Multi-scale inorganic structure and printing manufacturing method thereof

Abstract

The invention discloses a multi-scale inorganic structure and a printing and manufacturing method thereof, and the manufacturing method comprises the following steps: firstly, forming a compact liquid phase by using a cationic precursor and an anionic precursor in the presence of a molecular mediator and a solvent, and extracting printing fluid through a physical separation means; printing forming of a planar structure and a three-dimensional structure is achieved through the molecular mediation liquid-solid conversion and printing technology, then printing aftertreatment is conducted on the printed structure, and forming manufacturing of a multi-scale inorganic structure is achieved. The inorganic structure manufactured by the method is uniform in internal chemical component distribution and high in manufacturing precision; the manufacturing method has wide inorganic salt compatibility, the wide material compatibility enables the design to be more flexible, the most appropriate material system can be selected according to specific application requirements, and then the multi-scale inorganic structure with excellent performance is prepared.

Description

Technical Field

[0001] This invention relates to the field of materials science and technology, and in particular to a multi-scale inorganic structure and its printing manufacturing method. Background Technology

[0002] Inorganic compounds, in their original sense, are compounds that are not related to organisms (a few compounds that are related to organisms are also inorganic compounds, such as water). In contrast to organic compounds, they usually refer to compounds that do not contain carbon. However, they include carbon-containing carbon oxides, carbonates, cyanides, carbides, carboranes, carbonyl metals, alkyl metals, and organic ligand complexes of metals, which are carbon-containing species studied in inorganic chemistry. They are simply referred to as inorganic substances.

[0003] Multiscale inorganic structures refer to multiscale structures formed by inorganic materials through specific chemical or physical processes. Multiscale inorganic structures possess outstanding thermal and chemical stability, high mechanical strength, unique electrical and optical properties, and excellent biocompatibility / biodegradability. They can be used as dielectric structures for high-end electronic devices such as ceramic dielectric capacitors, field-effect transistors, and micro / nano sensors, and can also be applied in fields such as implantable (invasive) medical devices and brain-computer interfaces.

[0004] Printing technology is a manufacturing process that constructs planar and three-dimensional structures by precisely depositing or layering materials. Guided by digital models, this technology deposits or stacks materials as needed according to a pre-set program, ultimately achieving the complete formation of the pre-defined structure. Based on its principles, printing technology can be categorized into various process types, including electrohydraulic inkjet printing (EHD), direct-write printing (DIW), aerosol jet printing (AJP), and photopolymerization printing. Printing technology is suitable for both the precise construction of planar structures and the molding and manufacturing of three-dimensional structures. Due to its unique customization advantages and small-batch production capabilities, printing technology is currently widely used in high-end manufacturing, biomedicine, electronic devices, aerospace, and art design. Printing technology provides a new path for the high-precision manufacturing of multi-scale inorganic structures.

[0005] The current method for manufacturing multi-scale inorganic structures is mainly photopolymerization printing. Inorganic material powder is mixed with resin to form a slurry, which is placed in a material tank. A projected light spot is irradiated on the surface of the slurry according to the slicing data preset by the computer, so that it is cured. After the structure is cured, it is sintered to remove the resin and obtain the desired inorganic structure.

[0006] However, this mainstream approach still faces insurmountable technical bottlenecks. First, traditional methods (such as photopolymerization printing combined with sintering) typically rely on polymer resins as binders or photosensitive matrices. After printing, organic components must be removed through high-temperature heat treatment (usually >1000 °C). This process easily leads to significant shrinkage and cracking of the structure, limiting the molding accuracy and quality. Furthermore, because polymer resins are used as binders or photosensitive matrices, the organic components inside the structure cannot be completely removed after high-temperature heat treatment, resulting in component segregation and reduced structural uniformity. Second, existing technologies have limited material adaptability. Because the particles inside the printed ceramic blank are loose, porous, and low in density, high-temperature sintering is required to densify the particles. Therefore, the temperature of traditional heat treatment processes often reaches thousands of degrees Celsius, making heat-sensitive functional materials such as carbonates (e.g., calcium carbonate decomposes at 900 °C) incompatible with existing technologies. This material limitation makes it difficult to meet the diverse compositional requirements of inorganic structural materials in different application scenarios. Summary of the Invention

[0007] This invention proposes a multi-scale inorganic structure and its printing manufacturing method, which is a multi-scale inorganic structure printing manufacturing method based on molecular mediation leading to the formation of dense liquid phase and liquid-solid transformation. It aims to overcome the problems of high forming temperature, limited heat-sensitive materials, easy shrinkage and cracking of structures, and poor designability of microstructures in traditional processes.

[0008] Biomineralization is the process by which organisms generate inorganic minerals through the regulation of organic macromolecules. Its core mechanism involves molecular recognition and dynamic interactions between organic matter and inorganic ions at the interface, resulting in biominerals with hierarchical structures. Typical examples include the directional assembly of hydroxyapatite within collagen fibers in bones and the hierarchical stacking of calcium carbonate in shells. These biominerals, with their multi-scale structures regulated by organic matter, possess both excellent mechanical properties and biocompatibility, providing inspiration for the preparation of multi-scale inorganic structures.

[0009] This patent mimics the core mechanism of organic macromolecules regulating inorganic ions in biomineralization. Based on molecular-mediated formation of dense liquid phase and molecular-mediated liquid-solid transformation of inorganic compounds, it combines printing technology to realize the manufacturing of multi-scale inorganic structures, overcoming the limitations of traditional multi-scale inorganic structure photopolymerization manufacturing processes, which rely on high temperatures, have poor material compatibility, and are difficult to control in terms of structural precision.

[0010] To achieve the above objectives, the technical solution of the present invention is as follows: A multi-scale inorganic structure and its printing manufacturing method include the following steps: First, cationic and anionic precursors are mixed with molecular mediators and solvents to form a mixture containing a dense liquid phase. Then, the mixture is physically separated to obtain a printing fluid. The printing fluid is then used to print planar / three-dimensional structures. Through liquid-solid transformation of the printing fluid under the action of molecular mediators, the planar / three-dimensional structures are solidified and shaped to form the printed structure. Finally, the printed structure is post-processed to complete the printing and manufacturing of multi-scale inorganic structures.

[0011] Furthermore, the formation process of the molecularly mediated dense liquid phase and the liquid-solid transformation process both include at least one of inorganic ion polymerization, inorganic ion crosslinking, and inorganic ion polymerization-crosslinking reaction; The molecular mediator reversibly breaks the ionic bonds inside the cationic and anionic precursors through coordination, causing the cationic and anionic precursors to transform into a fluid. After the molecular mediator is removed through post-processing, the ionic bonds inside the fluid are remodeled, and the fluid solidifies into an inorganic solid. The molecular mediator plays a role in stabilizing the fluid state of the dense liquid phase and regulating the liquid-solid transformation process in the printing fluid forming process.

[0012] Further, the cation element in the cation precursor is selected from at least one element included in alkali metals, alkaline earth metals, transition metals, main group metals, lanthanides and actinides, and metalloids and nonmetals; wherein, alkali metals include Li, Na, K, Rb, Cs; alkaline earth metals include Be, Mg, Ca, Sr, Ba; transition metals include 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; main group metals include Al, Ga, In, Sn, Pb, Bi; lanthanides and actinides include La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, U; and metalloids and nonmetals include B, Si, Ge, As, Sb, Te. The anion in the anion precursor is selected from at least one of the following ions: hydroxide ions, carbonate ions, thiooxyate ions, carboxylate ions, chloroxyate ions, bromooxyate ions, iodooxyate ions, selenoxyate ions, telluroxyate ions, nitricoxyate ions, arsenoxyate ions, antimonyoxyate ions, silicate ions, germanate ions, stannate ions, leadate ions, and sulfonate ions. The hydroxide ions include OH- - The carbonate ions include CO3²⁻. - HCO3 -The sulfur oxide ions include SO4²⁻. - HSO4 - S2O7² - HS2O7 - S2O8² - HS2O8 - SO3² - HSO3 - S2O3² - S2O6² - HS2O6 - S3O6² - HS3O6 - SO5² - HSO5 - The carboxylate ions include HCOO. - CH3COO - C2O4² - C6H7O7 - C6H6O7² - C6H5O7³ - C4H5O6 - C4H4O6² - The chloroxylate ions include ClO - ClO2 - ClO3 - ClO4 - The bromooxyate ions include BrO. - BrO2 - BrO3 - BrO4 - The iodophosphate ions include IO3-. - IO2 - IO3 - IO4 - IO6 5- The selenoxylate ions include SeO4. 2- SeO3 2- The telluride ions include TeO3. 2- TeO4 2- The nitrogen oxyate ions include N2O2. 2- NO2 - NO3 - The arsenate ions include AsO3. 3- AsO4 3- The antimony oxyate ions include SbO2. - [Sb(OH)6] - The silicate ions include SiO3. 2-SiO4 4- Si2O7 6- The germanate ions include GeO3. 2- GeO4 4- The stannate ion Sn(OH)6 2- The lead-acid ions include PbO3. 2- PbO2 2- The sulfonate ions include R-SO3. - ; The cation precursor is an inorganic salt containing the cation element; The anionic precursor is selected from water and at least one of the following molecules: molecules that generate carbonate ions, molecules that generate thiooxyate ions, molecules that generate carboxylate ions, molecules that generate chloroxyate ions, molecules that generate bromooxyate ions, molecules that generate iodooxyate ions, molecules that generate selenoxyate ions, molecules that generate telluroxyate ions, molecules that generate nitricoxyate ions, molecules that generate arsenoxyate ions, molecules that generate antimonyoxyate ions, molecules that generate silicate ions, molecules that generate germanate ions, molecules that generate stannate ions, molecules that generate lead oxide ions, and molecules that generate sulfonate ions. The molecules that generate carbonate ions include carbon dioxide; the molecules that generate thiooxyate ions include sulfuric acid; the molecules that generate carboxylate ions include formic acid, acetic acid, oxalic acid, citric acid, and tartaric acid; the molecules that generate chloroxyate ions include hypochlorous acid, chlorite, chloric acid, and perchloric acid; the molecules that generate bromooxyate ions include hypobromous acid, bromous acid, bromic acid, and perbromic acid; the molecules that generate iodooxyate ions include hypoiodic acid, iodous acid, iodic acid, and periodic acid; the molecules that generate selenoxyate ions include selenite and selenic acid; the molecules that generate... The molecules that generate telluride ions include tellurite and telluric acid; the molecules that generate nitric acid ions include nitrous acid and nitric acid; the molecules that generate arsenic acid ions include arsenite and arsenic acid; the molecules that generate antimony ions include antimonyous acid and antimonyic acid; the molecules that generate silicate ions include orthosilicic acid and metasilicic acid; the molecules that generate germanate ions include metagermanic acid and orthogermanic acid; the molecules that generate stannate ions include stannic acid; the molecules that generate leadate ions include lead acid and leadite; and the molecules that generate sulfonate ions include sulfonic acid.

