Inorganic polymeric adhesives and repair applications thereof

Abstract

The invention discloses a series of inorganic polymeric adhesives and repair application thereof, the inorganic polymeric adhesives are oligomer structures formed by reaction of inorganic cation precursors and inorganic anions in the presence of capping agents, and the oligomer structures can be cured to form an inorganic polymeric network. The formula of the adhesive can be subjected to ion level regulation and control according to the specific composition of a to-be-repaired inorganic material product, ionic bond reconstruction between the adhesive and a base material is achieved in the heat treatment process, an inorganic interface bonding layer which is compact in structure, matched in crystal form and coordinated in thermal expansion is formed, and the adhesive has the advantages of being high in continuity, free of weak bonding areas, free of obvious pores and the like. The problems of thermal aging, falling, chromatic aberration and the like of a traditional binder can be effectively avoided, the service life of a repaired structure is prolonged, and the environmental stability is improved. The method has popularization and application potentials in the fields of aerospace, weaponry, advanced manufacturing, consumer electronics, medical health, cultural relic repair, jade repair, decorative art and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of materials science and technology, and particularly relates to an inorganic polymer adhesive and its repair application. Background Art

[0002] Inorganic material products refer to artificial or natural products composed of inorganic mineral materials, usually without metallic elements, mainly composed of oxides and salts of metallic or metalloid elements, and have characteristics such as high hardness, heat resistance, weather resistance, electrical insulation and chemical stability, and are widely used in fields such as architectural decoration, art furnishings, folk crafts, electronic devices, refractory components and high-performance structural materials. According to material sources, compositions and process characteristics, inorganic material products can be divided into two categories: natural and artificial. Natural types mainly include jade articles mainly composed of silicate minerals, such as tremolite nephrite (Ca2(Mg,Fe)5Si8O 22 (OH)2, belonging to the amphibole family of chain silicates), pyroxene jadeite (i.e., jadeite, NaAlSi2O6, belonging to single-chain silicates), serpentine jade (Mg3Si2O5(OH)4, layered silicate with hydroxyl structure) and turquoise (CuAl6(PO4)4(OH)8·4H2O, phosphate mineral); natural siliceous stones, such as granite (mainly composed of quartz SiO2, potassium feldspar KAlSi3O8, plagioclase (solid solution series from albite NaAlSi3O8 to anorthite CaAl2Si2O8) and mica K(Mg,Fe)3AlSi3O 10 (OH)2) and quartzite (recrystallized SiO2 content > 90%); carbonate-based stones, including calcite-type white marble (CaCO3), dolomite-type marble (CaMg(CO3)2) and bioclastic limestone (CaCO3 containing SiO2 and clay impurities); other mineral-based materials, such as natural gypsum carvings (gypsum dihydrate CaSO4·2H2O) and flint / obsidian artifacts (cryptocrystalline SiO2, amorphous volcanic glass SiO2 ≥ 70%). Artificial types cover ceramics, including traditional ceramics such as low-temperature porous pottery (made of kaolinite Al2Si2O5(OH)4, illite Kal2(AlSi3O 10)(Made by firing with (OH)2 as the main raw material), high-temperature dense porcelain (using a ternary formula of kaolin Al2O3·2SiO2·2H2O, quartz SiO2, and potassium feldspar KAlSi3O8), and stoneware (mainly composed of illite clay, with Fe2O3 as a colorant), as well as modern advanced ceramics such as alumina ceramics (α-Al2O3) and silicon carbide ceramics (β-SiC); glass products, including traditional potassium-calcium silicate glaze (K2O·CaO·6SiO2) and modern soda-lime glass (Na2O·CaO·6SiO2); gypsum products, such as plaster of Paris (hemihydrate CaSO4·0.5H2O) and gypsum fiberboard (a composite material of CaSO4·2H2O and plant fibers); cement-based products, including lime mortar (a mixture of Ca(OH)2 and SiO2 sand) and concrete (composed of portland cement Ca3SiO5 / Ca2SiO4 and aggregates). In addition, there are also some composite or derivative process products that combine natural properties with artificial synthesis technologies, such as glazed decorative ware (overglaze color: low-temperature frit of PbO-SiO2-K2O and metal oxide color developers; underglaze color: using high-temperature pigments such as CoO, Al2O3, Cr2O3; Tang Sancai: PbO-SiO2-Al2O3 alkali-lead glaze, adding CuO, Fe2O3, MnO2 for coloring), artificial bionic materials (glass-ceramics: Li2O-Al2O3-SiO2 crystallized glass; terrazzo: a composite material of CaCO3 aggregates and a cement matrix), and refractory materials (fireclay bricks: composed of kaolinite and mullite 3Al2O3·2SiO2; mullite bricks: synthetic 3Al2O3·2SiO2). Inorganic non-metallic products have high hardness, abrasion resistance, high temperature resistance, thermal shock resistance, corrosion resistance, and good insulation, and play an important role in fields such as aerospace, weaponry, advanced manufacturing, consumer electronics, medical and health, cultural relic restoration, jade restoration, and decorative arts.

[0003] Although inorganic materials have a diverse range of products and excellent properties, whether it is traditional ceramic products, ancient stoneware and jade articles, or modern glass components, advanced engineering ceramics, etc., they generally have inherent structural defects such as low fracture toughness, high brittleness, unstable thermal shock, and discontinuous interfaces. Under the action of complex working conditions such as external mechanical shock, thermal cycling, environmental aging, long-term burial, and underwater immersion, microcracks are extremely likely to initiate and further evolve into structural damage under the continuous stress or environmental action, ultimately leading to the fracture and fragmentation of the products, seriously affecting the historical integrity of cultural relics and the service reliability of modern components. In reality, the repair needs are concentrated in three typical scenarios: Firstly, the salvage of cultural relics from underwater shipwreck sites. For example, ceramics and bronzes salvaged from shipwrecks are eroded by seawater salts, attached by marine organisms, and impacted by water flow for a long time, resulting in the peeling of the glaze layer, the crumbling of the structure, and even the overall fragmentation of the products; Secondly, the excavation of underground buried cultural relics. Ceramics, jade articles, etc. found during engineering construction often show phenomena such as local layered peeling, overall fragmentation, and color deterioration due to soil compaction, groundwater infiltration, and oxidation; Thirdly, illegal excavation and improper preservation. The rough excavation by looters directly causes the fracture of the products, and problems such as out-of-control temperature and humidity (such as high humidity accelerating the weathering of gypsum and the precipitation of salt crystals on the glass surface), excessive light, etc. in museums or private collections will also cause further deterioration of the material and increase the risk of fragmentation.

[0004] In addition, the structural repair requirements for inorganic material products used in engineering in the modern industrial and national defense fields are particularly prominent: In the zirconia-based thermal barrier coating of aeroengines, due to phase change stress, local peeling or delamination occurs under extreme temperature gradients, and the missing area needs to be repaired to restore the high-temperature airtight barrier function; After the alumina bulletproof ceramic panel of an armored vehicle is impacted by a ballistic, the broken and peeled part needs to be bonded and repaired to maintain the secondary protection ability; The magnesia-alumina refractory lining of a steelmaking electric furnace shows local fracture and peeling due to thermal shock failure, affecting the structural stability of the furnace body, and local reinforcement is required; In the zirconia toughened ceramic valve in a petrochemical cracking device, under the combined action of long-term acidic medium corrosion and mechanical wear, surface chipping and damage often occur, and inorganic bonding repair materials with high temperature resistance and corrosion resistance are urgently needed to intervene. These scenarios all require that the repair material and the oxide matrix have chemical compatibility, high-temperature phase stability, and matching thermal expansion coefficients, while ensuring that the electrical and magnetic properties of the matrix are not disturbed.

