repair, achieving material compatibility and ensuring that the reinforced part and the original structure can work together under environmental changes and external forces.

[0003] Currently, the materials used for reinforcing inorganic porous materials can be mainly divided into three categories: traditional inorganic reinforcing agents, organic polymer reinforcing agents, and silicate ester reinforcing agents.

[0004] Traditional inorganic consolidating agents, such as calcium hydroxide (lime water) or alkali metal silicates (water glass), while chemically similar to inorganic structural substrates, have revealed numerous shortcomings in practical applications. These materials have limited penetration depth, often forming a dense but fragile hard shell on the surface of artifacts. This shell exhibits significant differences in physical and mechanical properties compared to the untreated internal material, making it prone to stress concentration under temperature and humidity changes, which actually accelerates surface peeling. Furthermore, the reaction process may generate soluble salt byproducts, which repeatedly crystallize during moisture migration, causing new and more destructive damage to the artifacts.

[0005] Organic polymers, such as acrylic and epoxy resins, have been widely used due to their excellent bonding properties. However, the inherent drawbacks of these organic materials limit their long-term application in structural reinforcement. They generally suffer from poor resistance to ultraviolet aging, easily yellowing and becoming brittle under light; their coefficients of thermal expansion differ significantly from those of inorganic stone substrates, leading to interfacial damage; more seriously, they significantly reduce the structure's permeability, hindering the normal evaporation of internal moisture, causing moisture to accumulate under the reinforcement layer, thus triggering deeper salt damage and freeze-thaw cycles.

[0006] Silicate-based reinforcing agents generate amorphous structures in situ within the porous network of the substrate through hydrolysis and condensation reactions, thereby re-cementing loose mineral particles. While silicate materials exhibit significant advantages in chemical stability and substrate compatibility, they possess an inherent and insurmountable drawback: during the curing transition, the continuous release of small-molecule byproducts from the hydrolysis and condensation reactions leads to drastic volume shrinkage. This shrinkage results in numerous microcracks within the newly formed reinforced structure, creating a discontinuous reinforcement system. These cracks not only weaken the reinforcement effect but may also form new capillary channels, and in some cases, even accelerate the erosion process by moisture.

[0007] In summary, no existing inorganic structural reinforcement agent can simultaneously satisfy the requirements of high permeability, good compatibility, and the formation of a stable reinforcement network. The core challenges of existing technologies are: first, the reinforcement agent must be effectively delivered to the deep layers of the structure; second, it must form a reinforcement structure at a designated location. A more challenging requirement is that this reinforcement structure ideally be chemically homologous to the matrix material and highly matched to the matrix in key physical properties such as the coefficient of thermal expansion and elastic modulus, thereby ensuring coordinated deformation of the old and new materials during long-term service. How to simultaneously meet the multiple requirements of permeability, structural formation, and performance matching is the key challenge for current technological breakthroughs. Summary of the Invention

[0008] To address the aforementioned technical problems, this invention provides an inorganic structural reinforcing agent, its preparation method, and its application.

[0009] This invention provides an inorganic structural reinforcing agent, comprising an inorganic cation, an anion, a molecular mediator, and a silicon / aluminum molecular precursor. By weight, the inorganic cation precursor is 0.1 to 200 parts, preferably 1 to 100 parts; the anionic precursor is 0.1 to 200 parts, preferably 1 to 100 parts; the molecular mediator is 0.1 to 500 parts, preferably 1 to 200 parts; and the silicon / aluminum molecular precursor is 0.1 to 200 parts, preferably 1 to 100 parts.

[0010] Furthermore, the inorganic cation element is selected from any one or more elements included in alkali metal elements, alkaline earth metal elements, transition metal elements, lanthanide and actinide elements, main group metal elements, and metalloid / nonmetal elements; Among them, alkali metals include Li, Na, K, Rb, and Cs; alkaline earth metals include Be, Mg, Ca, Sr, and Ba; transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Y, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg; lanthanides and actinides include La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, and U; main group metals include Al, Ga, In, Sn, Pb, and Bi; and metalloid / nonmetallic elements include B, Si, Ge, As, Sb, and Te. The anion is selected from hydroxide ions (OH-). - Any one or more of the following ions: silicate ions, carbonate ions, phosphooxyate ions, sulfooxyate ions, carboxylate ions, and sulfonate ions. Among them, silicate ions include SiO4 4- SiO3 2- Si2O7 6- Si4O 10 4- Carbonate ions include CO32-. 2- HCO3 - Phosphophosphate ions include PO4. 3- HPO4 2- H2PO 4- P2O7 4- P3O 10 5- H2PO3 - HPO3 2- H2PO2 - (PO3)3 3- (PO3)4 4- (PO3)6 6- P2O6 4- PO5 3- Sulfoxygenates include SO42-. 2- HSO4 - S2O7 2- S2O8 2- SO3 2- HSO3 - S2O3 2- S2O6 2- S3O6 2- SO5 2- SO2 2- Carboxylate ions include CH3COO - HCOO -C2O4 2- C6H5O7 3- C4H4O6 2- Sulfonate ions include R-SO3. - ; The molar ratio of the inorganic cations to anions is 1:100 to 100:1, preferably 1:10 to 10:1.

[0011] Furthermore, the molecular mediator can reversibly break the ionic bonds of the inorganic solid in the inorganic structure reinforcing agent through coordination, causing it to transform into a fluid. When it is removed, the ionic bonds are remodeled, and the fluid is solidified back into an inorganic solid, which is used to stabilize the fluid state of the inorganic structure reinforcing agent and regulate the liquid-solid transformation process during the application of the inorganic structure reinforcing agent. The molecular mediator is selected from at least one of the following compounds: aliphatic amines, nitrogen-containing heterocyclic compounds, acrylamides, (meth)acrylates, unsaturated carboxylic acids, and sulfur / phosphorus-containing vinyl heterocyclic compounds. Among them, aliphatic amines include diethylamine and triethylamine; nitrogen-containing heterocyclic compounds include pyridine, pyrrole, piperidine, pyrazine, and piperazine; acrylamides include N-hydroxyethyl acrylamide, acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, N-hydroxymethylacrylamide, and diacetone acrylamide; (meth)acrylates include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and 2-carboxyethyl acrylate; unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; and sulfur / phosphorus-containing vinyl heterocyclic compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazolium, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, and 2-hydroxyethyl methacrylate phosphate. The amount of the molecular mediator is 1 to 200 times the total amount of the inorganic cations and anions, preferably 5 to 100 times.