[0013] Further, the steps for preparing the printing fluid are as follows: the mixture obtained after molecular mediation leads to the formation of a dense liquid phase is physically separated to separate a gel-like fluid. Then, a solvent is added to the gel-like fluid for dilution and physical separation is performed again. The dilution and separation are repeated 1-50 times to remove impurities. The number of times the dilution and separation are repeated is preferably 5-10 times. After the dilution and separation are completed, the separated fluid is centrifuged and replaced with solvent and stirred for 0-48 h to obtain the printing fluid. The stirring time is preferably 4-12 h. In the mixture, the concentrations of both the anionic and cationic precursors are 0.1 M to 1 M, and the concentration of the molecular mediator is 0.1 M to 10 M. The viscosity of the printing fluid is 1 to 100,000,000 cp, and the mass fraction of the gel-like substance in the printing fluid is 30% to 99%.

[0014] Furthermore, the molecular mediator is selected from at least one of aliphatic amines, nitrogen-containing heterocyclic substances, aromatic and aryl amine mixtures, amides, sulfoxides, phosphorus ligands, carboxylic acids, and polycarboxylate salts. Aliphatic amines include diethylamine and triethylamine; nitrogen-containing heterocyclic substances include pyrrole, pyridine, piperidine, pyrazine, and piperazine; aromatic and aryl amine mixtures include aniline, N-benzyl-N-ethylaniline, N-methylaniline, and N,N-dimethylaniline; amides include formamide, acetamide, and benzamide; sulfoxides include dimethyl sulfoxide and methylphenyl sulfoxide; phosphorus ligands include trioctylphosphine oxide and triphenylphosphine; and carboxylic acids and polycarboxylate salts include polyacrylic acid, sodium oleate, aspartic acid, and glutamic acid. The solvent is selected from at least one of the following: water, alcohols, alkanes, alkenes, alkynes, ethers, ketones, esters, halogenated hydrocarbons, aromatics, nitriles, amides, and sulfoxides. The alcohols include methanol, ethanol, n-propanol, isopropanol, glycerol, n-butanol, and ethylene glycol; the alkanes include cyclohexane, n-hexane, n-pentane, and n-heptane; the alkenes include styrene and cyclohexene; the alkynes include 1-butyne and 1-pentyne; the ethers include tetrahydrofuran and diethyl ether; the ketones include acetone; the esters include ethyl acetate; the halogenated hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride; the aromatics include benzene, toluene, and xylene; the nitriles include acetonitrile; the amides include N,N-dimethylformamide; and the sulfoxides include dimethyl sulfoxide.

[0015] Furthermore, it also includes the step of adding a solvent to the printing fluid to regulate its viscosity.

[0016] Furthermore, before post-processing, the printing mechanism is subjected to room temperature air drying. The air drying conditions are: 0 hours to 7 days at room temperature, until the printed structure is fully air-dried before heat treatment. The post-processing is heat treatment, and the heat treatment conditions are: temperature range of 50 to 1500 ℃, heating and cooling rate of 1 to 30 ℃ / min, temperature control accuracy of 1 ℃, and the heat treatment atmosphere is air or at least one of the following gases: inert gas, oxidizing gas, and reducing gas. The inert gas includes nitrogen and argon; the oxidizing gas includes oxygen; and the reducing gas includes hydrogen, ammonia, and hydrogen sulfide.

[0017] Furthermore, the specific steps for preparing multi-scale inorganic structures include: 1) Configure the printing fluid: 1.1) The cationic precursor M is added to solvent a to obtain solution A; wherein M is a metal cation salt, including calcium chloride, calcium chloride dihydrate, magnesium chloride, copper chloride, or aluminum chloride; wherein solvent a is selected from at least one of the following: water, alcohols, alkanes, alkenes, alkynes, ethers, ketones, esters, halogenated hydrocarbons, aromatics, nitriles, amides, and sulfoxides. The alcohols include methanol, ethanol, n-propanol, isopropanol, glycerol, n-butanol, and ethylene glycol; the alkanes include cyclohexane, n-hexane, n-pentane, and n-heptane; the alkenes include styrene and cyclohexene; the alkynes include styrene and cyclohexene; the alkynes include 1-butyne and 1-pentyne; the ethers include tetrahydrofuran and diethyl ether; the ketones include acetone; the esters include ethyl acetate; the halogenated hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride; the aromatics include benzene, toluene, and xylene; the nitriles include acetonitrile; the amides include N,N-dimethylformamide; the sulfoxides include dimethyl sulfoxide; and in solution A, the concentration of the cationic precursor M is 0.1 M to 1 M. 1.2) Molecular mediator N is added to solution A to obtain solution B; the molecular mediator N is selected from at least one of aliphatic amines, nitrogen-containing heterocyclic substances, aromatic and aryl amine mixtures, amides, sulfoxides, phosphorus ligands, carboxylic acids and polycarboxylate salts; aliphatic amines include diethylamine and triethylamine; nitrogen-containing heterocyclic substances include pyrrole, pyridine, piperidine, pyrazine, and piperazine; aromatic and aryl amine mixtures include aniline, N-benzyl-N-ethylaniline, N-methylaniline, and N,N-dimethylaniline; amides include formamide, acetamide, and benzamide; sulfoxides include dimethyl sulfoxide and methylphenyl sulfoxide; phosphorus ligands include trioctylphosphine oxide and triphenylphosphine; carboxylic acids and polycarboxylate salts include polyacrylic acid, sodium oleate, aspartic acid, and glutamic acid; In solution B, the concentration of the molecular mediator N is 0.1 M to 10 M; in this step, the molecular mediator N is dispersed in solution A, and the molecular mediator N has not yet reacted with the cationic precursor M; 1.3) Anionic precursor O is added to solvent a to obtain solution C; the anionic precursor O is selected from water and at least one of the following: molecules that generate carbonate ions, molecules that generate thiophosphate ions, molecules that generate carboxylate ions, and molecules that generate sulfonate ions; the molecules that generate carbonate ions include carbonic acid; the molecules that generate thiophosphate ions include sulfuric acid; the molecules that generate carboxylate ions include formic acid, acetic acid, oxalic acid, citric acid, and tartaric acid; the molecules that generate chlorate ions include hypochlorous acid, chlorite, chloric acid, and perchloric acid; the molecules that generate bromophosphate ions include hypobromoic acid, bromoic acid, bromic acid, and perbromoic acid; the molecules that generate iodophosphate ions include... The molecules of the ions include hypoiodic acid, iodinium iodate, iodic acid, and periodic acid; the molecules that generate selenoxylate ions include selenite and selenic acid; the molecules that generate tellurite ions include tellurite and telluric acid; the molecules that generate nitric acid ions include nitrous acid and nitric acid; the molecules that generate arsenic acid ions include arsenite and arsenic acid; the molecules that generate antimonyate ions include antimonyite and antimonyic acid; the molecules that generate silicate ions include orthosilicic acid and metasilicic acid; the molecules that generate germanate ions include metagermanic acid and orthogermanic acid; the molecules that generate stannate ions include stannic acid; the molecules that generate leadate ions include lead acid and leadite; and the molecules that generate sulfonate ions include sulfonic acid. In solution C, the concentration of the anionic precursor O is 0.1 M to 1 M; 1.4) Slowly add solution B to solution C (or skip step 1.3 and directly introduce the corresponding reaction gas into solution B obtained in step 1.2, wherein the reaction gas is carbon dioxide, sulfur dioxide or sulfur trioxide), and stir magnetically at room temperature for 10 to 90 minutes to obtain suspension D, which is the preparation of the mixture; 1.5) Centrifuge the mixture, discard the supernatant after centrifugation, and take the gel-like fluid. Use either method one or method two to obtain the printing fluid from the gel-like fluid. Method 1: The mixture obtained after molecular mediation leads to the formation of a dense liquid phase is physically separated to separate a gel-like fluid. Then, solvent b is added to the gel-like fluid for dilution and physical separation is performed again. This dilution and separation process is repeated 1-50 times to remove impurities. The preferred number of dilution and centrifugation cycles is 5-10 times. The centrifugation speed is 1000-20000 rpm and the centrifugation time is 2-60 min. Then, solvent c is used to centrifuge and replace the separated gel-like fluid, and the mixture is stirred for 0-48 h, preferably 4-12 h, to obtain the printing fluid. Method 2: The mixture obtained after molecular mediation leads to the formation of a dense liquid phase is physically separated to separate the gel-like fluid. The separated fluid is centrifuged and stirred for 0-48 h, preferably 4-12 h, using solvent c to obtain the printing fluid. The viscosity of the printing fluid can be adjusted by adding solvent d. The mass fraction of the gel-like substance in the printing fluid is 30%~99%. Solvents b, c, and d are all organic solvents, water, or any one of the components listed in solvent a above. 2) Multi-scale inorganic structure deposition construction and heat treatment Using the printing fluid prepared in step 1) above as the material, printing is performed using printing methods, including electrohydraulic inkjet printing, direct-write printing, and aerosol jet printing. The specific steps of each printing method are as follows: 2.1) Steps for constructing multi-scale inorganic structures using electrofluid deposition: The substrate is positioned on a leveled, heated worktable, and structural deposition is performed using electrohydraulic inkjet printing equipment. The specific operation is as follows: printing fluid is loaded into a syringe, which is then fixed to a support via a syringe clamp. This support is mounted on the Z-axis of a motor. A DC or AC high-voltage power supply is connected to the syringe, providing a high-voltage electric field. A flow pump drives the syringe piston and controls the extrusion flow rate. Under computer control, the power supply adjusts the movement of the motor's Z, X, and Y axes. Under the influence of the high-voltage electric field between the syringe and the substrate, the fluid is refined into a conical jet and gradually ejected. The computer controls the motor's movement, depositing and constructing a multi-scale inorganic structure on the printing substrate. The electrohydraulic inkjet printing equipment parameters are adjusted as follows: electric field strength: 0.5 kV / cm ~ 3 kV / cm; nozzle diameter: 100 ~ 800 μm; nozzle-to-substrate distance: 0.01 ~ 5 mm; worktable temperature: 40 ~ 100 ℃; printing flow rate: 1 ~ 5. μL / min; the speeds of the three motion platforms of the electrohydraulic inkjet printing equipment on the X, Y, and Z axes are 0.1 ~ 20 mm / s, the temperature of the printing environment is 10 ~ 40 ℃, and the relative humidity is 40% ~ 60% to prevent the solvent from evaporating too quickly and to maintain the stability of the solution properties; the relative position between the syringe and the printing substrate and the resulting inorganic structure are monitored by an observation camera to ensure the smooth completion of the process.