[0005] In the field of restoration of inorganic materials products of cultural relics, in order to maintain the authenticity of the products, it is necessary to follow the three principles of minimum intervention, reversible operation, and material compatibility. Although the current mainstream physical restoration methods (such as rivet embedding, metal wire wrapping, hot melt glass sealing, etc.) can reconstruct the macro structure in the short term, the body damage caused by drilling, the phase change of the glaze layer caused by thermal stress, and the mismatch of the interface of heterogeneous materials are difficult to meet the long-term preservation needs of cultural relics. As an important skill for the restoration of ancient Chinese ceramics, the traditional "porcelain curing" process has cleverly achieved the reorganization of products, but due to the use of metal rivets for fixation, there are also problems of secondary damage to the body and high interface heterogeneity. In the engineering ceramics restoration scenario, traditional processes also face the challenge of insufficient adaptability to extreme working conditions: for example, the yttria-stabilized zirconia (YSZ) thermal barrier coating of aircraft engines has local peeling in long-term high-temperature cycles, and its repair needs to withstand high-temperature cycles of 1200–1300℃; the surface damage of bioceramic joint materials due to load impact requires the repair material to have both biocompatibility and dynamic load stability. These requirements are beyond the capabilities of existing physical repair technologies. Since the above-mentioned processes have obvious deficiencies in interface control, thermal expansion matching and structural continuity, current repair practices are gradually turning to chemical bonding methods based on adhesive materials.

[0006] At present, the commonly used restoration methods mainly include filling and sintering with organic adhesives (such as epoxy, acrylic), inorganic salt solution adhesives (such as sulfate, silicate) or inorganic non-metal slurries. However, these methods are difficult to simultaneously meet the comprehensive requirements of cultural relics restoration for structural matching, interface compatibility, long-term stability and microstructure scale control. Although organic adhesives have mild curing conditions and convenient construction, they have poor high temperature resistance and aging resistance, insufficient long-term stability, and are prone to color changes or performance degradation; although inorganic salt solution adhesive materials have certain heat resistance and environmental stability, they face significant material compatibility and matching problems in the construction of the interface layer. There are large differences in thermal expansion coefficient, elastic modulus, microstructure, etc. between them and the restoration objects such as ceramics, jade, and glass, making it difficult to achieve effective interface bonding; although the inorganic non-metal slurry system can achieve physical connection through high-temperature sintering, the process flow is complicated and the temperature control requirements are strict, making it difficult to adapt to the application requirements of on-site restoration and special-shaped interfaces. In addition, most existing repair materials exist in the form of low-concentration suspensions with low solid content and insufficient number of active particles, resulting in loose structure, high porosity and poor density of the bonding area formed after repair, making it difficult to provide stable and reliable interface bonding strength, and not conducive to the reconstruction of the deep structure inside the crack, limiting its application effect in high-demand cultural relic restoration scenarios. At the same time, traditional adhesive systems generally have the problem of high content of volatile components, which are prone to drastic volume changes during heat treatment, resulting in defects such as interface warping, crack expansion or loose bonding, further reducing the overall repair quality and structural stability. Summary of the invention

[0007] The present invention provides a series of inorganic polymeric adhesives and their repair applications to solve the above problems.

[0008] To achieve the above object, the technical solution of the present invention is as follows:

[0009] On the one hand, the present invention provides an inorganic polymeric adhesive, which is an oligomeric structure formed by the reaction of an inorganic cation precursor and an inorganic anion in the presence of a capping agent, and the oligomeric structure can be cured to form an inorganic polymeric network.

[0010] Further, the cation element in the inorganic cation precursor is selected from one or more of the following: Al, Zr, Ti, Y, La, Nb, Ta, Ca, Mg, Ba, Li, Na, K, Rb, Cs, Be, Sr, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, Cd, Hf, W, Re, Os, Ir, Pt, Au, Hg, Ga, In, Sn, Pb, Bi, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, U, B, Si, Ge, As, Sb, Te;

[0011] The anion ionized by the inorganic anion precursor during the formation of the oligomeric structure is selected from one or more of the following: OH - 、CO3 2- 、PO4 3- 、SiO4 4- 、SiO3 2- 、Si2O7 6- 、Si4O 10 4- 、AlO4 5- 、TiO3 2- 、NbO3 2- 、BO3 3- 、HCO3 - 、SO4 2- ,HSO4 - 、S2O7 2- 、S2O8 2- 、SO3 2- 、HSO3 - 、S2O3 2- 、S2O6 2- 、S3O6 2- 、SO5 2- 、SO2 2- 、PO4 3- 、HPO4 2- 、H2PO 4- 、P2O7 4- 、P3O10 5- , H2PO3 - , HPO3 2- , H2PO3 - , H2PO2 - , (PO3)3 3- , (PO3)4 4- , (PO3)6 6- , P2O6 4- , PO5 3- 。

[0012] Further, the capping agent is any one or more of diethylamine, triethylamine, pyridine, piperidine, pyrrole, piperazine organic amines and their derivatives, and the capping agent is a basic compound.

[0013] Further, the molar ratio of the inorganic cation precursor to the inorganic anion precursor is 1:10 to 10:1;

[0014] The amount of the capping agent is 1 to 500 times the total amount of the inorganic cation precursor and the inorganic anion precursor.

[0015] Further, the inorganic polymeric binder is diluted by adding an organic solvent to adjust its viscosity to 1 to 1,000,000 cP, and the mass fraction of the gel-like substance in the inorganic polymeric binder is 1% to 99%;

[0016] The organic solvent is selected from any one of methanol, ethanol, n-propanol, isopropanol, glycerol, n-butanol, ethylene glycol, acetonitrile, acetone, cyclohexane, n-hexane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, dichloromethane, chloroform, benzene, toluene, xylene, ether, carbon tetrachloride, n-pentane, n-heptane or any combination of the above.

[0017] Further, the conditions of the curing treatment are: the temperature is 10 to 1500 °C, the heating and cooling rate is 0.1 to 50 °C / min, the holding time is 1 min to 48 h, the treatment atmosphere is air, nitrogen, argon or vacuum, and the temperature control accuracy is 0.1 to 10 °C.

[0018] Another aspect of the present invention provides an application of the inorganic polymeric binder in the repair of inorganic material products.

[0019] Further, the application method of the inorganic polymeric binder in the repair of inorganic material products includes the following steps:

[0020] S1. The fracture part and the fragment splicing surface of the inorganic material product are subjected to surface cleaning treatment, and an organic solvent is used to remove oil stains, dust and other interfacial impurities to ensure the cleanliness of the bonding interface;

[0021] S2. Apply the inorganic polymer adhesive to the splicing surface of the inorganic material product fragments or the edge of the fracture site. By means of brushing, injection or capillary penetration, make the inorganic polymer adhesive fully cover the parts to be bonded;

[0022] S3. Align and position the inorganic material product fragments according to the original structure. After splicing and resetting, carry out a curing treatment to cause the inorganic components in the adhesive to undergo polymerization and / or cross-linking reactions, forming an adhesive structure at the joint, realizing the structural reconstruction and firm bonding between the inorganic material product fragments;

[0023] In S4, the temperature of the curing treatment is 10 - 1500 °C, the heating and cooling rate is 0.1 - 50 °C / min, the heat preservation time is 1 min - 48 h, the treatment atmosphere is air, nitrogen, argon or vacuum, and the temperature control accuracy is 0.1 - 10 °C.