[0012] Further, the silicon / aluminum molecular precursor is at least one of silicon molecular precursor and aluminum molecular precursor; the silicon molecular precursor is selected from at least one of alkoxysilanes, silicates, and compounds contained in silica sol; wherein the alkoxysilanes include methyl orthosilicate and tetraethyl orthosilicate; and the silicates include water glass; The aluminum molecular precursor is selected from at least one of the compounds contained in aluminum alkoxides and aluminum-containing inorganic salts; wherein, aluminum alkoxides include aluminum isopropoxide; and aluminum-containing inorganic salts include aluminum nitrate, aluminum chloride, and sodium aluminate. The molar ratio of the silicon molecular precursor to the aluminum molecular precursor is 1:100 to 100:1, preferably 1:10 to 10:1.

[0013] Furthermore, the reinforcing agent also includes at least one of functional additives and catalysts.

[0014] Further, the functional additive is at least one of surfactant, hydrophobic agent, leveling agent, and humectant; the surfactant is selected from at least one of polyether-modified polydimethylsiloxane, fluorocarbon surfactant, octylphenol polyoxyethylene ether, and isotrimethylene alcohol polyoxyethylene ether, and by weight, the amount of surfactant added in the inorganic structural reinforcing agent is 0.1 to 200 parts, preferably 1 to 50 parts; the hydrophobic agent is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, isobutyltriethoxysilane, n-octyltriethoxysilane, tridecafluorooctyltriethoxysilane, and hexamethyldisilazane, and by weight, the amount of hydrophobic agent added in the inorganic structural reinforcing agent is 0.1 to 200 parts, preferably 1 to 50 parts; the leveling agent is selected from at least one of polyacrylate, polyether-modified polysiloxane, and ethylene glycol butyl ether, and by weight, the amount of leveling agent added in the inorganic structural reinforcing agent is 0.1 to 200 parts. 200 parts, preferably 1 to 50 parts; the moisturizer is selected from at least one of glycerin, ethylene glycol, and propylene glycol, and the amount of the moisturizer added is 0.1 to 200 parts by weight, preferably 1 to 50 parts.

[0015] Furthermore, the catalyst includes an acidic catalyst and a basic catalyst; the acidic catalyst is selected from at least one of inorganic acids and substances contained in organic acids. The inorganic acids include hydrochloric acid and nitric acid; the organic acids include acetic acid; by weight, the amount of acidic catalyst added in the inorganic structural reinforcing agent is 0.1 to 100 parts, preferably 1 to 50 parts; the alkaline catalyst is selected from at least one of the substances contained in inorganic alkalis and organic amines. The inorganic alkaline substances include sodium hydroxide, potassium hydroxide, and ammonia; the organic amine substances include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and tert-butylamine. By weight, the amount of alkaline catalyst added to the inorganic structural reinforcing agent is 0.1 to 100 parts, preferably 1 to 50 parts.

[0016] Furthermore, the inorganic structural reinforcing agent also includes a solvent for adjusting viscosity, wherein the viscosity adjustment range of the inorganic structural reinforcing agent is 0.0001 ~ 1000000 cP, preferably 1 ~ 10000 cP; The solvent includes at least one of the following: water, alcohols, nitriles, ketones, alkanes, alkenes, alkynes, ethers, esters, halogenated hydrocarbons, aromatics, amides, and sulfoxides. The alcohols include methanol, ethanol, n-propanol, and isopropanol; the nitriles include acetonitrile; the ketones include acetone; the alkanes include cyclohexane and n-hexane; the alkenes include cyclohexene; the alkynes include 1-butyne and 1-pentyne; the ethers include tetrahydrofuran and diethyl ether; the esters include ethyl acetate; the halogenated hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride; the aromatics include benzene, toluene, and xylene; the amides include N,N-dimethylformamide; and the sulfoxides include dimethyl sulfoxide.

[0017] In another aspect, this invention provides a method for preparing an inorganic structural reinforcing agent, wherein the preparation method employs any one of the following two methods: The first preparation method includes the following preparation steps: A reactant providing inorganic cations is added to a solvent to form a first solution. A molecular mediator is then added to the first solution to obtain a second solution. A reactant providing anion is added to the second solution and stirred to obtain a first fluid mixture. A silicon / aluminum molecular precursor is added to the first fluid mixture and stirred to obtain a second fluid mixture. The second fluid mixture is then physically separated and washed to obtain the inorganic structure reinforcing agent. The second preparation method includes the following steps: A reactant providing inorganic cations is added to a solvent to form a first solution. A molecular mediator is then added to the first solution to obtain a second solution. A reactant providing anion is added to the second solution and stirred to obtain a first fluid mixture. The first fluid mixture is physically separated and washed to obtain a second fluid mixture. A silicon / aluminum molecular precursor is added to the second fluid mixture and stirred to obtain the inorganic structure reinforcing agent. The physical separation methods include centrifugation, filtration, sedimentation, or sieving. The solvents used in both the first and second preparation methods are at least one of the following: water, alcohols, nitriles, ketones, alkanes, alkenes, alkynes, ethers, esters, halogenated hydrocarbons, aromatics, amides, and sulfoxides. Specifically, the alcohols include methanol, ethanol, n-propanol, and isopropanol; the nitriles include acetonitrile; the ketones include acetone; the alkanes include cyclohexane and n-hexane; the alkenes include cyclohexene; the alkynes include 1-butyne and 1-pentyne; the ethers include tetrahydrofuran and diethyl ether; the esters include ethyl acetate; the halogenated hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride; the aromatics include benzene, toluene, and xylene; the amides include N,N-dimethylformamide; and the sulfoxides include dimethyl sulfoxide.

[0018] In another aspect, this invention provides an application of an inorganic structural reinforcement agent in the fields of cultural relic protection, historical building maintenance, and industrial facility reinforcement. The method for applying the inorganic structural reinforcement agent includes the following steps: (1) Before applying the reinforcing agent, the surface of the structure to be reinforced shall be cleaned to remove dust and other impurities. (2) The inorganic structural reinforcement agent is applied to the surface of the reinforced structure by spraying, brushing, injection, soaking or wet compressing, and left to stand for 1 min to 48 h, preferably 20 min to 2 h; (3) The reinforced material to which the inorganic reinforcing agent has been applied is cured under the following conditions: curing temperature 0 ~ 1000°C, preferably 20 ~ 600°C, humidity 5% ~ 99%, preferably 25% ~ 95%, curing time 1 min ~ 96 h, preferably 20 min ~ 24 h, and the treatment atmosphere is at least one of air, inert gas, oxidizing gas, and reducing gas; the inert gas can be nitrogen or argon, the oxidizing gas can be oxygen, and the reducing gas can be hydrogen, ammonia or hydrogen sulfide.