[0018] 2.2) Steps for direct-writing sedimentary construction of multi-scale inorganic structures: The substrate is positioned on a leveled, heated worktable, and a direct-write printing system is used for structural deposition. The specific operation is as follows: printing fluid is loaded into a syringe, which is then fixed to a support using a syringe clamp. The support is mounted on the Z-axis of a motor. Under computer control, the drive power supply adjusts the movement of the motor's Z, X, and Y axes. The syringe is connected to a pressure controller and air pump via an air tube. Under the stable air pressure provided by the air pump, the fluid is extruded at a stable flow rate. The computer controls the motor's movement to deposit multi-scale inorganic structures on the printing substrate. The parameters of the direct-write printing system are adjusted as follows: printhead diameter 100~800 μm, printhead-to-substrate distance 0.1~2 mm, worktable temperature 40~100 ℃, printing air pressure 20~150 kPa; X, Y, and Z axis movement speeds of the direct-write printing system 0.1~20 mm / s, ambient temperature 10~40 ℃, relative humidity 40%. 60% of the process is ensured by monitoring the relative position between the syringe and the printing substrate, as well as the resulting inorganic structure, using a camera to ensure successful completion. 2.3) Steps for constructing multi-scale inorganic structures using aerosol jet deposition: The substrate is positioned on a leveled, heatable stage, and the structure is deposited using an aerosol jet printing system. The specific operation involves using a high-frequency (MHz-level) ultrasonic atomizer to convert the fluid into micron-sized droplets. These droplets enter a carrier gas to form an aerosol, which is then transported to the nozzle. A surrounding gas is applied at the nozzle to confine the aerosol into a beam with a diameter of 10 μm to 1 mm, which is then ejected at high speed and deposited on the substrate surface. Under computer control, the drive power supply adjusts the movement of the motor along the Z, X, and Y axes to achieve the deposition of multi-scale inorganic structures. The aerosol jet printing system parameters are adjusted as follows: droplet size: 2 ~ 20 μm; nozzle diameter: 100 ~ 5000 μm; sheath gas flow rate: 20 ~ 1000 sccm; carrier gas flow rate: 10 ~ 100 sccm; nozzle-to-substrate distance: 2 ~ 5 mm; substrate temperature: 10 ~ 100 ℃; printing speed: 1 ~ 50 mm / s; printing fluid viscosity: 1... ~1000 cp; The process is ensured to be completed smoothly by monitoring the relative position between the syringe and the printing substrate and the resulting inorganic structure using an observation camera; 2.4) After the multi-scale inorganic structure is constructed, it can be air-dried at room temperature before heat treatment. The air-drying conditions are: place it at room temperature for 0 hours to 7 days, and then carry out heat treatment after the structure is fully air-dried. The printed structure formed by the printing fluid obtained by printing fluid method one is post-processed by heat treatment using a heat treatment device to polymerize / crosslink inorganic ions, achieving solidification and ultimately obtaining a multi-scale inorganic structure. The heating parameters are set as follows: temperature range 50 ~ 1500 ℃, heating / cooling rate 1 ~ 30 ℃ / min, temperature control accuracy 1 ℃, and the heat treatment atmosphere is air or at least one of the following: inert gas, oxidizing gas, and reducing gas. Inert gases include nitrogen and argon; oxidizing gases include oxygen; and reducing gases include hydrogen, ammonia, and hydrogen sulfide.

[0019] The printed structure formed by the printing fluid obtained by printing fluid method two undergoes post-processing including heat treatment and water immersion. The heat treatment conditions are: temperature range 50 ~ 1500 ℃, heating / cooling rate 1 ~ 30 ℃ / min, temperature control accuracy 1 ℃, and the heat treatment atmosphere is one or a mixture of air, inert gas, oxidizing gas, and reducing gas. The water immersion conditions are: immersing the heat-treated inorganic structure in water for 0 h to 3 days. When preparing multi-scale inorganic structures, byproducts may exist in the printing fluid. When the byproducts have no impact on the performance and application of the obtained multi-scale inorganic structure, the immersion time is 0 h, meaning the post-processing step is only heat treatment, without water immersion.

[0020] This invention also provides a multi-scale inorganic structure manufactured by this method, wherein the composition of the multi-scale inorganic structure includes at least one element selected from alkali metals, alkaline earth metals, transition metals, main group metals, lanthanides and actinides, and metalloids and nonmetals; wherein the alkali metals include Li, Na, K, Rb, and Cs; the alkaline earth metals include Be, Mg, Ca, Sr, and Ba; and the transition metals include Sc, Ti, V, Cr, Mn, and Fe. The elements included are: Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg; main group metals include Al, Ga, In, Sn, Pb, and Bi; lanthanides and actinides include La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, and U; and metalloids and nonmetals include B, Si, Ge, As, Sb, and Te. The multi-scale inorganic structure is any one of the following: oxides, hydroxides, and substances contained in carbonates, thiooxyates, carboxylates, chloroxyates, bromooxyates, iodooxyates, selenoxyates, telluroxyates, nitrooxyates, arsenoxyates, antimonyoxyates, silicates, germanates, stannates, leadates, or sulfonates. The carbonates include carbonates and bicarbonates; the thiosulfates include sulfates, bisulfates, pyrosulfates, persulfates, sulfites, bisulfites, thiosulfates, dithionites, trithionites, permonites, and hyposulfites; the carboxylates include formates, acetates, oxalates, citrates, and tartrates; the chloroxylates include hypochlorites, chlorites, chlorates, and perchlorates; the bromooxyates include hypobromoates, bromates, bromates, and perbromates; and the iodooxyates... The substances include hypoiodide, iodate, iodate, and periodate; the selenoxylate substances include selenate and selenite; the telluroxylate substances include tellurate and tellurite; the nitrogenoxylate substances include hyponitrate, nitrite, and nitrate; the arsenoxylate substances include arsenite and arsenate; the antimonyoxylate substances include antimonite and antimonate; the silicate substances include metasilicate and silicate; the germanate substances include metagermanate and progermanate; and the leadate substances include leadate and leadite. The components of the multi-scale inorganic structure include at least one of the following ions: halide ions, carbon-containing ions, sulfur-containing ions, and nitrogen-containing ions. The halide ions include F - Cl - ,Br -I - The carbon-containing ions include CO3. 2- The sulfur-containing ions include SO42-. 2- The nitrogen-containing ions include NO3-. - .

[0021] Furthermore, the multi-scale inorganic structure includes multi-scale structures with three-dimensional morphology and planar structures, with a size range of 50 nm to 10 cm; The shape of the planar structure includes amorphous, linear, dot-shaped, circular, triangular, square, rectangular, rhomboid, elliptical, quadrilateral, regular polygon, irregular polygon, sector, ring, arc, crescent, star, heart, and composite shapes composed of any of the above shapes; The three-dimensional morphology includes amorphous bodies, sheet-like bodies, cubes, spheres, ellipsoids, hollow spheres, cylinders, cones, frustums, polyhedra, curved surfaces, spindles, needle-like shapes, granular shapes, flower-like shapes, ring-like shapes, spiral shapes, leaf-like shapes, tenon-like shapes, and composite shapes composed of any of the above shapes.

[0022] Furthermore, the atomic spatial arrangement of the multi-scale inorganic structure is either long-range ordered or long-range disordered; The internal microstructure of the multi-scale inorganic structure is one or more of the following: single crystal, polycrystalline, and long-range disordered structure. Both the single crystal and the polycrystalline structure are one or more of the following crystal systems: isometric, tetragonal, trigonal, hexagonal, orthorhombic, and monoclinic.