[0024] Furthermore, the atomic spatial arrangement of the adhesive structure formed after the curing treatment of the inorganic polymer adhesive is long-range ordered or long-range disordered;

[0025] The internal microstructure of the multi-scale inorganic structure is any one or more of single crystal, polycrystal, and long-range disordered structure;

[0026] Both the single crystal and the polycrystal structure are any one or more of cubic system, tetragonal system, trigonal system, hexagonal system, orthorhombic system, monoclinic system, and triclinic system.

[0027] Furthermore, the adhesive structure is an oxide, carbonate, phosphate, orthosilicate, metasilicate, pyrosilicate, tetrasilicate, aluminate, titanate, niobate, borate, bicarbonate, sulfate, bisulfate, pyrosulfate, persulfate, sulfite, bisulfite, thiosulfate, dithiosulfate, trithiosulfate, peroxymonosulfate, sulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, tripolyphosphate, hydrogen metaphosphate, metaphosphate, hydrogen metaphosphate, hypophosphate, tripoly metaphosphate, tetrapoly metaphosphate, hexapoly metaphosphate, dipoly metaphosphate, perphosphate of one or more metal elements and metalloid elements, and any combination of the above;

[0028] The metal elements are Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Sn, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th or U; the metalloid elements are B, Si, Ge, As, Sb or Te.

[0029] Further, a method for preparing an inorganic polymer adhesive specifically includes the following steps:

[0030] Preparing an inorganic polymer adhesive fluid:

[0031] 1.1) Add an inorganic cation precursor M to a solvent a to obtain a solution A. The M is a soluble inorganic salt containing one or more cations of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Sn, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, U, B, Si, Ge, As, Sb, Te; the solvent a is one or more mixtures of methanol, ethanol, n-propanol, isopropanol, glycerol, n-butanol, ethylene glycol, acetonitrile, acetone, cyclohexane, n-hexane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, dichloromethane, chloroform, benzene, toluene, xylene, ether, carbon tetrachloride, n-pentane, n-heptane, with a volume fraction of 1% to 99%; in the solution A, the concentration of M is 1 mM to 10 M;

[0032] 1.2) Add a capping agent N to the solution A to obtain a solution B; the capping agent is any one of organic amines and their derivatives such as diethylamine, triethylamine, pyridine, piperidine, pyrrole, piperazine or any combination of the above, and the capping agent is generally a basic compound, which is used to regulate the stability of the oligomer structure formed during the oligomerization reaction and prevent premature gelation of the precursor; the concentration of the capping agent is 1 mM to 100 M; in this step, the capping agent is dispersed in A and does not undergo a substantial reaction with M;

[0033] 1.3) Add an inorganic anion precursor O to the solvent a to obtain a solution C; the anions ionized by O during the formation of the oligomer structure are selected from one or more of the following ions: OH - 、CO3 2- 、PO43- , SiO4 4- , SiO3 2- , Si2O7 6- , Si4O 10 4- , AlO4 5- , TiO3 2- , NbO3 2- , BO3 3- , HCO3 - , SO4 2- , HSO4 - , S2O7 2- , S2O8 2- , SO3 2- , HSO3 - , S2O3 2- , S2O6 2- , S3O6 2- , SO5 2- , SO2 2- , PO4 3- , HPO4 2- , H2PO 4- , P2O7 4- , P3O 10 5- , H2PO3 - , HPO3 2- , H2PO3 - , H2PO2 - , (PO3)3 3- , (PO3)4 4- , (PO3)6 6- , P2O6 4- , PO5 3- ; The concentration range of O in solution C is 1 mM to 10 M;

[0034] 1.4) Slowly add solution B to solution C (or omit step 1.3 and directly introduce reactive gases carbon dioxide, sulfur dioxide or sulfur trioxide into solution B), and magnetically stir for 30 - 90 min at room temperature to obtain suspension D, i.e., ionic suspension;

[0035] 1.5) Centrifuge the mixture to remove the supernatant and retain the gel-like substance; The rotation speed of the centrifugation is 1000 - 20000 rpm and the time is 2 - 60 min;

[0036] 1.6) Redisperse the gel in solvent a, and control the viscosity and surface tension of the system by adjusting the amount of solvent to obtain an inorganic polymer adhesive fluid suitable for repairing inorganic material products; the solid mass fraction of this inorganic polymer adhesive fluid is 1% - 99%, and its rheological properties can be adjusted according to the repair requirements to adapt to different penetration, filling or coating methods.

[0037] Furthermore, the specific steps for applying the inorganic polymer adhesive to the repair and curing treatment of inorganic material products are as follows:

[0038] Use the above-obtained inorganic polymer adhesive fluid as a repair material, and apply it to the fragmented parts of inorganic material products by means of coating, filling, spraying or impregnation, etc., and achieve dense curing through curing treatment, thereby completing the bonding of the structure of inorganic material products;

[0039] Coating method: Use a brush, scraper or coater to evenly apply it to the fragmented parts of inorganic material products, which is suitable for bonding larger areas or surface fragments. Typical parameters include: coating thickness 10 - 1000 μm, applicable viscosity 500 - 5000 mPa·s, coating ambient temperature 0 - 100 °C, humidity 40% - 70%;

[0040] Filling method: Adopt injection or manual filling methods to accurately inject the inorganic polymer adhesive into the gaps between the fragmented parts of inorganic material products, which is suitable for the case where the joint surface width is 5 - 500 μm and the bonding depth can reach 10 mm. Its parameters are: fluid viscosity 1000 - 10000 mPa·s, initial curing time after filling 10 - 300 min;

[0041] Spraying method: Use a spray gun or atomizing device to evenly cover the joint surface of the fragmented parts of inorganic material products, which is suitable for thin-layer bonding and uniform coverage. The process parameters are: nozzle diameter 50 - 500 μm, spraying pressure 10 - 100 kPa, spray particle size 1 - 50 μm, ambient temperature -20 - 200 °C, humidity 30% - 80%;

[0042] Impregnation method: Through soaking or local coating, make the inorganic polymer adhesive penetrate into the microscopic structure of the joint surface of inorganic material products to enhance the bonding effect of fragments. Its process parameters are: for pore or void size 50 nm - 10 μm, impregnation time 5 - 1500 min, temperature 10 - 300 °C, inorganic polymer adhesive concentration 5 - 50 wt%.

[0043] Curing treatment: After the inorganic polymer adhesive is deposited, the inorganic components are further polymerized and cross-linked through curing treatment to form a dense bonding structure. The curing treatment parameters are: temperature range 10 ~ 1500 ° C, heating / cooling rate 0.1 ~ 50 ° C / min, temperature control accuracy 0.1-10 ° C, can be carried out in air, nitrogen, argon, ammonia, hydrogen sulfide, hydrogen, oxygen and other atmospheres.