[0019] Furthermore, the application operation described in step (2) can be performed manually or mechanically automatically, depending on the surface morphology characteristics of the structure being reinforced.

[0020] Furthermore, the inorganic structural reinforcing agent, after curing, can form a reinforced structure whose chemical composition is either completely or not completely the same as that of the object being reinforced.

[0021] The beneficial effects of this invention are: (1) This invention provides an inorganic structural reinforcement system, the core advantage of which lies in achieving "homogeneous reinforcement" of the substrate. This inorganic structural reinforcement integrates multiple inorganic components through the regulation of a molecular mediator, thereby achieving the construction of an in-situ reinforcement network from deep penetration. During the application stage, this system can maintain good fluidity, allowing it to fully penetrate into the pores of the inorganic substrate and effectively preventing premature gelation or crystallization of the reinforcement components before penetration. With the removal of the molecular mediator, this system can undergo in-situ polymerization inside the substrate, forming a reinforcement structure that is homologous to the chemical composition of the substrate and matches its physical properties.

[0022] (2) This invention surpasses organic polymer reinforcing agents in terms of material compatibility and durability. Since the system of this inorganic structural reinforcing agent belongs to an inorganic material system, it utilizes the inherent stability of inorganic materials to overcome the defects of organic polymer materials, such as poor aging performance, easy yellowing under light, and embrittlement. Simultaneously, because the reinforcing structure formed by this inorganic structural reinforcing agent is homologous to the chemical composition of the substrate, it ensures a high degree of matching in the coefficients of thermal expansion, thus avoiding the disadvantage of a large difference in the coefficients of thermal expansion between organic materials and inorganic substrates. Furthermore, it avoids the problem of traditional inorganic reinforcing agents forming a fragile hard shell with significantly different physical and mechanical properties on the surface due to poor permeability, leading to stress concentration and surface peeling.

[0023] (3) The components of the present invention can be selected according to the chemical composition of the inorganic structural substrate. This homology in chemical composition enables the newly formed reinforcing phase to form a seamless or even epitaxial growth-like interface with the inorganic structural substrate, which greatly enhances the bonding strength and long-term stability, and avoids the problems caused by interface incompatibility of traditional materials.

[0024] (4) The inorganic structural reinforcing agent of the present invention is a fluid when applied, and can penetrate deeply through capillary action. Its curing process is triggered by the removal of the molecular mediator, which means that premature gelation or crystallization will not occur before the reinforcing agent has fully penetrated into the inorganic structure, ensuring the depth and uniformity of the reinforcement. The present invention can protect the original state of the inorganic structure while achieving reinforcement. Moreover, compared with traditional reinforcing materials that produce soluble salt byproducts and cause secondary damage, the polymerization process of the present invention is mild and controllable, and does not introduce or generate harmful soluble salts.

[0025] (5) The inorganic structural reinforcing agent of the present invention successfully constructs a high-strength inorganic framework by introducing silicon / aluminum molecular precursors. During the curing process, the silicon / aluminum molecular precursors can not only form a silicon-oxygen or aluminum-oxygen framework through hydrolysis and condensation, but also chemically bond and crosslink in situ with the inorganic cation / anion precursors. The three-dimensional inorganic network generated by this synergistic effect can improve the mechanical strength and weather resistance of the reinforced structure and achieve broad compatibility with a variety of substrates. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art 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.

[0027] Figure 1 This is a schematic diagram illustrating the mechanism of action of the inorganic structural reinforcing agent disclosed in an embodiment of the present invention; Figure 2 This is a schematic diagram of the preparation process of the inorganic structural reinforcing agent disclosed in the embodiments of the present invention; Figure 3 This is a flowchart illustrating the process of using an inorganic structural reinforcing agent to reinforce sandstone images, as disclosed in Embodiment 1 of the present invention. Figure 4 This is a flowchart illustrating the process of using an inorganic structural reinforcing agent to reinforce pottery, as disclosed in Embodiment 2 of the present invention. Figure 5 This is a flowchart of the inorganic structural reinforcing agent for reinforcing building bricks and stones, as disclosed in Embodiment 4 of the present invention; Figure 6 This is a flowchart illustrating the process of using an inorganic structural reinforcing agent to reinforce a limestone image, as disclosed in Embodiment 5 of the present invention. Figure 7 This is a flowchart of the inorganic structural reinforcement agent used to reinforce bone structures, as disclosed in Embodiment 6 of the present invention. Figure 8 This is a flowchart of the inorganic structural reinforcing agent used to reinforce jade objects, as disclosed in Embodiment 8 of the present invention. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0029] This invention provides a method for preparing an inorganic structural reinforcing agent, as follows: Figure 2 As shown, different ionic precursor components react under the action of a molecular mediator to obtain a fluid mixture. An inorganic structural reinforcing agent is then obtained through physical separation and enrichment. When applied to an inorganic structure, the reinforcing agent undergoes in-situ curing under specific curing conditions following the removal of the molecular mediator, thus filling and reinforcing the inorganic structure.

[0030] The specific reinforcement process in this invention includes: first, dissolving an inorganic cationic precursor, adding a molecular mediator, and then adding an anionic precursor to react and form a fluid mixture. Subsequently, depending on the preparation route, one approach is to first add a silicon / aluminum molecular precursor to the fluid mixture, stir until homogeneous, and then perform physical separation and washing; another approach is to first physically separate and wash the fluid mixture, enrich it to obtain an amorphous fluid or gel-like substance, and then add the silicon / aluminum molecular precursor. Finally, a solvent and optional functional additives are added to the obtained fluid mixture for redispersion and formulation, adjusting the system viscosity to ultimately obtain the inorganic structural reinforcement agent. Before reinforcement, the surface of the structure to be reinforced needs to be pretreated by physical cleaning or organic solvent cleaning to remove dust, oil, loose layers, and other impurities, ensuring effective contact between the reinforcement agent and the substrate interface. The prepared inorganic structural reinforcement agent is then applied to the surface or interior of the structure to be reinforced by spraying, brushing, injection, or wet application. After application, the reinforced structure is placed in a controlled environment for curing. Under the influence of molecularly mediated agent removal and specific temperature and humidity conditions, the inorganic structural reinforcing agent undergoes in-situ polymerization, ultimately forming an inorganic mineral reinforcing network within the substrate pores that matches the substrate's coefficient of thermal expansion. A schematic diagram of the mechanism of action of the inorganic structural reinforcing agent is shown below. Figure 1 As shown.