[0023] The beneficial effects of this invention are: (1) The printing fluid prepared by this invention has excellent rheological properties and component uniformity, and is suitable for high-precision printing technologies such as electrohydraulic inkjet printing and direct-write printing. By precisely controlling the printing parameters and the molecular-mediated liquid-solid conversion process, high-resolution manufacturing up to 50 μm can be achieved, and the chemical composition of the formed structure is uniformly distributed, without the cracking or component segregation problems common in traditional sintering processes, thus ensuring the fidelity of complex and fine structures.

[0024] (2) This invention achieves the molding of inorganic structures through molecular mediation leading to the formation of a dense liquid phase and liquid-solid transformation. This method can complete the curing of inorganic structures at significantly lower temperatures, enabling heat-sensitive inorganic materials such as carbonates (e.g., calcium carbonate) to be processed and molded, greatly expanding the available material systems.

[0025] (3) The molding principle of this invention is based on molecular-mediated liquid-solid transformation. This process does not depend on specific physical or chemical properties of the material, such as photosensitivity, and therefore has a wider range of material adaptability. In addition, the method of this invention shows good compatibility with various combinations of cations and anions. This universality allows the method to freely select and switch material systems according to different application scenarios, thereby preparing high-performance multi-scale inorganic structures. 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 manufacturing principle of the multi-scale inorganic structure of this invention. Figure 2 This is a flowchart of the printing of inorganic structures for this invention; Figure 3 The image shows the XRD pattern of ammonium salt impurities in Example 1 of this invention. Figure 4 Ca in Embodiment 1 of the present invention 2+ CO3 2- Print fluid photographs; Figure 5 Ca in Embodiment 1 of the present invention 2+ CO3 2- Print fluid direct-write line photos; Figure 6 Ca in Embodiment 1 of the present invention 2+ CO3 2- Printing fluid-direct-write printing of 3D structure photographs; Figure 7 Ca in Embodiment 1 of the present invention 2+ CO3 2- Microscopic photograph of lines printed using fluid direct-write printing; Figure 8 Ca in Embodiment 1 of the present invention 2+ CO3 2 XRD images of fluid-cured (500℃, 2 h) samples were printed; Figure 9 Ca in Embodiment 1 of the present invention 2+ CO3 2- Electron micrographs of the printed fluid-cured (500℃, 2 h) sample; Figure 10Ca in Embodiment 3 of the present invention 2+ CO3 2- Print fluid photographs; Figure 11 Ca in Embodiment 3 of the present invention 2+ CO3 2- Printing fluid aerosols to create line photos; Figure 12 Ca in Embodiment 3 of the present invention 2+ CO3 2- Microscopic image of lines printed by aerosol jet printing; Figure 13 Ca in Embodiment 3 of the present invention 2+ CO3 2- Electron micrographs of the cured fluid aerosol-printed lines (50℃, 0.5 h); Figure 14 Ca in Embodiment 4 of the present invention 2+ CO3 2- Printing fluid electrohydraulic inkjet line photos; Figure 15 Ca in Embodiment 5 of the present invention 2+ SO4 2- Print fluid photographs; Figure 16 Ca in Embodiment 5 of the present invention 2+ SO4 2- Print fluid direct-write line photos; Figure 17 Ca in Embodiment 5 of the present invention 2+ SO4 2- Printing fluid-direct-write printing of 3D structure photographs; Figure 18 Ca in Embodiment 5 of the present invention 2+ SO4 2- Microscopic photograph of lines printed using fluid direct-write printing; Figure 19 Ca in Embodiment 5 of the present invention 2+ SO4 2- XRD images of fluid-cured (120℃, 3 h) samples were printed; Figure 20 Ca in Embodiment 5 of the present invention 2+ SO4 2- Electron micrographs of the printed fluid-cured sample (120℃, 3 h); Figure 21 Ca in Embodiment 6 of the present invention 2+ OH - Print fluid photographs; Figure 22 Ca in Embodiment 6 of the present invention 2+ OH - Print fluid direct-write line photos; Figure 23 Ca in Embodiment 6 of the present invention 2+ OH - Printing fluid direct-write printing of 3D structure photos Figure 24 Ca in Embodiment 6 of the present invention 2+ OH - Microscopic photograph of lines printed using fluid direct-write printing; Figure 25 Ca in Embodiment 6 of the present invention 2+ OH - XRD images of fluid-cured samples (100℃, 1 h) were printed; Figure 26 Ca in Embodiment 6 of the present invention 2+ OH - Electron micrographs of the printed fluid-cured (100℃, 1 h) sample; Figure 27 Al in Embodiment 7 of the present invention 3+ OH - Print fluid photographs; Figure 28 Al in Embodiment 7 of the present invention 3+ OH - Print fluid direct-write line photos; Figure 29 Al in Embodiment 7 of the present invention 3+ OH - Printing fluid-direct-write printing of 3D structure photographs; Figure 30 Al in Embodiment 7 of the present invention 3+ OH - Microscopic photograph of lines printed using fluid direct-write printing; Figure 31 Al in Embodiment 7 of the present invention 3+ OH - XRD images of fluid-cured (1500℃, 2 h) samples were printed; Figure 32 Al in Embodiment 7 of the present invention 3+ OH - Electron micrographs of the printed fluid-cured (1500℃, 2 h) sample; Figure 33 Al in Embodiment 8 of the present invention 3+ OH - Photographs of the printing process using electrohydraulic inkjet printing; Figure 34 Al in Embodiment 8 of the present invention 3+ OH - Printing fluid electrohydraulic inkjet line photos; Figure 35 Cu in Example 9 of the present invention 2+ CO3 2- Print fluid photographs; Figure 36 Cu in Example 9 of the present invention 2+ CO3 2- Print fluid direct-write line photos; Figure 37 Cu in Example 9 of the present invention 2+ CO3 2-- Printing fluid-direct-write printing of 3D structure photographs; Figure 38 Cu in Example 9 of the present invention 2+ CO3 2-- Microscopic photograph of lines printed using fluid direct-write printing; Figure 39 Cu in Example 9 of the present invention 2+ CO3 2-- XRD images of fluid-cured (120℃, 2 h) samples were printed; Figure 40 Cu in Example 9 of the present invention 2+ CO3 2-- Electron micrographs of the printed fluid-cured sample (120℃, 2 h); Figure 41 This is a schematic diagram of the direct-write printing device of the present invention; Figure 42 This is a schematic diagram of the electrohydraulic inkjet printing equipment of the present invention; Figure 43 This is a schematic diagram of the aerosol jet printing equipment of the present invention.

[0028] In the picture: 1. Printer nozzle; 2. Printing substrate; 3. Air tube; 4. Gas pressure controller; 5. Air pump; 6. Flow pump; 7. Atomizer. Detailed Implementation

[0029] 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.

[0030] The principle of this application: This invention provides a method for printing and manufacturing multi-scale inorganic structures, and uses this method to manufacture multi-scale inorganic structures. For example... Figure 1 , Figure 2 The diagram illustrates the manufacturing process of the multi-scale inorganic structure of this invention. During manufacturing, cationic and anionic precursors first form a dense liquid phase in the presence of a molecular mediator and solvent. The printing fluid (also known as dense fluid) is extracted through physical separation. This fluid is then deposited onto a substrate using molecularly mediated liquid-solid conversion and printing technology. The printing process utilizes a precisely controlled motor to extrude the printing fluid through a fine nozzle, forming an "H"-shaped inorganic structure as shown in the diagram. Subsequently, the printed inorganic structure undergoes post-printing processing to form a high-precision multi-scale inorganic structure with uniform composition and a dense structure. The manufacturing principle of the multi-scale inorganic structure is shown in the diagram. Figure 1 As shown.

[0031] The printing equipment used in this embodiment is as follows: Direct-write printing equipment such as Figure 41 As shown, the direct-write printing equipment includes a printhead 1, a printing substrate 2, an air pipe 3, a gas pressure controller 4, and an air pump 5. The printhead 1 is located above the printing substrate 2 and can move laterally above the printing substrate by a translation mechanism. The gas pressure controller 4 and the air pump 5 are placed on the outside of the equipment body, adjacent to each other. One end of the air pipe 3 is connected to the gas pressure controller 4, and the other end extends to the equipment body and is connected to the printhead 1. The air pump 5 is connected to the gas pressure controller 4 through a pipeline to provide the equipment with the compressed air source required for printing. The gas pressure controller 4 is connected to the printhead 1 through the air pipe 3 to deliver gas at a stable pressure to the printhead, and is used to control the on / off state of the gas pressure and the magnitude of the printing gas pressure. The printhead 1 and the printing substrate 2 are not directly physically connected; they maintain a certain distance. The printhead completes the printing operation above the printing substrate to obtain multi-scale inorganic structures.

[0032] Electron printing equipment such as Figure 42As shown, the electrohydrodynamic printing equipment includes a printhead 1, a printing substrate 2, and a flow pump 6. The printhead 1 is located above the printing substrate 2, with a certain distance between them, providing space for the electric field to act on the electrohydrodynamic jet. The printhead can move above the substrate. The flow pump 6 is connected to the printhead 1 through a pipeline, precisely controlling the flow rate of the printing material and providing a stable feed for the electrohydrodynamic jet. There is no direct physical connection between the printhead 1 and the printing substrate 2; they are respectively connected to the two poles of a high-voltage power supply to form an electric field that drives the electrohydrodynamic jet within the printhead, completing the printing process on the printing substrate.