[0044] The obtained inorganic material product bonding structure contains Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Sn, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, U, B, Si, Ge, As, Sb or Te metal elements and metalloid elements. The metal elements and metalloid elements can form oxides, phosphates, carbonates and sulfates, and have a planar or three-dimensional morphology with a size range of 50nm to 10cm. The inorganic material product bonding structure morphology includes point-shaped, linear, sheet-shaped, spherical, annular and conical geometric composite forms, and has good interface matching and thermomechanical resistance.

[0045] The beneficial effects of the present invention are:

[0046] The inorganic polymer adhesive system provided by the present invention has a highly consistent chemical composition and physical structure with the target repair material in terms of ion composition, crystal structure and cured product, and can achieve in-situ reconstruction bonding repair within the temperature range that the material can withstand by means of local heating or programmed temperature control. 2+ 、Al 3+ 、Zr 4+ Ion migration and covalent / ionic bond reconstruction occur with the substrate surface to form a continuous inorganic ceramic structure that matches the structure of the parent material, thereby achieving interface reconstruction of the material's own components without introducing a heterogeneous bonding phase, effectively avoiding problems such as interface thermal mismatch, aging, discoloration and peeling;

[0047] Compared with traditional ceramic repairs that rely on high-temperature sintering (often above 1000°C) or organic resin bonding, the adhesive of the present invention can achieve dense bonding between materials under controllable heat treatment conditions of 200-1500°C, taking into account both medium and low temperature adaptability and high temperature thermal stability, and is particularly suitable for bonding and repairing inorganic material products that are not resistant to high temperatures or have sensitive surfaces (such as bone china, white marble) and high-performance oxide ceramics (such as zirconia, sapphire, etc.);

[0048] Through the synergistic effect of ionic interdiffusion and in-situ transformation of the gel network, the interface of this system forms a dense transition zone without pores and weak bonding areas, with excellent mechanical strength, thermal stability and interface integrity. The error of the coefficient of thermal expansion matching can be controlled within ±20%, effectively improving the reliability of the repaired structure under thermal cycling, mechanical stress and service aging conditions. The final adhesive layer is an inorganic substance such as dense oxides, carbonates or phosphates similar to the original material, realizing the transformation from "structural adhesion" to "self-weight reconstruction repair with consistent composition", and having significant material compatibility, function retention and cultural heritage repair value. In addition, this inorganic polymer adhesive also has the potential for popularization and application in the fields of aerospace, weaponry, advanced manufacturing, consumer electronics, medical and health, cultural relics restoration, jade restoration, decorative arts, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0049] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for the description of the embodiments or the prior art. Obviously, the drawings in the following description are some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0050] Figure 1 It is a process diagram for the preparation of the inorganic polymer adhesive of the present invention;

[0051] Figure 2 It is a flow chart for the inorganic polymer adhesive of the present invention to repair the ceramic of inorganic material products;

[0052] Figure 3 It is a flow chart for the inorganic polymer adhesive of the present invention to repair the marble of inorganic material products;

[0053] Figure 4 It is a flow chart for the inorganic polymer adhesive of the present invention to repair the white marble of inorganic material products;

[0054] Figure 5 It is a flow chart for the inorganic polymer adhesive of the present invention to repair the jade of inorganic material products;

[0055] Figure 6 It is a flow chart for the inorganic polymer adhesive of the present invention to repair the gypsum of inorganic material products;

[0056] Figure 7 It is a photo of the inorganic polymer adhesive of the present invention;

[0057] Figure 8 It is a photo of the calcium-based adhesive bonding the bone china plate in Example 3 of the present invention;

[0058] Figure 9This is a photo of the bone china plate bonded with the calcium-based binder after curing in Example 3 of the present invention;

[0059] Figure 10 This is a photo of the Zr-OH oligomer fluid obtained in Example 8 of the present invention. Detailed implementation manners

[0060] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0061] As Figure 1 shown, the principle of this method lies in selecting soluble inorganic cation precursors and anion precursors to form a stable inorganic ion oligomer system in the presence of a capping agent. This system has good rheological properties and thermal reaction activity within a certain concentration range. After centrifugal enrichment, the obtained gel-like substance can be redispersed in a low-volatility organic solvent to prepare an inorganic polymerization binder for repairing inorganic material products. A photo of the inorganic polymerization binder is as Figure 7 shown.

[0062] During the repair process, the binder can be precisely deposited on the crack, hole, or edge defect area of the inorganic material product with high spatial resolution through processes such as coating, filling, spraying, or impregnation, to achieve the controllable construction of irregular curved surfaces and micro-defects. After deposition, heat treatment is carried out in the range of 200-700 °C to cause the inorganic ions in the binder to undergo polycondensation, oxygen bridge connection, or cross-linking reactions to in-situ form a dense inorganic oxide structure.

[0063] The present invention uses a continuous process path of ion oligomerization - deposition - heat treatment to construct a repair layer on the surface of the inorganic material product that is continuous with the matrix structure and has a thermal expansion match, avoiding problems such as organic aging, high-temperature sintering, and interface cracks in traditional repair technologies.

[0064] As Figures 2 - 6As shown, they are respectively the repair flowcharts of typical inorganic material products (ceramics, marble, white marble, jadeite, gypsum). The specific repair process includes: First, inorganic cation and anion precursors react in the presence of a solvent and a capping agent to form a suspension, and a high-concentration gel substance is obtained by centrifugal enrichment. This substance is formulated with a solvent and used as a repair adhesive, and a repair structure (such as a schematic "H" structure) is deposited along the crack path by means of coating, filling, spraying, or impregnation; Subsequently, the capping agent is removed by heat treatment and the inorganic polymerization reaction is promoted to completion to form a continuous and dense inorganic ceramic repair band.

[0065] The repair structure can be made of materials such as zirconia, alumina, calcium oxide, carbonate, silicate, titanate, etc., and the structural morphology can be linear, banded, or shell-like, and is suitable for the fragment bonding repair of porcelain, pottery, jade, gypsum, marble, white marble, jadeite, Hetian jade, etc.

[0066] Example 1: Aluminum-based inorganic polymerization adhesive and its application in pottery bonding repair

[0067] Pottery usually uses minerals such as kaolin, feldspar, and quartz as the main raw materials, and its common chemical components include silicon dioxide (SiO2), aluminum oxide (Al2O3), iron oxide (Fe2O3), and calcium oxide (CaO). For the Al2O3 in the pottery matrix, an inorganic polymerization adhesive of the Al 3+ system achieves better compatibility in composition.

[0068] 1. Prepare the aluminum-based inorganic polymerization adhesive:

[0069] 1.1) Weigh 6.00 g of aluminum chloride (AlCl3, concentration 0.9 M) and add it to 50 mL of absolute ethanol, stir evenly to obtain solution A;

[0070] 1.2) Add 2.53 g of triethylamine (concentration 0.5 M) to solution A and continue stirring for 15 min to generate solution B;

[0071] 1.3) Slowly add 1.0 mL of deionized water to solution B and stir for 40 min to form an Al-OH suspension C;

[0072] 1.4) Centrifuge C (7000 rpm, 10 min), discard the supernatant, and collect the lower-layer gel-like substance;

[0073] 1.5) Resuspend the gel in an ethanol / glycerol (volume ratio 3:1) mixture and adjust the viscosity to about 2500 cP, and the solid content is about 35%.