[0031] Example 1: Reinforcement of Sandstone Statues The base minerals of sandstone statues are mainly quartz grains, feldspar grains, and clay minerals that act as binders. Their chemical composition primarily includes silicon dioxide (SiO2) and aluminum oxide (Al2O3). Weathering of this type of rock manifests as the breakdown of the cementing system and damage to the matrix structure. Using Al³... + The system reinforcement agent can achieve good reinforcement.

[0032] 1. Preparation of inorganic structural reinforcing agents: The raw material components, by weight, are: 6.0 parts aluminum chloride, 60.0 parts ethanol, 25.3 parts triethylamine, 0.8 parts deionized water, 4.1 parts aluminum isopropoxide, 20.8 parts tetraethyl orthosilicate, 5.0 parts hydrophobic agent methyltriethoxysilane, and 5.0 parts surfactant polyether-modified polydimethylsiloxane.

[0033] 1.1) Prepared using the first method, the preparation steps are as follows: 1.1.1) Weigh 6.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.1.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain a fluid mixture; 1.1.4) Add 4.1 parts of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate to the first fluid mixture, and continue stirring for 30 minutes to obtain the second fluid mixture; 1.1.5) Centrifuge the second fluid mixture (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.1.6) The gel was redispersed in 20 parts of ethanol, 5.0 parts of hydrophobic agent methyltriethoxysilane and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added, and the mixture was stirred for 20 min to obtain the final inorganic structure reinforcing agent.

[0034] 1.2) Alternatively, the second method can be used for preparation, with the following steps: 1.2.1) Weigh 6.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.2.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.2.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain the first fluid mixture; 1.2.4) Centrifuge the first fluid mixture (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.2.5) Weigh 4.1 parts aluminum isopropoxide and 20.8 parts tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) The second fluid mixture was redispersed in 20 parts of ethanol, and 5.0 parts of hydrophobic agent methyltriethoxysilane and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added. The mixture was stirred for 20 min to obtain the final inorganic structure reinforcing agent.

[0035] 2. Reinforcement Applications: 2.1) Select the weathered sandstone sample to be reinforced, clean the surface, and keep the surface dry; 2.2) Apply degreased cotton soaked in the inorganic structural reinforcing agent prepared by any of the above methods to the powdered area and let it stand for 30 to 60 minutes to allow the reinforcing agent to continue to penetrate. 2.3) Remove the wet compress material and place the stone statue in a well-ventilated environment with a relative humidity of 70% to 80% and a temperature of 25°C, and allow it to cure naturally for 48 hours; 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, ultimately forming a reinforced structure within the reinforced area, thus achieving reinforcement of the substrate. The flowchart of the process for reinforcing sandstone statues using the inorganic structural reinforcing agent prepared in this embodiment is as follows: Figure 3 As shown.

[0036] Example 2: Reinforcement of Pottery The base material of pottery is low-temperature sintered aluminosilicate, whose chemical composition mainly includes silicon dioxide (SiO2) and aluminum oxide (Al2O3), as well as small amounts of other metal oxides, resulting in a relatively loose structure. Weathering of pottery leads to a loosening of the body structure and a decrease in mechanical strength. Using Al... 3+ The system reinforcement agent can achieve good reinforcement.

[0037] 1. Preparation of inorganic structural reinforcing agents: The raw material components by weight are: 4.0 parts aluminum chloride, 60.0 parts ethanol, 25.3 parts triethylamine, 0.8 parts deionized water, 8.2 parts aluminum isopropoxide, 10.4 parts tetraethyl orthosilicate, and 5.0 parts surfactant (polyether modified polydimethylsiloxane).

[0038] 1.1) Prepared using the first method 1.1.1) Weigh 4.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.1.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain a fluid mixture; 1.1.4) Weigh 8.2 parts of aluminum isopropoxide and 10.4 parts of tetraethyl orthosilicate and add them to the first fluid mixture. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.1.5) Centrifuge the second fluid mixture (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.1.6) The gel was redispersed in 20 parts of ethanol, and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added. The mixture was stirred for 40 min to obtain the final inorganic structure reinforcing agent.

[0039] 1.2) Alternatively, the second method can be used for preparation, with the following steps: 1.2.1) Weigh 4.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.2.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain solution B; 1.2.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain the first fluid mixture C; 1.2.4) Centrifuge the first fluid mixture (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and centrifuge three times. 1.2.5) Weigh 8.2 parts of aluminum isopropoxide and 10.4 parts of tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) The second fluid mixture was redispersed in 20 parts of ethanol, and 5.0 parts of surfactant (polyether modified polydimethylsiloxane) were added. The mixture was stirred for 40 min to obtain the final inorganic structure reinforcing agent.

[0040] 2. Reinforcement Applications: 2.1) Select the pottery to be reinforced, clean the surface and pores of any deposits, and keep the surface clean; 2.2) Using a brush or a soft coating tool, apply the inorganic structural reinforcement agent prepared by any of the above methods evenly to the weathered surface of the pottery, and keep the surface moist during the coating process to promote penetration, and let it stand for 20 to 30 minutes. 2.3) Place the treated pottery in an environmental chamber with a relative humidity of 85% and a temperature of 40-50℃, and allow it to cure naturally for 24 hours; 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, ultimately forming a reinforced structure within the reinforced area, thus achieving reinforcement of the substrate. The flowchart of the process for reinforcing ceramics using the inorganic structural reinforcing agent prepared in this embodiment is as follows: Figure 4 As shown.

[0041] Example 3: Reinforcement of Glassware Glass is primarily made from quartz sand, and its main chemical component is silicon dioxide (SiO2). Due to long-term weathering and environmental influences, it also contains a certain amount of aluminum oxide (Al2O3). Weathering leads to decreased stability and surface deterioration of the glass. Using Al... 3+ The system reinforcement agent can achieve good reinforcement.

[0042] 1. Preparation of inorganic structural reinforcing agents: The raw material components by weight are: 6.0 parts aluminum chloride, 60.0 parts ethanol, 25.3 parts triethylamine, 0.8 parts deionized water, 4.1 parts aluminum isopropoxide, 20.8 parts tetraethyl orthosilicate, and 2.0 parts polyether-modified polysiloxane leveling agent.

[0043] 1.1) Prepared using the first method, the preparation steps are as follows: 1.1.1) Weigh 6.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.1.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain the first fluid mixture; 1.1.4) Weigh 4.1 parts of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate and add them to the first fluid mixture. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.1.5) Centrifuge D (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and repeat centrifugation three times; 1.1.6) Redisperse the gel in 20 parts of ethanol, add 2.0 parts of leveling agent polyether modified polysiloxane, and stir for 40 min to obtain the final inorganic structure reinforcing agent.