[0033] Aerosol jet printing equipment such as Figure 43 As shown, the aerosol jet printing equipment includes an atomizer 7, a print head 1, a printing substrate 2, a gas pressure controller 4, an air pipe 2, and an air pump 5. The atomizer 7 and printhead 1 are integrated and mounted on top of the equipment, directly above the printing substrate 2. The printhead 1 can move above the printing substrate 2. A gas pressure controller 4 is located at the front of the main body of the equipment, and an air pump 5 is placed on the outside of the equipment. The air pump 5 is connected to the gas pressure controller 4 via an air pipe 3. The output of the gas pressure controller 4 is then connected to the atomizer 7 and the printhead 1 via an air pipe. The air pump 6 provides a stable air source for the equipment; the gas pressure controller 4 can precisely control the pressure of the ejected gas. After the atomizer 1 atomizes the printing material gas, it is delivered to the printhead 2, where a stable aerosol jet is formed under the action of air pressure and airflow, and sprayed onto the printing substrate 3 below to complete the deposition and molding process. The aforementioned gas pressure controller 4 is a conventional device, and its specific process and principle of controlling air pressure will not be elaborated here.

[0034] Example 1: Ca 2+ CO3 2- The steps of direct-write printing of fluids and their multi-scale inorganic structures include: First step, take Ca 2+ CO3 2- Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 0.735 g of calcium chloride dihydrate (cationic precursor) and add it to 50 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of calcium chloride dihydrate is 0.1 M; 1.2) Add 25.2 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 5 M; 1.3) Carbon dioxide gas (anion precursor) was introduced into solution A and magnetically stirred at room temperature. The gas flow rate was 80 mL / min and the aeration and stirring time was 30 min, resulting in suspension D as a mixture. 1.4) Centrifuge the mixture at 5000 rpm for 10 min. After separation, discard the supernatant and collect the gel-like fluid. 1.5) Dilute the obtained gel-like fluid with a solvent consisting of 15 mL ethanol and 15 mL water. After dilution, centrifuge at 5000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like fluid. Repeat this step 5 times to remove ammonium salt impurities. The X-ray diffraction peaks of the impurities are as follows: Figure 3 As shown, the Ca obtained 2+ CO3 2- Printing fluids such as Figure 4 As shown; 1.6) Add 2% by mass of glycerol to the obtained printing fluid to adjust the viscosity; The second step is to position the substrate on a leveled, heated stage. Printing fluid is then injected into the syringe, using methods such as... Figure 41 The direct-write printing equipment shown was used for structural printing. The relevant printing program was input into the printing equipment, and the equipment parameters were set as follows: extrusion nozzle diameter 800 μm, nozzle-to-substrate / printed structure distance 0.1 mm, stage temperature 20 ℃; printing air pressure 200 kPa, X-axis, Y-axis, and Z-axis speeds 0.1 mm / s; ambient temperature 10 ℃, relative humidity 40%. A camera was used to monitor the relative position between the syringe and the printing substrate, as well as the resulting structure, to ensure successful completion of the process. The printed structure is shown below. Figure 5 , Figure 6 As shown; The third step is to heat-treat the obtained structure in an air atmosphere at a temperature of 500 ℃, with a heating / cooling rate of 30 ℃ / min and a holding time of 2 h, in order to form the desired structure.

[0035] Through the above steps, inorganic cylindrical structures and inorganic linear structures were successfully prepared. The inorganic linear structure has a linewidth of approximately 550 μm. Figure 7 As shown in the figure. The X-ray diffraction pattern shows that the intensity of the X-ray diffraction peaks of the obtained inorganic linear structure matches that of calcium carbonate, proving that the inorganic linear structure is a mixture containing calcium carbonate. Figure 8 As shown; scanning electron microscopy confirms that the material has a uniform and dense structure, such as Figure 9 As shown, these structures exhibit good consistency and repeatability, verifying the effectiveness and feasibility of the technical solution.

[0036] Comparative example: Ca 2+ CO3 2- The steps of direct-write printing of fluids and their multi-scale inorganic structures include: First step, take Ca 2+ CO3 2- Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 0.735 g of calcium chloride dihydrate and add it to 50 mL of ethanol to obtain solution A, in which the concentration of calcium chloride dihydrate is 0.1 M; 1.2) Carbon dioxide gas was introduced into solution A and magnetically stirred at room temperature. The gas flow rate was 80 mL / min, and the aeration and stirring time was 30 min. Suspension D could not be obtained. Because a dense fluid could not be formed due to the lack of a molecular mediator, the printing and manufacturing of multi-scale inorganic structures could not be achieved.

[0037] Example 2: Ca 2+ CO3 2- The steps of direct-write printing of fluids and their multi-scale inorganic structures include: First step, take Ca 2+ CO3 2- Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 0.735 g of calcium chloride dihydrate (cationic precursor) and add it to 50 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of calcium chloride dihydrate is 0.1 M; 1.2) Add 25.2 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 5 M; 1.3) Carbon dioxide gas (anion precursor) was introduced into solution A and magnetically stirred at room temperature. The gas flow rate was 80 mL / min and the aeration and stirring time was 30 min, resulting in suspension D as a mixture. 1.4) Centrifuge the mixture at 5000 rpm for 10 min. Discard the supernatant after separation and use the gel-like fluid as Ca. 2+ CO3 2- Printing fluid; 1.5) Add 2% by mass of glycerol to the obtained printing fluid to adjust the viscosity; The second step is to position the substrate on a leveled, heated stage. Printing fluid is then injected into the syringe, using methods such as... Figure 41The direct-write printing equipment shown was used for structural printing. The relevant printing program was input into the printing equipment, and the equipment parameters were set as follows: extrusion nozzle diameter 800 μm, nozzle-to-substrate / printed structure distance 0.1 mm, stage temperature 20 ℃; printing air pressure 200 kPa, X-axis, Y-axis, and Z-axis speeds 0.1 mm / s; printing environment temperature 10 ℃, relative humidity 40%. A camera was used to monitor the relative position between the syringe and the printing substrate, as well as the resulting structure, to ensure successful process completion. The third step is to heat-treat the obtained structure in an air atmosphere at a temperature of 500 ℃, with a heating and cooling rate of 30 ℃ / min and a holding time of 2 h to form the desired structure. After heat treatment, the structure is immersed in water for 3 days to remove impurities.

[0038] Through the above steps, inorganic cylindrical and inorganic linear structures were successfully prepared. X-ray diffraction patterns showed that the peak intensities of the obtained inorganic linear structures were consistent with those of calcium carbonate, proving that the inorganic linear structures were composed of a calcium carbonate-containing mixture. Scanning electron microscopy confirmed that the material structure was uniform and dense. These structures exhibited good consistency and repeatability, verifying the effectiveness and feasibility of the proposed technique.

[0039] Example 3: Ca 2+ CO3 2- The steps of aerosol jet printing manufacturing of fluids and their multi-scale inorganic structures include: First step, take Ca 2+ CO3 2- Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 2.94 g of calcium chloride dihydrate (cationic precursor) and add it to 50 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of calcium chloride dihydrate is 0.4 M; 1.2) Add 50.59 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 10 M; 1.3) Carbon dioxide gas (anion precursor) was introduced into solution A and magnetically stirred at room temperature. The gas flow rate was 50 mL / min and the aeration and stirring time was 30 min, resulting in suspension D as a mixture. 1.4) Centrifuge the mixture at 5000 rpm for 10 min. After separation, discard the supernatant and collect the gel-like fluid. 1.5) Dilute the obtained gel-like fluid with a solvent consisting of 15 mL ethanol and 15 mL water. After dilution, centrifuge at 5000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like fluid. Repeat this step 50 times to remove impurities. Then, centrifuge and stir the resulting fluid with propylene glycol for 12 h to obtain Ca. 2+ CO3 2- Printing fluids such as Figure 10 As shown; 1.6) Add 30% by volume of ethanol to the obtained printing fluid to adjust the viscosity; The second step is to position the substrate on a leveled, heatable worktable, using methods such as... Figure 43 The aerosol printing equipment shown is used for structural printing. A high-frequency (MHz-level) ultrasonic atomizer is used to convert the printing fluid into micron-sized droplets. These droplets enter the carrier gas to form an aerosol, which is then transported to the nozzle. An surrounding gas is applied at the nozzle to confine the aerosol into a beam, which is then ejected at high speed and deposited on the substrate surface. The equipment parameters are adjusted as follows: droplet size 1 μm; nozzle diameter 100 μm; sheath gas flow rate 20 sccm; carrier gas flow rate 10 sccm; distance between the nozzle and the printing substrate 5 mm; printing substrate temperature 100 ℃; ambient relative humidity 60%; X-axis, Y-axis, and Z-axis speeds are all 0.1 mm / s. A camera monitors the relative position between the syringe and the printing substrate, as well as the resulting inorganic structure, to ensure successful process completion. The printed structure is shown below. Figure 11 As shown; The third step is to heat-treat the obtained structure in an air atmosphere at a temperature of 50 ℃, with a heating / cooling rate of 1 ℃ / min and a holding time of 0.5 h, in order to form the desired structure.

[0040] Through the above steps, an inorganic linear structure with a linewidth of approximately 50 μm was successfully prepared, such as... Figure 12 As shown. X-ray diffraction experiments confirmed that the obtained inorganic linear structure is a calcium carbonate-containing compound with long-range ordered atomic spatial arrangement and a spherical surface morphology, as shown. Figure 13 As shown. The inorganic structures prepared in this embodiment exhibit excellent uniformity and accuracy. The successful preparation of these structures further confirms the applicability and feasibility of the technical solution.