[0074] 2. Steps for the application of pottery fragment bonding:

[0075] 2.1) Select ceramic chips, clean the surface, and place them on a preheated workbench at 50 °C;

[0076] 2.2) Use a coating tool to evenly coat the edge of the ceramic fragment with the adhesive;

[0077] 2.3) Heat it to 1000 °C at a heating rate of 2 °C / min in a nitrogen atmosphere, hold for 60 min, and then cool naturally;

[0078] 2.4) A continuous and dense Al2O3 structure is formed in the repaired area, with a smooth surface, no shedding or cracks, a natural transition with the pottery matrix, and good structural bonding.

[0079] Example 2: Aluminum-based inorganic polymer adhesive and its application in porcelain bonding and repair

[0080] Porcelain is made from kaolin, feldspar, and quartz as raw materials and is sintered at high temperature to form a dense ceramic structure. Its main components are SiO2 and Al2O3, and it often contains flux oxides such as K2O, Na2O, and CaO. The glaze surface is a silicon-rich glass phase, showing high gloss and good thermal stability. To improve the matching of the repair layer with the porcelain glaze in terms of chemical composition, structural density, and thermal expansion coefficient, an inorganic polymer adhesive of the Al 3+ system is selected in this example.

[0081] 1. Prepare the aluminum-based inorganic polymer adhesive:

[0082] 1.1) Weigh 4.00 g of aluminum chloride (AlCl3, concentration 0.6 M) and dissolve it in 50 mL of absolute ethanol, stir evenly to obtain solution A;

[0083] 1.2) Add 2.53 g of triethylamine (concentration 0.5 M) to solution A and continue stirring for 15 min to form solution B;

[0084] 1.3) Slowly add 0.8 mL of deionized water to solution B and continue stirring for 40 min to obtain an Al-OH suspension C;

[0085] 1.5) Centrifuge C (8000 rpm, 30 min), discard the supernatant, and collect the gel-like substance;

[0086] 1.6) Resuspend the gel in an ethanol / glycerol mixture (volume ratio 3:1), adjust the viscosity to about 2800 cP, and the solid content is about 38%.

[0087] 2. Steps for porcelain fragment bonding application:

[0088] 2.1) Select porcelain fragments, clean and fix them on a constant temperature platform (50 °C), and keep the surface dry;

[0089] 2.2) Use a coating tool to evenly coat the adhesive on the edge of the fragment;

[0090] 2.3) Place the treated sample in an air atmosphere, heat it to 400 °C at a heating rate of 2 °C / min, hold for 60 min, and then cool it naturally;

[0091] 2.4) A continuous and dense Al2O3 ceramic structure is formed in the repair area, with a smooth surface, high transparency, a flat interface without bubbles, cracks or peeling, a natural color transition, and good fusion with the enamel.

[0092] Example 3: Calcium-based inorganic polymer adhesive and its application in bone china bonding and repair

[0093] Bone china usually uses animal bone ash, kaolin, feldspar, quartz, etc. as the main raw materials. It has a moderate sintering temperature and after being fired into porcelain, it has the characteristics of dense texture, warm color, and good semi-transparency. Its common chemical components include silicon dioxide (SiO2), aluminum oxide (Al2O3), calcium phosphate (Ca2H2(PO4)2), etc., among which Ca2H2(PO4)2 and SiO2 are the main sources of the inorganic framework. Aiming at the Ca2H2(PO4)2 component existing in bone china, this example uses Ca 2+ The inorganic polymer adhesive of the system achieves good compatibility in terms of structural composition and thermal expansion performance.

[0094] 1. Calcium-based inorganic polymer adhesive

[0095] 1.1) Weigh 3.68 g of calcium chloride dihydrate (CaCl2·2H2O, concentration 0.5 M) and add it to 50 mL of absolute ethanol, stir evenly to obtain solution A;

[0096] 1.2) Add 4.04 g of triethylamine (concentration 1 M), continue to stir for 15 min to obtain solution B;

[0097] 1.3) Slowly drop 1.0 mL of phosphoric acid solution (H3PO4, concentration 0.5 M) into solution B, continue to stir for 40 min to form a suspension C;

[0098] 1.4) Centrifuge C (8000 rpm, 10 min), discard the supernatant, and collect the gel-like substance;

[0099] 1.5) Resuspend the gel in an ethanol / glycerol mixture (volume ratio 3:1), adjust the viscosity to about 2800 cP, and the solid content to about 38%.

[0100] 2. Steps for bone china fragment bonding application:

[0101] 2.1) Select bone china fragments, clean them and fix them on the platform, and set the surface preheating temperature to 50 °C;

[0102] 2.2) Use a coating tool to evenly coat the adhesive on the edges of the fragments ( Figure 8 );

[0103] 2.3) Heat it to 40 °C at a heating rate of 2 °C / min in an air atmosphere, hold for 60 min, and cool naturally ( Figure 9 );

[0104] 2.4) A dense and continuous hydroxyapatite ceramic structure is formed in the repair area, with a natural surface transition, tight bonding with the bone china matrix, and no cracks, peeling, or obvious color difference.

[0105] Example 4: Calcium-based inorganic polymer adhesive and its application in the bonding repair of white marble

[0106] White marble is a dense stack of calcium carbonate (CaCO3 content ≥ 95%) crystal phases, often resulting in grain boundary fractures and the formation of stepped cleavage planes due to stress concentration or environmental corrosion. Considering the main component characteristics of white marble, an inorganic adhesive of the Ca 2+ system is selected in this example to achieve epitaxial regeneration of calcium carbonate crystals through calcium ion migration.

[0107] 1. Preparation of calcium-based inorganic polymer adhesive:

[0108] 1.1) Weigh 3.68 g of calcium chloride dihydrate (CaCl2·2H2O, concentration 0.5 M) and add it to 50 mL of absolute ethanol, stir evenly to obtain solution A;

[0109] 1.2) Add 2.53 g of triethylamine (concentration 0.5 M) to solution A and continue stirring for 15 min to form solution B;

[0110] 1.3) Pass carbon dioxide gas into solution B and stir magnetically at room temperature, with a gas flow rate of 50 mL / min, and the gas passing and stirring time is 30 min to obtain suspension C;

[0111] 1.4) Centrifuge C (7000 rpm, 10 min), discard the supernatant, and collect the lower gel-like substance;

[0112] 1.5) Resuspend the gel in a mixture of ethanol / glycerol (volume ratio 3:1), adjust the viscosity to about 2500 cP, and the solid content is about 35%.

[0113] 2. Steps for the bonding application of white marble fragments:

[0114] 2.1) Select white marble fragments, clean the surface, and place them on a preheated workbench at 50 °C;

[0115] 2.2) Use a coating tool to evenly coat the adhesive on the edges of the white marble fragments;

[0116] 2.3) Heat it to 300 °C at a heating rate of 2 °C / min in a nitrogen atmosphere, keep it for 60 min, and then cool it naturally;

[0117] 2.4) A continuous and dense CaCO3 structure is formed in the repaired area, with a smooth surface, no peeling or cracking, a natural transition with the marble matrix, and good structural bonding.