[0044] 1.2) Alternatively, the second method can be used for preparation, with the following steps: 1.2.1) Weigh 6.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.2.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain solution B; 1.2.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain the first fluid mixture; 1.2.4) Centrifuge the first fluid mixture (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.2.5) Weigh 4.1 parts aluminum isopropoxide and 20.8 parts tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) The second fluid mixture is redispersed in 20 parts of ethanol, and 2.0 parts of leveling agent polyether modified polysiloxane are added. Stir for 40 min to obtain the final reinforcing agent.

[0045] 2. Reinforcement Applications: 2.1) Take the glass device to be reinforced, clean its surface, and ensure that the reinforcement interface is free of oil and foreign impurities, and keep the operating environment clean and dry; 2.2) Use a soft brush to evenly coat the inorganic structural reinforcement agent prepared by any of the above methods onto the surface of the weathered glass device, and keep the surface moist to promote penetration, and let it stand for 20 to 30 minutes. 2.3) Place the sample in a well-ventilated environment with a relative humidity of 70%~80% and a temperature of 25℃, and allow it to cure naturally for 48 hours; 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, eventually forming a reinforced structure within the reinforced area, thus achieving the reinforcement treatment of the substrate.

[0046] Example 4: Reinforcement of Building Masonry Traditional building bricks and stones are made from sintered clay. Their chemical composition includes silicon dioxide (SiO2) and aluminum oxide (Al2O3). Due to environmental erosion, the material properties of traditional building bricks and stones deteriorate and their surfaces deteriorate, leading to reduced structural stability. Using Al³⁺... + The system reinforcement agent can achieve good reinforcement.

[0047] 1. Preparation of inorganic structural reinforcing agents: The raw material components by weight are: 6.0 parts aluminum chloride, 60.0 parts ethanol, 25.3 parts triethylamine, 0.8 parts deionized water, 4.1 parts aluminum isopropoxide, 20.8 parts tetraethyl orthosilicate, and 5.0 parts surfactant polyether modified polydimethylsiloxane.

[0048] 1.1) Prepared using the first method, the preparation steps are as follows: 1.1.1) Weigh 6.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.1.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain a fluid mixture; 1.1.4) Add 4.1 parts of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate to the first fluid mixture, and continue stirring for 30 minutes to obtain the second fluid mixture; 1.1.5) Centrifuge the second fluid mixture (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.1.6) The gel was redispersed in 20 parts of ethanol, and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added. The mixture was stirred for 20 min to obtain the final inorganic structure reinforcing agent.

[0049] 1.2) Alternatively, the second method can be used for preparation, with the following steps: 1.2.1) Weigh 6.0 parts of aluminum chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.2.2) Add 25.3 parts of triethylamine to the first solution and continue stirring for 15 min to obtain solution B; 1.2.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain the first fluid mixture; 1.2.4) Centrifuge the first fluid mixture (7000 rpm, 20 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.2.5) Weigh 4.1 parts aluminum isopropoxide and 20.8 parts tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) The second fluid mixture was redispersed in 20 parts of ethanol, and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added. The mixture was stirred for 20 min to obtain the final inorganic structure reinforcing agent.

[0050] 2. Reinforcement Applications: 2.1) Take a sample of the brick and stone of the building to be reinforced, clean its surface to remove surface attachments and impurities, and keep the surface clean; 2.2) The inorganic structural reinforcement agent prepared by any of the above methods is uniformly sprayed onto the surface of the severely weathered brick and stone sample and left to stand for 30 to 50 minutes to allow the reinforcement agent to continue to penetrate. 2.3) Place the treated brick and stone samples in a curing environment with a relative humidity of 85% to 90% and a temperature of 20 to 25°C, and let them stand and cure for 72 hours. 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, ultimately forming a reinforced structure within the reinforced area, thus achieving reinforcement of the substrate. The flowchart for reinforcing building masonry using the inorganic structural reinforcing agent prepared in this embodiment is as follows: Figure 5 As shown.

[0051] Example 5: Reinforcement of Limestone Carvings The base minerals of limestone carvings are primarily calcium carbonate (CaCO3), with small amounts of silica (SiO2) and alumina (Al2O3). After weathering, the calcium carbonate matrix is ​​lost, and the internal silica-alumina components (clay minerals) deteriorate, necessitating a reinforcing agent that can simultaneously address both calcium and silica-alumina components. Using Ca... 2+ The system reinforcement agent can achieve good reinforcement.

[0052] 1. Preparation of inorganic structural reinforcing agents: The raw material components, by weight, are: calcium chloride dihydrate 3.7 parts, ethanol 50.0 parts, triethylamine 10.0 parts, aluminum isopropoxide 4.1 parts, tetraethyl orthosilicate 20.8 parts, and surfactant (polyether-modified polydimethylsiloxane) 5.0 parts. Carbon dioxide is used to generate anions.

[0053] 1.1) Prepared using the first method, the steps are as follows: 1.1.1) Weigh 3.7 parts of calcium chloride dihydrate and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 10.0 parts of triethylamine to solution A and continue stirring for 15 min to obtain the second solution; 1.1.3) Carbon dioxide gas was introduced into the second solution and magnetically stirred at room temperature. The gas flow rate was 50 mL / min, and the aeration and stirring time was 30 min to obtain the first fluid mixture. 1.1.4) Weigh 4.1 parts of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate and add them to the first fluid mixture. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.1.5) Centrifuge the second fluid mixture (7000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.1.6) The gel was redispersed in 10 parts of ethanol, and 5.0 parts of surfactant (polyether modified polydimethylsiloxane) were added. The mixture was stirred for 20 min to obtain the final inorganic structure reinforcing agent.

[0054] 1.2) Alternatively, the second method can be used for preparation, with the following steps: 1.2.1) Weigh 3.7 parts of calcium chloride dihydrate and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.2.2) Add 10.0 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the solution; 1.2.3) Carbon dioxide gas was introduced into the second solution and magnetically stirred at room temperature. The gas flow rate was 50 mL / min, and the aeration and stirring time was 30 min to obtain the first fluid mixture. 1.2.4) Centrifuge the first fluid mixture (7000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.2.5) Weigh 4.1 parts aluminum isopropoxide and 20.8 parts tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) The second fluid mixture was redispersed in 10 parts of ethanol, and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added. The mixture was stirred for 20 min to obtain the final reinforcing agent.