[0041] Example 4: Ca 2+ CO3 2- The steps of electrofluid printing manufacturing of fluids and their multi-scale inorganic structures include: First step, take Ca 2+ CO3 2-Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 6.9 g of calcium chloride dihydrate (cationic precursor) and add it to 50 mL of isopropanol (organic solvent) to obtain solution A, in which the concentration of calcium chloride dihydrate is 1M; 1.2) 14.63 g of diethylamine (molecular mediator) was added to solution A to obtain solution B, in which the concentration of diethylamine was 4 M; 1.3) Carbon dioxide gas (anion precursor) was introduced into solution A and magnetically stirred at room temperature. The gas flow rate was 50 mL / min and the aeration and stirring time was 30 min, resulting in suspension D as a mixture. 1.4) Centrifuge the mixture at 6000 rpm for 10 min. After separation, discard the supernatant and collect the gel-like fluid. 1.5) Dilute the obtained gel-like fluid with a solvent prepared by mixing 15 mL isopropanol and 15 mL water. After dispersion, centrifuge at 5000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like substance. Repeat this step three times to remove impurities, thus obtaining Ca. 2+ CO3 2- Printing fluid; 1.6) Add 5 mL of isopropanol to the obtained printing fluid to adjust the viscosity; The second step involves positioning the substrate on a leveled, heatable stage; injecting the printing fluid into the syringe, using methods such as... Figure 42 The electrohydraulic inkjet printing equipment shown was used for structural printing. The relevant printing program was input into the printing equipment, and the equipment parameters were set as follows: electric field strength 3kV / cm, nozzle diameter 800 μm, distance between nozzle and substrate / printed structure 5 mm, stage temperature 20℃, printing flow rate 5 μL / min, X-axis, Y-axis, and Z-axis speeds all 20 mm / s, ambient temperature 20℃, relative humidity 40%. A camera was used to monitor the relative position between the syringe and the printing substrate, as well as the resulting structure, to ensure successful completion of the process. The printed structure is shown below. Figure 14 As shown; The third step is to heat-treat the obtained structure in an argon atmosphere at a temperature of 600 ℃, with a heating / cooling rate of 1 ℃ / min and a holding time of 2 h, in order to form the desired structure.

[0042] Through the above steps, an inorganic linear structure with a line length of approximately 40 mm and a linewidth of approximately 400 μm was successfully prepared. X-ray diffraction experiments verified that the obtained inorganic linear structure is composed of a calcium carbonate-containing compound, with a long-range ordered atomic spatial arrangement. The inorganic structure prepared in this embodiment exhibits excellent uniformity and accuracy.

[0043] The successful fabrication of these structures further confirms the applicability and feasibility of the technical solution.

[0044] Example 5: Ca 2+ SO4 2- The steps of direct-write printing of fluids and their multi-scale inorganic structures include: First step, take Ca 2+ SO4 2- Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 0.735 g of calcium chloride dihydrate (cationic precursor) and add it to 50 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of calcium chloride dihydrate is 0.1 M; 1.2) Add 0.51 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 0.1 M; 1.3) 0.49 g of sulfuric acid (anionic precursor) was added to 50 mL of ethanol (organic solvent) to obtain solution C, in which the concentration of sulfuric acid was 0.1 M; 1.4) Add solution B to solution C and stir magnetically for 40 min at room temperature to obtain suspension D as a mixture; 1.5) Centrifuge the mixture at 10,000 rpm for 10 min. After separation, discard the supernatant and collect the gel-like fluid. 1.6) Dilute the obtained gel-like fluid with a solvent prepared by mixing 15 mL of ethanol and 15 mL of water. After dilution, centrifuge at 10000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like fluid. Repeat this step three times to remove impurities, thus obtaining the Ca. 2+ SO4 2- Printing fluids such as Figure 15 As shown; The second step involves positioning the glass substrate on a leveled, heated stage; injecting the printing fluid into the syringe and using a direct-write printing device to print the structure; inputting the relevant printing program into the printing equipment with the following parameters: extrusion nozzle diameter 100μm, nozzle-to-substrate / printed structure distance 2 mm, stage temperature 300 ℃; printing air pressure 5 kPa, X-axis, Y-axis, and Z-axis speeds 20 mm / s; ambient temperature 40 ℃, relative humidity 60%. A camera monitors the relative position between the syringe and the printing substrate, as well as the resulting structure, to ensure successful completion of the process. The printed structure is shown below. Figure 16 , Figure 17 As shown; The third step is to air-dry the structure at room temperature before heat treatment. The air-drying conditions are: place it at room temperature for 7 days. After that, the obtained structure is heat-treated in air atmosphere, the temperature is set to 120 ℃, the heating and cooling rate is 3 ℃ / min, and the holding time is 3 h, so as to form the desired structure. Through the above steps, inorganic wire structures and inorganic cylindrical structures were successfully prepared. The linewidth of the inorganic wire structure was approximately 560 μm. Figure 18 As shown. X-ray diffraction experiments confirmed that the obtained inorganic structure is composed of calcium sulfate, with a long-range ordered atomic spatial arrangement, as shown... Figure 19 As shown, the microstructure is columnar, such as Figure 20 As shown, these structures exhibit good morphological consistency and repeatability, verifying the effectiveness and feasibility of the proposed technical solution.

[0045] Example 6: Ca 2+ OH - The steps of direct-write printing of fluids and their multi-scale inorganic structures include: First step, take Ca 2+ OH - Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 1.47 g of calcium chloride dihydrate (cationic precursor) and add it to 20 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of calcium chloride dihydrate is 0.5 M; 1.2) Add 10.95 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 5.4 M; 1.3) Add 0.18 g of water (anionic precursor) to solution B and stir magnetically for 20 min at room temperature to obtain suspension D as a mixture; 1.4) Centrifuge the mixture obtained in the first step at a speed of 8000 rpm for 10 min. After separation, discard the supernatant and take the gel-like fluid. 1.5) Dilute the obtained gel-like fluid with a solvent prepared by mixing 15 mL of ethanol and 15 mL of water. After dilution, centrifuge at 8000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like fluid. Repeat this step three times to remove impurities, thus obtaining the Ca. 2+ OH - Printing fluids such as Figure 21 As shown; 1.6) Add 4% by mass of glycerol to the obtained printing fluid to adjust the viscosity; The second step involves positioning the glass substrate on a leveled, heated stage; injecting the printing fluid into the syringe and using a direct-write printing device to print the structure; inputting the relevant printing program into the printing equipment with the following parameters: nozzle diameter 500 μm, nozzle-to-substrate / printed structure distance 0.5 mm, stage temperature 60 ℃; printing air pressure 100 kPa, X, Y, and Z axis speeds 5 mm / s; ambient temperature 20 ℃, relative humidity 45%. A camera monitors the relative position between the syringe and the printing substrate, as well as the resulting structure, to ensure successful completion of the process. The printed structure is shown below. Figure 22 , Figure 23 As shown; The third step is to air-dry the structure at room temperature before heat treatment. The air-drying conditions are: place it at room temperature for 12 hours, and then heat-treat the resulting structure. The heat treatment atmosphere is air, the temperature is set to 100 ℃, the heating and cooling rate is 1℃ / min, and the holding time is 1 h, so as to form the desired structure. Through the above steps, inorganic wire structures and inorganic cylindrical structures were successfully prepared. The linewidth of the inorganic wire structure was approximately 635 μm. Figure 24 As shown. X-ray diffraction experiments confirmed that the obtained inorganic structure is composed of calcium hydroxide, with a long-range ordered atomic spatial arrangement and a hexagonal crystal system. Figure 25 As shown, its microstructure is a sheet-like structure, such as... Figure 26 As shown.

[0046] Example 7: Al 3+ OH - The steps of direct-write printing of fluids and their multi-scale inorganic structures include: First step, take Al 3+ OH - Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 0.534 g of aluminum chloride (cationic precursor) and add it to 20 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of aluminum chloride is 0.2 M; 1.2) Add 0.81 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 0.4 M; 1.3) Add 0.216 g of water (anionic precursor) to the solution and stir magnetically for 20 min at room temperature to obtain suspension D as a mixture; 1.4) Centrifuge the mixture at 8000 rpm for 10 min. After separation, discard the supernatant and collect the gel-like fluid. 1.5) Dilute the obtained gel-like fluid with a solvent consisting of 15 mL ethanol and 15 mL water. After dilution, centrifuge at 8000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like fluid. Repeat this step once to remove impurities, thus obtaining Al. 3+ OH - Printing fluids such as Figure 27 As shown; 1.6) Add 2% by mass of glycerol to the obtained printing fluid to adjust the viscosity; The second step involves positioning the glass substrate on a leveled, heated worktable; injecting the printing fluid into the syringe and using a direct-write printing device to print the structure; inputting the relevant printing program into the printing equipment with the following parameters: nozzle diameter 500 μm, nozzle-to-substrate / printed structure distance 1 mm, worktable temperature 25 ℃; printing air pressure 60 kPa, X, Y, and Z axis speeds 1 mm / s; ambient temperature 25 ℃, relative humidity 60%. A camera monitors the relative position between the syringe and the printing substrate, as well as the resulting structure, to ensure successful completion of the process. The printed structure is shown below. Figure 28 , Figure 29 As shown; The third step is to heat-treat the obtained structure in an air atmosphere at a temperature of 1500 ℃, with a heating / cooling rate of 5 ℃ / min and a holding time of 2 h, in order to form the desired structure.

[0047] Through the above steps, Al-containing materials were successfully prepared. 3+ OH - The inorganic wire structure and inorganic cylindrical structure, the inorganic wire structure has a linewidth of approximately 1 mm, such as Figure 30 As shown. X-ray diffraction experiments verified that the spatial arrangement of the inorganic atoms was long-range disorder, as... Figure 31 As shown, the surface morphology is spherical, such as Figure 32As shown.