[0118] Example 5: Calcium-based inorganic polymer adhesive and its application in marble bonding and repair

[0119] Marble is composed of calcite (CaCO3) and dolomite (CaMg(CO3)2) (CaO 30 - 45%, MgO 10 - 20%, SiO2 2 - 15%), and transgranular fracture is likely to occur at the multiphase interface. In this example, an inorganic adhesive for the Ca 2+ system is designed to achieve the bonding and repair of marble fragments.

[0120] 1. Prepare the calcium-based inorganic polymer adhesive

[0121] 1.1) Weigh 0.882 g of calcium chloride dihydrate (CaCl2·2H2O, concentration 0.2 M) and dissolve it in 50 mL of absolute ethanol to prepare solution A;

[0122] 1.2) Add 5.06 g of triethylamine (concentration 1 M) and stir for 20 min to obtain solution B;

[0123] 1.3) Pass carbon dioxide gas into solution B and stir magnetically at room temperature. The gas flow rate is 60 mL / min, and the gas passing and stirring time is 20 min to obtain suspension C as the ionic oligomer solution;

[0124] 1.4) Centrifuge C (8000 rpm, 10 min), discard the supernatant, and collect the gel-like substance;

[0125] 1.5) Resuspend the gel in an ethanol / glycerol mixture (volume ratio 2:1), and adjust the viscosity to about 3500 cP and the solid content to about 42%.

[0126] 2. Steps for the application of marble fragments bonding:

[0127] 2.1) Place the marble fragments on a 60 °C platform and keep the surface clean;

[0128] 2.2) Use a coating tool to evenly coat the adhesive on the edges of the fragments;

[0129] 2.3) Heat it to 450 °C at a heating rate of 2 °C / min in an air atmosphere, keep it for 90 min, and then cool it naturally;

[0130] 2.4) The obtained repair layer has a CaCO3 structure, with good interfacial bonding and no chalking or sense of boundary on the surface.

[0131] Example 6: Aluminum-based inorganic polymer adhesive and its application in jadeite bonding and repair

[0132] Jadeite (jade) is mainly composed of aluminosilicate minerals (Na(AlSi2O6)), with a dense and delicate structure and excellent mechanical toughness. The proportion of Al element in jadeite is relatively high. In this example, an inorganic polymer adhesive with an Al3+ system is used for bonding and repairing jadeite fragments.

[0133] 1. Preparation of aluminum-based inorganic polymer adhesive

[0134] 1.1) Weigh 4.28 g of aluminum chloride (AlCl3, concentration 0.9 M) and add it to 50 mL of methanol, stir evenly to obtain solution A;

[0135] 1.2) Add 2.53 g of triethylamine (concentration 0.5 M), stir for 15 min to obtain solution B;

[0136] 1.3) Slowly drop 1.0 mL of deionized water into B, continue to stir for 40 min to form suspension C;

[0137] 1.4) Centrifuge C (4000 rpm, 5 min), discard the supernatant, and retain the gel-like substance;

[0138] 1.5) Resuspend the gel in a methanol / glycerol mixture (volume ratio 4:1), adjust the viscosity to about 3000 cP, and the solid content to about 45%.

[0139] 2. Steps for jadeite fragment bonding application:

[0140] 2.1) Place the jadeite fragment sample on a constant temperature platform, and control the surface temperature at 60 °C;

[0141] 2.2) Use the inorganic polymer adhesive to accurately coat along the bonding edge of the fragments.

[0142] 2.3) Heat up to 1200 °C at a heating rate of 2 °C / min in an air atmosphere, keep warm for 48 h, and cool naturally;

[0143] 2.4) The obtained repair band has a transparent and dense Al2O3 structure, with a continuous and flat interface, consistent color, and no peeling in the repair area.

[0144] Example 7: Aluminum-based inorganic polymer adhesive and its application in turquoise bonding and repair

[0145] Turquoise (CuAl6(PO4)4(OH)8·4H2O) is a typical aluminum-containing phosphate mineral, rich in Al2O3 in its structure, and has good chemical stability and decorative properties. In this example, an inorganic polymer binder of the Al3+ system is used for fragment bonding and repair of turquoise.

[0146] 1. Preparation of magnesium-aluminum-based inorganic polymer binder

[0147] 1.1) Weigh 2.04 g of aluminum chloride (AlCl3, concentration 0.4 M) and dissolve it in 50 mL of absolute ethanol, stir evenly to obtain solution A;

[0148] 1.2) Add 2.53 g of triethylamine (concentration 0.5 M), stir for 20 min to form solution B;

[0149] 1.3) Slowly add 1.0 mL of deionized water to B, continue to stir for 40 min to form an Al-OH oligomer suspension C;

[0150] 1.4) Centrifuge C (5000 rpm, 10 min), discard the supernatant, and collect the gel-like substance;

[0151] 1.5) Resuspend the gel in an ethanol / glycerol mixture (volume ratio 3:1), adjust the viscosity to about 3000 cP, and the solid content to about 40%.

[0152] 1.1) Weigh 2.56 g of magnesium chloride (MgCl2, concentration 0.5 M) and 2.04 g of aluminum chloride (AlCl3, concentration 0.4 M) and dissolve them separately in 50 mL of absolute ethanol, mix and stir evenly to obtain solution A;

[0153] 2. Application steps for bonding turquoise fragments

[0154] 2.1) Place the turquoise fragments on a thermostatic platform, set the surface temperature to 65 °C, and keep the surface dry;

[0155] 2.2) Use the inorganic polymer binder to evenly and precisely coat along the edges of the fragments;

[0156] 2.3) In an air atmosphere, heat up to 800 °C at a heating rate of 2 °C / min, hold for 6 h, and cool naturally;

[0157] 2.4) A continuous and dense alumina structure is formed in the repair area, which has good compatibility with the turquoise matrix in terms of microstructure and chemical composition, high bonding strength, smooth surface, and natural repair transition.

[0158] Example 8: Zirconium-based inorganic polymer binder and its application in bonding and repairing medical zirconia ceramics

[0159] 1. Zirconium-based inorganic polymer binder:

[0160] 1.1) Weigh 2.33 g of zirconium chloride (ZrCl4, concentration 0.2 M) and slowly add it dropwise to 50 mL of absolute ethanol, stir evenly to obtain solution A;

[0161] 1.2) Add 2.02 g of triethylamine (concentration 0.5 M), stir for 15 min to obtain solution B;

[0162] 1.3) Slowly add dropwise 0.5 mL of deionized water and continue to stir for 30 min to form a Zr-OH suspension C;

[0163] 1.4) Centrifuge C (8000 rpm, 10 min), discard the supernatant, and collect the lower gel-like substance;

[0164] 1.5) Resuspend the gel in isopropanol, adjust the viscosity to about 2500 cP, and the solid content to about 35%, and the prepared Zr-OH oligomer fluid is as Figure 3 shown.

[0165] 2. Application steps for bonding medical zirconia ceramic fragments:

[0166] 2.1) Select zirconia ceramic implant fragments and fix them on a constant temperature platform (set temperature 60 °C);

[0167] 2.2) Use a coating tool to evenly coat the adhesive on the edges of the fragments;

[0168] 2.3) Heat it to 350 °C at a heating rate of 2 °C / min in an argon atmosphere, keep it warm for 90 min, and cool it naturally;

[0169] 2.4) A ZrO2 structure is formed in the repair area, with strong adhesion, a flat interface, no particle shedding or edge warping, meeting the requirements for bonding the microstructure of medical ceramics.