[0055] 2. Reinforcement Applications: 2.1) Select the weathered limestone sample block or stone carving area to be reinforced, and use a soft brush and low-pressure air blower to remove surface dust and loose particles to ensure that the reinforcement interface is free of oil and foreign impurities. 2.2) Apply the inorganic structural reinforcing agent prepared by any of the above methods evenly to the surface of the stone carving and let it stand for 20 to 30 minutes; 2.3) Place the treated stone carving in a curing environment with a relative humidity of 85% to 90% and a temperature of 20 to 25°C, and let it stand and cure for 36 hours; 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, ultimately forming a reinforced structure within the reinforced area, thus achieving reinforcement of the substrate. The flowchart of the process for reinforcing a limestone image using the inorganic structural reinforcing agent prepared in this embodiment is as follows: Figure 3 As shown.

[0056] Example 6: Bone reinforcement Bone artifacts, due to long-term burial underground, have absorbed a large amount of minerals from the soil. Their chemical composition, besides the inherent hydroxyapatite (Ca), includes... 10 In addition to (PO4)6(OH)2, it also includes silicon dioxide (SiO2) and aluminum oxide (Al2O3). A reinforcement method is needed that can simultaneously accommodate calcium-phosphorus bone and silicon-aluminum impurities for reinforcement, using Ca... 2+ The system reinforcement agent can achieve good reinforcement.

[0057] 1. Preparation of inorganic structural reinforcing agents: The raw material components by weight are: calcium chloride dihydrate 3.7 parts, ethanol 50.0 parts, triethylamine 12.0 parts, phosphoric acid 1.5 parts, aluminum isopropoxide 2.0 parts, tetraethyl orthosilicate 20.8 parts, and surfactant (polyether modified polydimethylsiloxane) 5.0 parts.

[0058] 1.1) Prepared using the first method, the preparation steps are as follows: 1.1.1) Weigh 3.7 parts of calcium chloride dihydrate and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 12.0 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.1.3) Add 1.5 parts of phosphoric acid to the second solution and continue stirring for 40 minutes to form the first fluid mixture; 1.1.4) Weigh 2.0 parts of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate and add them to the first fluid mixture. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.1.5) Centrifuge the second fluid mixture (8000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.1.6) The gel was redispersed in 10 parts of ethanol, and 5.0 parts of surfactant (polyether modified polydimethylsiloxane) were added. The mixture was stirred for 30 min to obtain the final inorganic structure reinforcing agent.

[0059] 1.2) Alternatively, the second method can be used for preparation, and the preparation steps are as follows: 1.2.1) Weigh 3.7 parts of calcium chloride dihydrate and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.2.2) Add 12.0 parts of triethylamine to the first solution A, and continue stirring for 15 min to obtain the second solution; 1.2.3) Add 1.5 parts of phosphoric acid to the second solution and continue stirring for 40 minutes to form the first fluid mixture; 1.2.4) Centrifuge the first fluid mixture (8000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.2.5) Weigh 2.0 parts of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) The second fluid mixture was redispersed in 10 parts of ethanol, and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added. The mixture was stirred for 30 min to obtain the final inorganic structure reinforcing agent.

[0060] 2. Reinforcement Applications: 2.1) Take a sample of the bone object to be reinforced, clean its surface, remove loose soil, and keep the surface clean; 2.2) Using a soft brush or micro-applier, apply the inorganic structural reinforcement agent prepared by any of the above methods to the bone surface by coating, and let it stand for 20 to 30 minutes to allow it to penetrate into the deep layers. 2.3) Place the treated sample in a cool, dry place (temperature 20℃, humidity 60%) and allow it to cure slowly for 50 hours; 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, ultimately forming a reinforced structure within the reinforced area, thus achieving reinforcement of the substrate. A flowchart illustrating the process of reinforcing bone objects using the inorganic structural reinforcing agent prepared in this embodiment is shown below. Figure 7 As shown.

[0061] Example 7: Reinforcement of the ground layer of murals The ground layer of a mural is composed of clay, lime, fiber, and sand, and its chemical composition mainly includes calcium carbonate (CaCO3), silicon dioxide (SiO2), and calcium sulfate (CaSO4). Weathering of the ground layer damages its matrix structure, leading to a decrease in the strength of the support structure. Using Ca... 2+ The system reinforcement agent can achieve good reinforcement.

[0062] 1. Preparation of inorganic structural reinforcing agents: The raw material components, by weight, are: calcium chloride dihydrate 3.7 parts, ethanol 50.0 parts, triethylamine 6.0 parts, aluminum isopropoxide 1.0 part, tetraethyl orthosilicate 20.8 parts, and humectant (glycerin) 2.0 parts. Carbon dioxide is used to generate anions.

[0063] 1.1) The preparation is carried out using the first method, with the following steps: 1.1.1) Weigh 3.7 parts of calcium chloride dihydrate and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 6.0 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.1.3) Carbon dioxide gas was introduced into the second solution and magnetically stirred at room temperature. The gas flow rate was 50 mL / min, and the aeration and stirring time was 30 min to obtain the first fluid mixture. 1.1.4) Weigh 1.0 part of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate and add them to the first fluid mixture. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.1.5) Centrifuge the second fluid mixture (5000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.1.6) Redisperse the gel in 10 parts ethanol, add 2.0 parts humectant (glycerin), and stir for 20 min to obtain the final reinforcing agent.

[0064] 1.2) Alternatively, the second method can be used for preparation, with the following steps: 1.2.1) Weigh 3.7 parts of calcium chloride dihydrate and add it to 40.0 parts of ethanol, stir well to obtain solution A; 1.2.2) Add 6.0 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.2.3) Carbon dioxide gas was introduced into the second solution and magnetically stirred at room temperature. The gas flow rate was 50 mL / min, and the aeration and stirring time was 30 min to obtain the first fluid mixture. 1.2.4) Centrifuge the first fluid mixture (5000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.2.5) Weigh 1.0 part aluminum isopropoxide and 20.8 parts tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) Redisperse the second fluid mixture in 10 parts of ethanol, add 2.0 parts of humectant glycerin, and stir for 20 minutes to obtain the final reinforcing agent.

[0065] 2. Reinforcement Applications: 2.1) Select a sample of the mural ground layer to be reinforced, clean its surface to remove surface dust and loose particles, and ensure that there are no foreign impurities at the reinforcement interface; 2.2) Apply the inorganic structural reinforcement agent prepared by any of the above methods to the sample surface and let it stand for 20 to 30 minutes to allow the reinforcement agent to penetrate into the ground layer sample; 2.3) Place the treated mural ground layer sample in a curing environment with a relative humidity of 85% ~ 90% and a temperature of 20 ~ 25℃, and let it stand and cure for 72 hours; 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, eventually forming a reinforced structure within the reinforced area, thus achieving the reinforcement treatment of the substrate.