[0048] Example 8: Al 3+ OH - The steps of electrofluid printing manufacturing of fluids and their multi-scale inorganic structures include: First step, take Al 3+ OH - The printing fluid, used as a printing material, involves the following steps: 1.1) Take 0.534 g of aluminum chloride (cationic precursor) and add it to 20 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of aluminum chloride is 0.2 M; 1.2) Add 0.81 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 0.4 M; 1.3) Add 0.216 g of water (anionic precursor) to the solution and stir magnetically for 20 min at room temperature to obtain suspension D as a mixture; 1.4) Centrifuge the mixture at 6000 rpm for 10 min. After separation, discard the supernatant and collect the gel-like fluid. 1.5) Dilute the obtained gel-like fluid with a solvent prepared by mixing 15 mL of ethanol and 15 mL of water. After dilution, centrifuge at 6000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like fluid. Repeat this step three times to remove impurities. Then, add 3 mL of propylene glycol to the obtained fluid, centrifuge to replace the precipitate, and stir for 4 h to obtain Al. 3+ OH - Printing fluid; 1.6) Add 5 mL of ethanol to the obtained printing fluid to adjust the viscosity; The second step involves positioning the substrate on a leveled, heatable worktable; injecting the printing fluid into the syringe and using electrohydraulic inkjet printing equipment to print the structure; inputting the relevant printing program into the printing equipment with the following parameters: electric field strength of 0.5 kV / cm, nozzle diameter of 100 μm, distance between the nozzle and the substrate / printed structure of 0.1 mm, worktable temperature of 300 ℃, fluid flow rate of 1 μL / min, X, Y, and Z axis speeds of 0.1 mm / s, ambient temperature of 40 ℃, and relative humidity of 60%. A camera is used to monitor the relative position between the syringe and the printed substrate, as well as the resulting structure, to ensure successful completion of the process. The printing process is as follows: Figure 33 As shown, the printed structure is as follows Figure 34 As shown; The third step is to heat-treat the obtained structure in an air atmosphere at a temperature of 180 ℃, with a heating / cooling rate of 5 ℃ / min and a holding time of 2 h, in order to form the desired structure. Through the above steps, Al-containing materials were successfully prepared. 3+ OH - An inorganic wire structure with a length of approximately 40 mm and a width of approximately 800 μm was obtained. X-ray diffraction experiments confirmed that the atomic spatial arrangement of the obtained inorganic structure was long-range disorder.

[0049] Example 9: Cu 2+ CO3 2- The steps of direct-write printing of fluids and their multi-scale inorganic structures include: First step, take Cu 2+ CO3 2- Printing fluids, using them as materials for printing, involves the following steps: 1.1) Take 3.36 g of copper chloride (cationic precursor) and add it to 50 mL of ethanol (organic solvent) to obtain solution A, in which the concentration of copper chloride is 0.5 M; 1.2) Add 2.52 g of triethylamine (molecular mediator) to solution A to obtain solution B, in which the concentration of triethylamine is 0.5 M; 1.3) Carbon dioxide gas (anion precursor) was introduced into solution A and magnetically stirred at room temperature. The gas flow rate was 80 mL / min and the aeration and stirring time was 30 min, resulting in suspension D as a mixture. 1.4) Centrifuge the mixture at 8000 rpm for 10 min. After separation, discard the supernatant and collect the gel-like fluid. 1.5) Dilute the obtained gel-like fluid with a solvent prepared by mixing 15 mL of ethanol and 15 mL of water. After dispersion, centrifuge at 8000 rpm for 10 min. Discard the supernatant after separation and collect the gel-like fluid. Repeat this step three times to remove impurities, thus obtaining Cu. 2+ CO3 2- Printing fluids such as Figure 35 As shown; 1.6) Add 2% by mass of glycerol to the obtained printing fluid to adjust the viscosity; The second step involves positioning the glass substrate on a leveled, heated stage; injecting the printing fluid into the syringe and using a direct-write printing device to print the structure; inputting the relevant printing program into the printing equipment with the following parameters: nozzle diameter 500 μm, nozzle-to-substrate / printed structure distance 0.5 mm, stage temperature 80 ℃; printing air pressure 100 kPa, X, Y, and Z axis speeds 10 mm / s; ambient temperature 25 ℃, relative humidity 40%. A camera monitors the relative position between the syringe and the printing substrate, as well as the resulting structure, to ensure successful completion of the process. The printed structure is shown below. Figure 36 , Figure 37 As shown; The third step is to heat-treat the obtained structure in an air atmosphere at a temperature of 120 ℃, with a heating / cooling rate of 1 ℃ / min and a holding time of 2 h, in order to form the desired structure. Through the above steps, inorganic linear structures and inorganic cylindrical structures were successfully prepared. The inorganic linear structure has a linewidth of approximately 700 μm. Figure 38 As shown. X-ray diffraction experiments confirmed that the obtained inorganic structure is Cu₂(OH)₃Cl, with a long-range ordered atomic spatial arrangement, as shown. Figure 39 As shown, the microscopic morphology is spherical, such as Figure 40 As shown.

[0050] 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. A method for printing and manufacturing multi-scale inorganic structures, characterized in that, Includes the following steps: First, cationic and anionic precursors are mixed with molecular mediators and solvents to form a mixture containing a dense liquid phase. Then, the mixture is physically separated to obtain a printing fluid. The printing fluid is then used to print planar / three-dimensional structures. Through liquid-solid transformation of the printing fluid under the action of molecular mediators, the planar / three-dimensional structures are solidified and shaped to form the printed structure. Finally, the printed structure is post-processed to complete the printing and manufacturing of multi-scale inorganic structures.

2. The method for printing and manufacturing multi-scale inorganic structures according to claim 1, characterized in that, The formation of the molecularly mediated dense liquid phase and the liquid-solid transformation process both include at least one of inorganic ion polymerization, inorganic ion crosslinking, and inorganic ion polymerization-crosslinking reaction; The molecular mediator reversibly breaks the ionic bonds inside the cationic and anionic precursors through coordination, causing the cationic and anionic precursors to transform into a fluid. After the molecular mediator is removed through post-processing, the ionic bonds inside the fluid are remodeled, and the fluid solidifies into an inorganic solid. The molecular mediator plays a role in stabilizing the fluid state of the dense liquid phase and regulating the liquid-solid transformation process in the printing fluid forming process.

3. The method for printing and manufacturing multi-scale inorganic structures according to claim 1, characterized in that, The cation element in the cation precursor is selected from at least one element included in alkali metals, alkaline earth metals, transition metals, main group metals, lanthanides and actinides, and metalloids and nonmetals; wherein, alkali metals include Li, Na, K, Rb, Cs; alkaline earth metals include Be, Mg, Ca, Sr, Ba; transition metals include 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; main group metals include Al, Ga, In, Sn, Pb, Bi; lanthanides and actinides include La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, U; and metalloids and nonmetals include B, Si, Ge, As, Sb, Te. The anion in the anion precursor is selected from at least one of the following ions: hydroxide ions, carbonate ions, thiooxyate ions, carboxylate ions, chloroxyate ions, bromooxyate ions, iodooxyate ions, selenoxyate ions, telluroxyate ions, nitricoxyate ions, arsenoxyate ions, antimonyoxyate ions, silicate ions, germanate ions, stannate ions, leadate ions, and sulfonate ions. The hydroxide ions include OH- - The carbonate ions include CO3²⁻. - HCO3 - The sulfur oxide ions include SO4²⁻. - HSO4 - S2O7² - HS2O7 - S2O8² - HS2O8 - SO3² - HSO3 - S2O3² - S2O6² - HS2O6 - S3O6² - HS3O6 - SO5² - HSO5 - The carboxylate ions include HCOO. - CH3COO - C2O4² - C6H7O7 - C6H6O7² - C6H5O7³ - C4H5O6 - C4H4O6² - The chloroxylate ions include ClO - ClO2 - ClO3 - ClO4 - The bromooxyate ions include BrO. - BrO2 - BrO3 - BrO4 - The iodophosphate ions include IO3-. - IO2 - IO3 - IO4 - IO6 5- The selenoxylate ions include SeO4. 2- SeO3 2- The telluride ions include TeO3. 2- TeO4 2- The nitrogen oxyate ions include N2O2. 2- NO2 - NO3 - The arsenate ions include AsO3. 3- AsO4 3- The antimony oxyate ions include SbO2. - [Sb(OH)6] - The silicate ions include SiO3. 2- SiO4 4- Si2O7 6- The germanate ions include GeO3. 2- GeO4 4- The stannate ion Sn(OH)6 2- The lead-acid ions include PbO3. 2- PbO2 2- The sulfonate ions include R-SO3. - ; The cation precursor is an inorganic salt containing the cation element; The anionic precursor is selected from water and at least one of the following molecules: molecules that generate carbonate ions, molecules that generate thiooxyate ions, molecules that generate carboxylate ions, molecules that generate chloroxyate ions, molecules that generate bromooxyate ions, molecules that generate iodooxyate ions, molecules that generate selenoxyate ions, molecules that generate telluroxyate ions, molecules that generate nitricoxyate ions, molecules that generate arsenoxyate ions, molecules that generate antimonyoxyate ions, molecules that generate silicate ions, molecules that generate germanate ions, molecules that generate stannate ions, molecules that generate lead oxide ions, and molecules that generate sulfonate ions. The molecules that generate carbonate ions include carbonic acid; the molecules that generate thiocarboxylate ions include sulfuric acid; the molecules that generate carboxylate ions include formic acid, acetic acid, oxalic acid, citric acid, and tartaric acid; the molecules that generate chlorate ions include hypochlorous acid, chlorite, chloric acid, and perchloric acid; the molecules that generate bromoate ions include hypobromous acid, bromous acid, bromic acid, and perbromic acid; the molecules that generate iodoate ions include hypoiodic acid, iodous acid, iodic acid, and periodic acid; the molecules that generate selenate ions include selenite and selenic acid; the molecules that generate tellurium... The molecules that generate oxyacid ions include tellurite and telluric acid; the molecules that generate nitric acid ions include nitrous acid and nitric acid; the molecules that generate arsenic acid ions include arsenite and arsenic acid; the molecules that generate antimony acid ions include antimonyous acid and antimonyic acid; the molecules that generate silicate ions include orthosilicic acid and metasilicic acid; the molecules that generate germanate ions include metagermanic acid and orthogermanic acid; the molecules that generate stannate ions include stannic acid; the molecules that generate leadate ions include lead acid and lead(II) acid; and the molecules that generate sulfonate ions include sulfonic acid.