[0170] Example 9: Zirconium-based inorganic polymer adhesive and its application in bonding and repairing aerospace zirconia-based ceramics

[0171] 1. Prepare zirconia adhesive:

[0172] 1.1) Weigh 4.66 g of zirconium chloride (ZrCl4, concentration 0.4 M) and add it to 50 mL of absolute ethanol, stir evenly to obtain solution A;

[0173] 1.2) Add 1.01 g of triethylamine (concentration 0.25 M), continue to stir for 20 min to obtain solution B;

[0174] 1.3) Slowly add dropwise 1.0 mL of deionized water and continue to stir for 40 min to generate a Zr-OH suspension C;

[0175] 1.4) Centrifuge C (9000 rpm, 10 min), discard the supernatant, and collect the gel-like substance;

[0176] 1.5) Resuspend the gel in an ethanol / glycerol mixture (volume ratio 2:1), adjust the viscosity to about 4000 cP, and the solid content to about 45%, to obtain the Zr-OH oligomer fluid as Figure 10 shown.

[0177] 2. Application steps for bonding aerospace zirconia-based ceramic fragments:

[0178] 2.1) Select aerospace zirconia ceramic fragments, fix them on the working platform, and set the platform temperature to 80 °C;

[0179] 2.2) Use a coating tool to evenly coat the adhesive on the edges of the fragments;

[0180] 2.3) Heat up to 600 °C at a heating rate of 2 °C / min in an air atmosphere, keep warm for 90 min, and then cool naturally;

[0181] 2.4) The repaired zone forms a dense and continuous ZrO2 structure, the interface transition is smooth, and the cracks do not expand, meeting the requirements of the thermal cycle stability and mechanical integrity of the thermal protection structure.

[0182] Example 10: Aluminum-based inorganic polymer adhesive and its application in bonding and repairing sapphire electronic devices

[0183] The sapphire crystal is a high-purity α-Al2O3 single crystal, with high hardness, high light transmittance, and excellent thermal and chemical stability. It is widely used in the field of high-performance electronic devices, such as LED epitaxial substrates, power semiconductor substrates, and sensor windows (the Al2O3 content is usually greater than 99.99%). Due to its relatively high brittleness, it is prone to fracture or fragmentation during processing or service, affecting the structural integrity and functional performance of electronic devices. In view of the application characteristics of sapphire as an electronic substrate in this example, an inorganic polymer adhesive based on the Al 3+ ion system is designed for high-strength repair of the interfaces of sapphire crystal fragments.

[0184] 1. Preparation of aluminum-based inorganic polymer adhesive

[0185] 1.1) Weigh 4.08 g of anhydrous aluminum chloride (AlCl3, concentration 0.9 M), add it to 50 mL of anhydrous ethanol, and stir evenly to obtain solution A;

[0186] 1.2) Add 2.53 g of triethylamine (concentration 0.5 M), and stir for 20 min to obtain solution B;

[0187] 1.3) Slowly add 1.0 mL of deionized water to B, and continue stirring for 40 min to form an Al-OH suspension C;

[0188] 1.4) Centrifuge C (5000 rpm, 10 min), discard the supernatant, and collect the gel-like substance;

[0189] 1.5) Resuspend the gel in an ethanol / glycerol mixture (volume ratio 3:1), adjust the viscosity to about 3200 cP, and the solid content to about 43%.

[0190] 2. Steps for the bonding application of sapphire fragments:

[0191] 2.1) Place the sapphire fragments on a thermostatic heating platform, control the surface temperature at 80 °C, and keep the surface dry and clean;

[0192] 2.2) Use a microcoating tool to evenly coat the adhesive along the edge of the fragment cross-section;

[0193] 2.3) In an air atmosphere, heat it to 1100 °C at a heating rate of 2 °C / min, hold for 60 min, and then cool naturally;

[0194] 2.4) The obtained repair layer is a continuous and dense α-Al2O3 structure, with a tightly bonded interface, the refractive index is the same as that of the base material, the mechanical strength and optical properties of the repair area are good, and there is no obvious visible boundary.

[0195] Example 11: Aluminum-based inorganic polymer adhesive and its application in bonding and repairing ruby optical base crystals

[0196] Ruby crystals belong to α-Al2O3 single crystals doped with Cr 3+ ions, with excellent thermal stability, chemical stability, and unique laser luminescence properties (the main component Al2O3 > 99%, doped with Cr2O3 about 0.05% - 0.5%). As a classic laser substrate material, ruby crystals are widely used in high-energy lasers, optical amplifiers, and other fields. However, due to the relatively high brittleness of the crystal itself, microcracks or fractures are likely to occur at its interface, which in turn affects the laser output stability and optical properties. In this example, aiming at the functional requirements of ruby as an optical substrate, an inorganic polymer adhesive based on the Al3+ ion system is used to achieve the repair of ruby crystals.

[0197] 1. Preparation of aluminum-based inorganic polymer adhesive

[0198] 1.1) Weigh 4.08 g of anhydrous aluminum chloride (AlCl3, concentration 0.9 M) and dissolve it in 50 mL of anhydrous ethanol, stir evenly to obtain solution A;

[0199] 1.2) Add 2.53 g of triethylamine (concentration 0.5 M), stir for 20 min to obtain solution B;

[0200] 1.3) Slowly drop 1.0 mL of deionized water into B, and continue stirring for 40 min to form an Al-OH suspension C;

[0201] 1.4) Centrifuge C (8000 rpm, 10 min), discard the supernatant, and collect the gel-like substance;

[0202] 1.5) Resuspend the gel in an ethanol / glycerol mixture (volume ratio 3:1), adjust the viscosity to about 3200 cP, and the solid content to about 43%.

[0203] 2. Steps for bonding and applying ruby fragments:

[0204] 2.1) Place the ruby crystal fragments on a thermostatic heating platform, control the surface temperature at 80 °C, and keep the surface dry and clean;

[0205] 2.2) Use a microcoating tool to evenly coat the adhesive along the bonding edge of the fragments;

[0206] 2.3) In an air atmosphere, heat up to 1450 °C at a heating rate of 2 °C / min, hold for 60 min, and cool naturally;

[0207] 2.4) The obtained repair layer is a continuous and dense α-Al2O3 structure, with a dense interface bond, uniform color, no obvious boundary in the repair area, and excellent laser transmittance.

[0208] Example 12: Potassium titanium-based inorganic polymer adhesive and its application in bonding and repairing nonlinear optical crystals

[0209] The KTP (KTiOPO4) crystal belongs to the phosphate-based nonlinear optical crystal system, and has excellent second harmonic generation conversion efficiency, wide optical transmission bandwidth, and good electro-optic performance. Due to the low hardness, high brittleness, and high sensitivity to the humid and hot environment of the KTP crystal, the device is prone to fracture or fragmentation problems during processing and service, affecting the nonlinear conversion efficiency and overall optical performance. In this example, a potassium titanium phosphate-based inorganic polymer adhesive is used to bond and repair KTP crystal fragments.