[0066] Example 8: Jade Reinforcement In this embodiment, the jade substrate mineral being reinforced is primarily serpentine (Mg3Si2O5(OH)4). After weathering, serpentine jade suffers from mineral component failure and matrix structural damage. A reinforcing agent capable of filling micropores and replenishing magnesium and silicon components is needed. Mg²⁺ is used. + The system reinforcement agent can achieve good reinforcement.

[0067] 1. Preparation of inorganic structural reinforcing agents: The raw material components, by weight, are: 4.1 parts magnesium chloride, 50.0 parts ethanol, 15.0 parts triethylamine, 0.8 parts deionized water, 1.0 part aluminum isopropoxide, 20.8 parts tetraethyl orthosilicate, and 5.0 parts surfactant polyether modified polydimethylsiloxane.

[0068] 1.1) Prepared using the first method, the preparation steps are as follows: 1.1.1) Weigh 4.1 parts of magnesium chloride and add it to 40.0 parts of ethanol, stir well to obtain the first solution; 1.1.2) Add 15.0 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.1.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain the first fluid mixture; 1.1.4) Weigh 1.0 part of aluminum isopropoxide and 20.8 parts of tetraethyl orthosilicate and add them to the first fluid mixture. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.1.5) Centrifuge the second fluid mixture (7000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.1.6) The gel was redispersed in ethanol, and 5.0 parts of surfactant polyether modified polydimethylsiloxane were added. The mixture was stirred for 20 min to obtain the final inorganic structure reinforcing agent.

[0069] 1.2) Alternatively, the second method can be used for preparation, and the preparation steps are as follows: 1.2.1) Weigh 4.1 parts of magnesium chloride and add it to 40.0 parts of ethanol, stir well to obtain solution A; 1.2.2) Add 15.0 parts of triethylamine to the first solution and continue stirring for 15 min to obtain the second solution; 1.2.3) Slowly add 0.8 parts of deionized water to the second solution and continue stirring for 40 min to obtain the first fluid mixture; 1.2.4) Centrifuge the first fluid mixture C (7000 rpm, 10 min), discard the supernatant, collect the lower gel-like substance, and repeat the centrifugation three times; 1.2.5) Weigh 1.0 part aluminum isopropoxide and 20.8 parts tetraethyl orthosilicate and add them to the gel-like substance. Continue stirring for 30 minutes to obtain the second fluid mixture. 1.2.6) The second fluid mixture D is redispersed in ethanol, and 5.0 parts of surfactant polyether modified polydimethylsiloxane are added. The mixture is stirred for 20 min to obtain the final inorganic structure reinforcing agent.

[0070] 2. Reinforcement Applications: 2.1) Select the jade object to be reinforced, clean its surface, and remove impurities; 2.2) Apply the inorganic structural reinforcing agent prepared by any of the above methods evenly to the surface of the jade artifact, and keep the surface moist during the coating process to promote penetration, and let it stand for 20 to 30 minutes; 2.3) Place the treated jade in a constant temperature chamber with a relative humidity of 85% ~ 90% and a temperature of 35℃, and slowly cure for 72 hours; 2.4) The inorganic structural reinforcing agent undergoes in-situ curing in the reinforced area, ultimately forming a reinforced structure within the reinforced area, thus achieving reinforcement of the substrate. The flowchart for reinforcing jade using the inorganic structural reinforcing agent prepared in this embodiment is as follows: Figure 8 As shown.

[0071] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention 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; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An inorganic structural reinforcing agent, characterized in that, The inorganic structural reinforcing agent includes inorganic cations, anions, molecular mediators, and silicon / aluminum molecular precursors.

2. The inorganic structural reinforcing agent according to claim 1, characterized in that, The inorganic cation element is selected from any one or more elements included in alkali metal elements, alkaline earth metal elements, transition metal elements, lanthanide and actinide elements, main group metal elements, and metalloid / nonmetal elements. Among them, alkali metals include Li, Na, K, Rb, and Cs; alkaline earth metals include Be, Mg, Ca, Sr, and Ba; transition metals include Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Y, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg; lanthanides and actinides include La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, and U; main group metals include Al, Ga, In, Sn, Pb, and Bi; and metalloid / nonmetallic elements include B, Si, Ge, As, Sb, and Te. The anion is selected from any one or more of the following ions: hydroxide ions, silicate ions, carbonate ions, phosphooxyate ions, sulfooxyate ions, carboxylate ions, and sulfonate ions. Among them, silicate ions include SiO4 4- SiO3 2- Si2O7 6- Si4O 10 4- Carbonate ions include CO32-. 2- HCO3 - Phosphophosphate ions include PO4. 3- HPO4 2- H2PO 4- P2O7 4- P3O 10 5- H2PO3 - HPO3 2- H2PO2 - (PO3)3 3- (PO3)4 4- (PO3)6 6- P2O6 4- PO5 3- Sulfoxygenates include SO42-. 2- HSO4 - S2O7 2- S2O8 2- SO3 2- HSO3 - S2O3 2- S2O6 2- S3O6 2- SO5 2- SO2 2- Carboxylate ions include CH3COO - HCOO - C2O4 2- C6H5O7 3- C4H4O6 2- Sulfonate ions include R-SO3 - ; The molar ratio of the inorganic cations to anions is 1:100 to 100:

1.

3. The inorganic structural reinforcing agent according to claim 1, characterized in that, The molecular mediator is selected from at least one of the following compounds: aliphatic amines, nitrogen-containing heterocyclic compounds, acrylamides, (meth)acrylates, unsaturated carboxylic acids, and sulfur / phosphorus-containing vinyl heterocyclic compounds. Among them, aliphatic amines include diethylamine and triethylamine; nitrogen-containing heterocyclic compounds include pyridine, pyrrole, piperidine, pyrazine, and piperazine; acrylamides include N-hydroxyethyl acrylamide, acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, N-hydroxymethylacrylamide, and diacetone acrylamide; (meth)acrylates include hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, and 2-carboxyethyl acrylate; unsaturated carboxylic acids include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and fumaric acid; and sulfur / phosphorus-containing vinyl heterocyclic compounds include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazolium, sodium vinyl sulfonate, sodium styrene sulfonate, 2-acrylamido-2-methylpropanesulfonic acid, and 2-hydroxyethyl methacrylate phosphate. The amount of the molecular mediator is 1 to 200 times the total amount of the inorganic cations and anions.