[0210] 1. Preparation of phosphate-based inorganic polymer adhesive:

[0211] 1.1) Weigh 1.74 g of potassium dihydrogen phosphate (KH2PO4) and 2.56 g of titanium isopropoxide (Ti(OiPr)4), and dissolve them in 25 mL of anhydrous ethanol respectively to obtain solutions A and B;

[0212] 1.2) Slowly drop solution B into solution A under stirring conditions, and stir for 30 min to obtain a mixed solution C;

[0213] 1.3) Slowly add 1 mL of deionized water dropwise to C, and continue stirring for 40 min to form a K-Ti-P-O system suspension;

[0214] 1.4) Centrifuge the mixture C (2000 rpm, 10 min), discard the supernatant, and collect the gel-like substance;

[0215] 1.5) Resuspend the gel in a mixture of ethanol / glycerol (volume ratio 2:1), adjust the viscosity to about 1000 cP, and the solid content to about 40%.

[0216] 2. Application steps for bonding KTP crystal fragments:

[0217] 2.1) Place the KTP crystal fragments on a constant-temperature heating platform, control the surface temperature at 50 °C, and keep the surface dry and clean;

[0218] 2.2) Use a microcoating tool to evenly coat the adhesive along the edge of the fragment cross-section;

[0219] 2.3) Heat up to 350 °C at a heating rate of 2 °C / min in an air atmosphere, hold for 60 min, and cool naturally;

[0220] 2.4) The obtained repair band is a continuous and dense KH2PO4 phase interface, the crystal surface is well bonded, the nonlinear optical performance remains stable, there is no obvious boundary in the repair area, and there are no light scattering defects.

[0221] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions described in the foregoing embodiments, or perform equivalent replacements on some or all of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An inorganic polymer binder, characterized in that: The inorganic polymer binder is an oligomer structure formed by the reaction of an inorganic cationic precursor and an inorganic anion in the presence of a capping agent, and the oligomer structure can be cured to form an inorganic polymer network.

2. The inorganic polymer binder according to claim 1, characterized in that The cationic element in the inorganic cationic precursor is selected from one or more of the following: Al, Zr, Ti, Y, La, Nb, Ta, Ca, Mg, Ba, Li, Na, K, Rb, Cs, Be, Sr, Sc, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ru, Rh, Pd, Ag, Cd, Hf, W, Re, Os, Ir, Pt, Au, Hg, Ga, In, Sn, Pb, Bi, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, U, B, Si, Ge, As, Sb, Te; The anions ionized from the inorganic anion precursor during the formation of the oligomer structure are selected from one or more of the following: OH - 、CO3 2- PO4 3- 、SiO4 4- 、SiO3 2- 、Si2O7 6- 、Si4O 10 4- 、AlO4 5- 、TiO3 2- 、NbO3 2- , BO3 3- 、HCO3 - 、SO4 2- , HSO4 - 、S2O7 2- 、S2O8 2- 、SO3 2- 、HSO3 - 、S2O3 2- 、S2O6 2- 、S3O6 2- 、SO5 2- 、SO2 2- PO4 3- 、HPO4 2- 、H2PO 4- 、P2O7 4- 、P3O 10 5- 、H2PO3 - 、HPO3 2- 、H2PO3 - 、H2PO2 - 、(PO3)3 3- 、(PO3)4 4- 、(PO3)6 6- 、P2O6 4- PO5 3- .

3. The inorganic polymer binder according to claim 1, characterized in that The capping agent is any one or more of an organic amine and its basic derivatives; The organic amines include diethylamine, triethylamine, pyridine, piperidine, pyrrole and piperazine.

4. The inorganic polymer binder according to claim 1, characterized in that The molar ratio of the inorganic cation precursor to the inorganic anion precursor is 1:10 to 10:1; The amount of the capping agent is 1 to 500 times the total amount of the inorganic cation precursor and the inorganic anion precursor.

5. The inorganic polymer binder according to claim 1, characterized in that The inorganic polymer binder can be diluted by adding an organic solvent as needed to adjust its viscosity to 1 to 1,000,000 cP, and the mass fraction of the gel-like substance in the inorganic polymer binder after dilution is 1% to 99%; The organic solvent is selected from any one of methanol, ethanol, n-propanol, isopropanol, glycerol, n-butanol, ethylene glycol, acetonitrile, acetone, cyclohexane, n-hexane, tetrahydrofuran, dimethyl sulfoxide, N,N-dimethylformamide, ethyl acetate, dichloromethane, chloroform, benzene, toluene, xylene, ether, carbon tetrachloride, n-pentane, and n-heptane, or any combination of the above.

6. The inorganic polymer binder according to claim 1, characterized in that The curing treatment conditions are: temperature of 10-1500°C, heating and cooling rate of 0.1-50°C / min, insulation time of 1min-48h, treatment atmosphere of air, nitrogen, argon or vacuum, and temperature control accuracy of 0.1-10°C.

7. Use of the inorganic polymer adhesive according to claim 1 in repairing inorganic material products.

8. The use of the inorganic polymer adhesive in repairing inorganic material products according to claim 8, characterized in that: The method for applying the inorganic polymer adhesive in repairing inorganic material products comprises the following steps: S1. Clean the fractured parts and splicing surfaces of inorganic material products, and use organic solvents to remove oil, dust and other interface impurities to ensure the cleanliness of the bonding interface; S2. Applying an inorganic polymer adhesive to the splicing surface of the fragments or the edge of the fractured part, by brushing, injection or capillary penetration, so that the inorganic polymer adhesive fully covers the part to be bonded; S3, aligning and positioning the fragments of the inorganic material product according to the original structure, reassembling and resetting them, and then curing them to make the inorganic components in the adhesive undergo polymerization and / or cross-linking reactions to form a bonding structure at the joints, thereby achieving structural reconstruction and firm bonding between the fragments of the inorganic material product; In S3, the curing treatment temperature is 10-1500°C, the heating and cooling rate is 0.1-50°C / min, the insulation time is 1min-48h, the treatment atmosphere is air, nitrogen, argon or vacuum, and the temperature control accuracy is 0.1-10°C.

9. Use of the inorganic polymer adhesive according to claim 8 in repairing inorganic material products, characterized in that: The atomic spatial arrangement of the bonding structure formed after the inorganic polymer adhesive is cured is long-range ordered or long-range disordered; The internal microstructure of the multi-scale inorganic structure is any one or more of a single crystal, a polycrystalline, and a long-range disordered structure; The single crystal and the polycrystalline structure are any one or more of an equiaxed system, a tetragonal system, a trigonal system, a hexagonal system, an orthorhombic system, a monoclinic system, and a triclinic system.

10. Use of the inorganic polymer adhesive according to claim 9 in repairing inorganic material products, characterized in that: The bonding structure is an oxide, carbonate, phosphate, orthosilicate, metasilicate, pyrosilicate, tetrasilicate, aluminate, titanate, niobate, borate, bicarbonate, sulfate, hydrogen sulfate, pyrosulfate, persulfate, sulfite, hydrogensulfite, thiosulfate, dithiosulfate, trithiosulfate, peroxymonosulfate, sulfite, phosphate, hydrogenphosphate, dihydrogenphosphate, pyrophosphate, tripolyphosphate, hydrogen metaphosphate, metaphosphate, hydrogen metaphosphate, hypophosphite, trimetaphosphate, tetrametetaphosphate, hexametaphosphate, dimetaphosphate, superphosphate or any combination thereof having one or more metal elements and metalloid elements; The metal element is Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, Al, Ga, In, Sn, Pb, Bi, La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th or U; the metalloid element is B, Si, Ge, As, Sb or Te.

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