4. The inorganic structural reinforcing agent according to claim 1, characterized in that, The silicon / aluminum molecular precursor is at least one of silicon molecular precursor and aluminum molecular precursor; the silicon molecular precursor is selected from at least one of alkoxysilanes, silicates, and compounds contained in silica sols; wherein the alkoxysilanes include methyl orthosilicate and tetraethyl orthosilicate; and the silicates include water glass. The aluminum molecular precursor is selected from at least one of the compounds contained in aluminum alkoxides and aluminum-containing inorganic salts; wherein, aluminum alkoxides include aluminum isopropoxide; and aluminum-containing inorganic salts include aluminum nitrate, aluminum chloride, and sodium aluminate. The molar ratio of the silicon molecular precursor to the aluminum molecular precursor is 1:100 to 100:

1.

5. The inorganic structural reinforcing agent according to claim 1, characterized in that, The reinforcing agent also includes at least one of functional additives and catalysts.

6. The inorganic structural reinforcing agent according to claim 5, characterized in that, The functional additive is at least one of surfactant, hydrophobic agent, leveling agent, and humectant; the surfactant is selected from at least one of polyether-modified polydimethylsiloxane, fluorocarbon surfactant, octylphenol polyoxyethylene ether, and isothietrol polyoxyethylene ether, and the amount of surfactant added in the inorganic structure reinforcing agent is 0.1 to 200 parts by weight; the hydrophobic agent is selected from at least one of methyltrimethoxysilane, methyltriethoxysilane, isobutyltriethoxysilane, n-octyltriethoxysilane, tridecafluorooctyltriethoxysilane, and hexamethyldisilazane, and the amount of hydrophobic agent added in the inorganic structure reinforcing agent is 0.1 to 200 parts by weight; the leveling agent is selected from at least one of polyacrylate, polyether-modified polysiloxane, and ethylene glycol butyl ether, and the amount of leveling agent added in the inorganic structure reinforcing agent is 0.1 to 200 parts by weight. 200 parts; the moisturizer is selected from at least one of glycerin, ethylene glycol, and propylene glycol, and the amount of the moisturizer added is 0.1 to 200 parts by weight.

7. The inorganic structural reinforcing agent according to claim 5, characterized in that, The catalyst includes acidic catalysts and basic catalysts; the acidic catalyst is selected from at least one of inorganic acids and substances contained in organic acids. The inorganic acids include hydrochloric acid and nitric acid; the organic acids include acetic acid; and the amount of acidic catalyst added in the inorganic structural reinforcing agent is 0.1 to 100 parts by weight. The alkaline catalyst is selected from at least one of the substances contained in inorganic alkaline substances and organic amine substances; The inorganic alkaline substances include sodium hydroxide, potassium hydroxide, and ammonia; the organic amine substances include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, and tert-butylamine. By weight, the amount of alkaline catalyst added in the inorganic structural reinforcing agent is 0.1 to 100 parts.

8. The inorganic structural reinforcing agent according to claim 1, characterized in that, The inorganic structural reinforcing agent also includes a solvent for adjusting viscosity, wherein the viscosity adjustment range of the inorganic structural reinforcing agent is 0.0001 ~ 1000000 cP; The solvent includes at least one of the following: water, alcohols, nitriles, ketones, alkanes, alkenes, alkynes, ethers, esters, halogenated hydrocarbons, aromatics, amides, and sulfoxides. The alcohols include methanol, ethanol, n-propanol, and isopropanol; the nitriles include acetonitrile; the ketones include acetone; the alkanes include cyclohexane and n-hexane; the alkenes include cyclohexene; the alkynes include 1-butyne and 1-pentyne; the ethers include tetrahydrofuran and diethyl ether; the esters include ethyl acetate; the halogenated hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride; the aromatics include benzene, toluene, and xylene; the amides include N,N-dimethylformamide; and the sulfoxides include dimethyl sulfoxide.

9. The method for preparing the inorganic structural reinforcing agent according to claim 1, characterized in that, The preparation method described herein adopts any one of the following two methods: The first preparation method includes the following preparation steps: A reactant that provides inorganic cations is added to a solvent to form a first solution. Then, a molecular mediator is added to the first solution to obtain a second solution. A reactant that provides anions is added to the second solution and stirred to obtain a first fluid mixture. A silicon / aluminum molecular precursor is added to a first fluid mixture and stirred to obtain a second fluid mixture. The second fluid mixture is then physically separated and washed to obtain the inorganic structure reinforcing agent. The second preparation method includes the following steps: A reactant providing inorganic cations is added to a solvent to form a first solution. A molecular mediator is then added to the first solution to obtain a second solution. A reactant providing anion is added to the second solution and stirred to obtain a first fluid mixture. The first fluid mixture is physically separated and washed to obtain a second fluid mixture. A silicon / aluminum molecular precursor is added to the second fluid mixture and stirred to obtain the inorganic structure reinforcing agent. The physical separation methods include centrifugation, filtration, sedimentation, or sieving. The solvents used in both the first and second preparation methods are at least one of the following: water, alcohols, nitriles, ketones, alkanes, alkenes, alkynes, ethers, esters, halogenated hydrocarbons, aromatics, amides, and sulfoxides. Specifically, the alcohols include methanol, ethanol, n-propanol, and isopropanol; the nitriles include acetonitrile; the ketones include acetone; the alkanes include cyclohexane and n-hexane; the alkenes include cyclohexene; the alkynes include 1-butyne and 1-pentyne; the ethers include tetrahydrofuran and diethyl ether; the esters include ethyl acetate; the halogenated hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride; the aromatics include benzene, toluene, and xylene; the amides include N,N-dimethylformamide; and the sulfoxides include dimethyl sulfoxide.

10. The application of the inorganic structural reinforcement agent according to claim 1 in the fields of cultural relic protection, historical building maintenance, and industrial facility reinforcement, characterized in that, The application method of the inorganic structural reinforcement agent includes the following steps: (1) Clean the reinforced structure; (2) Apply the inorganic structural reinforcement agent to the surface of the reinforced structure by spraying, brushing, injection, soaking or wet compressing, and let it stand for 1 min to 48 h. (3) The reinforced material to which the inorganic reinforcing agent has been applied is cured under the following conditions: curing temperature 0 ~ 1000°C, humidity 5% ~ 99%, curing time 1 min ~ 96 h, and the treatment atmosphere is selected from at least one of air, inert gas, oxidizing gas and reducing gas.

11. The application of the inorganic structural reinforcing agent according to claim 10, characterized in that, The inorganic structural reinforcing agent can form a reinforced structure after curing, and the chemical composition of the reinforced structure may be exactly the same as or not exactly the same as the composition of the object being reinforced.

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