4. The method for printing and manufacturing multi-scale inorganic structures according to claim 1, characterized in that, The method for obtaining the printing fluid is either Method 1 or Method 2: Method 1: Physically separate the mixture obtained after molecular mediation leads to the formation of a dense liquid phase to separate the gel fluid. Then, add solvent to the gel fluid for dilution and perform physical separation again. Repeat the dilution and separation 1-50 times. Then, use solvent to centrifuge and replace the separated fluid and stir for 0-48 h to obtain the printing fluid. Method 2: Physically separate the mixture obtained after molecular mediation leads to the formation of a dense liquid phase to separate the gel-like fluid. Use a solvent to centrifuge and replace the separated fluid and stir for 0-48 h to obtain the printing fluid. In the mixture, the concentrations of both the anionic and cationic precursors are 0.1 M to 1 M, and the concentration of the molecular mediator is 0.1 M to 10 M. The viscosity of the printing fluid is 1 to 100,000,000 cp, and the mass fraction of the gel-like substance in the printing fluid is 30% to 99%.

5. The method for printing and manufacturing multi-scale inorganic structures according to claim 4, characterized in that, The molecular mediator is selected from at least one of the following: aliphatic amines, nitrogen-containing heterocyclic substances, aromatic and aryl amine mixtures, amides, sulfoxides, phosphorus ligands, carboxylic acids, and polycarboxylate salts. Aliphatic amines include diethylamine and triethylamine; nitrogen-containing heterocyclic substances include pyrrole, pyridine, piperidine, pyrazine, and piperazine; aromatic and aryl amine mixtures include aniline, N-benzyl-N-ethylaniline, N-methylaniline, and N,N-dimethylaniline; amides include formamide, acetamide, and benzamide; sulfoxides include dimethyl sulfoxide and methylphenyl sulfoxide; phosphorus ligands include trioctylphosphine oxide and triphenylphosphine; and carboxylic acids and polycarboxylate salts include polyacrylic acid, sodium oleate, aspartic acid, and glutamic acid. The solvent is selected from water and at least one of the following substances: alcohols, alkanes, alkenes, alkynes, ethers, ketones, esters, halogenated hydrocarbons, aromatics, nitriles, amides, and sulfoxides. The alcohols include methanol, ethanol, n-propanol, isopropanol, glycerol, n-butanol, and ethylene glycol; the alkanes include cyclohexane, n-hexane, n-pentane, and n-heptane; the alkenes include styrene and cyclohexene; the alkynes include 1-butyne and 1-pentyne; the ethers include tetrahydrofuran and diethyl ether; the ketones include acetone; the esters include ethyl acetate; the halogenated hydrocarbons include dichloromethane, chloroform, and carbon tetrachloride; the aromatics include benzene, toluene, and xylene; the nitriles include acetonitrile; the amides include N,N-dimethylformamide; and the sulfoxides include dimethyl sulfoxide.

6. The method for printing and manufacturing multi-scale inorganic structures according to claim 4, characterized in that, It also includes the step of adding a solvent to the printing fluid to regulate its viscosity.

7. The method for printing and manufacturing multi-scale inorganic structures according to claim 1, characterized in that, The printing technologies include electrohydraulic inkjet printing, direct-write printing, and aerosol jet printing.

8. The method for printing and manufacturing multi-scale inorganic structures according to claim 7, characterized in that, When manufacturing multi-scale inorganic structures using electrohydraulic inkjet printing, the aforementioned printing fluid is used as the material, and electrohydraulic inkjet printing equipment is used for printing with the following parameters: electric field strength of 0.5 kV / cm ~ 3 kV / cm, nozzle diameter of 100 ~ 800 μm, distance between nozzle and printing substrate of 0.1 ~ 5 mm, stage temperature of 20 ~ 300 ℃, and printing flow rate of 1 ~ 5 μL / min; the speeds of the three motion platforms of the electrohydraulic inkjet printing equipment (X-axis, Y-axis, Z-axis) are 0.1 ~ 20 mm / s, the printing environment temperature is 20 ~ 40 ℃, and the relative humidity is 40% ~ 60%. When manufacturing multi-scale inorganic structures using direct-write printing, the aforementioned printing fluid is used as the material, and direct-write printing is performed using a direct-write printing device with the following parameters: printhead diameter of 100~800 μm, distance between printhead and printing substrate of 0.1~2 mm, stage temperature of 20~300 ℃, printing air pressure of 5~200 kPa; X-axis, Y-axis, and Z-axis movement speed of the direct-write printing device of 0.1~20 mm / s, ambient temperature of 10~40 ℃, and relative humidity of 40%~60%. When manufacturing multi-scale inorganic structures using aerosol jet printing, the aforementioned printing fluid is used as the material, and aerosol jet printing equipment is used for aerosol jet printing with the following parameters: droplet size of 1 ~ 20 μm; nozzle diameter of 100 ~ 5000 μm; sheath gas flow rate of 20 ~ 1000 sccm; carrier gas flow rate of 10 ~ 500 sccm; distance between nozzle and printing substrate of 1 ~ 5 mm; printing substrate temperature of 10 ~ 100 ℃; printing speed of 0.1 ~ 50 mm / s; and printing fluid viscosity of 1 ~ 1000 cp.

9. The method for printing and manufacturing multi-scale inorganic structures according to claim 4, characterized in that, Before post-processing, the printed structure formed by the printing fluid is also subjected to a room temperature air-drying process. The air-drying conditions are: 0 h to 7 days at room temperature, until the printed structure is fully air-dried before post-processing. The printed structure formed by the printing fluid obtained by printing fluid method one is subjected to heat treatment. The heat treatment conditions are: temperature range of 50 ~ 1500℃, heating and cooling rate of 1 ~ 30 ℃ / min, temperature control accuracy of 1 ℃, and the heat treatment atmosphere is at least one of air, inert gas, oxidizing gas, and reducing gas. The printed structure formed by the printing fluid obtained by printing fluid method two has the following post-processing steps: heat treatment and water immersion treatment. The heat treatment conditions are: temperature range of 50 ~ 1500 ℃, heating and cooling rate of 1 ~ 30 ℃ / min, temperature control accuracy of 1 ℃, and the heat treatment atmosphere is at least one of air, inert gas, oxidizing gas, and reducing gas. The water immersion treatment conditions are: immersing the heat-treated inorganic structure in water for 0 h to 3 days.

10. A multi-scale inorganic structure manufactured by the printing method for multi-scale inorganic structures according to claim 1, characterized in that, The multi-scale inorganic structure comprises at least one element selected from alkali metals, alkaline earth metals, transition metals, main group metals, lanthanides and actinides, and metalloids and nonmetals. 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, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, Hf, Ta, W, Re, Os, Ir, Pt, Au, and Hg; main group metals include Al, Ga, In, Sn, Pb, and Bi; lanthanides and actinides include La, Ce, Pr, Nd, Sm, Eu, Gd, Dy, Er, Yb, Th, and U; and metalloids and nonmetals include B, Si, Ge, As, Sb, and Te. The multi-scale inorganic structure is any one of the following: oxides, hydroxides, and substances contained in carbonates, thiooxyates, carboxylates, chloroxyates, bromooxyates, iodooxyates, selenoxyates, telluroxyates, nitrooxyates, arsenoxyates, antimonyoxyates, silicates, germanates, stannates, leadates, or sulfonates. The carbonates include carbonates and bicarbonates; the thiosulfates include sulfates, bisulfates, pyrosulfates, persulfates, sulfites, bisulfites, thiosulfates, dithionites, trithionites, permonites, and hyposulfites; the carboxylates include formates, acetates, oxalates, citrates, and tartrates; the chloroxylates include hypochlorites, chlorites, chlorates, and perchlorates; the bromooxyates include hypobromoates, bromates, bromates, and perbromates; and the iodooxyates... The substances include hypoiodide, iodate, iodate, and periodate; the selenoxylate substances include selenate and selenite; the telluroxylate substances include tellurate and tellurite; the nitrogenoxylate substances include hyponitrate, nitrite, and nitrate; the arsenoxylate substances include arsenite and arsenate; the antimonyoxylate substances include antimonite and antimonate; the silicate substances include metasilicate and silicate; the germanate substances include metagermanate and progermanate; and the leadate substances include leadate and leadite. The components of the multi-scale inorganic structure include at least one of the following ions: halide ions, carbon-containing ions, sulfur-containing ions, and nitrogen-containing ions. The halide ions include F - Cl - ,Br - I - The carbon-containing ions include CO3. 2- The sulfur-containing ions include SO42-. 2- The nitrogen-containing ions include NO3-. - .

11. The multi-scale inorganic structure according to claim 10, characterized in that, The multi-scale inorganic structures include multi-scale structures with three-dimensional morphology and planar structures, with a size range of 50 nm to 10 cm. The shape of the planar structure includes amorphous, linear, dot-shaped, circular, triangular, square, rectangular, rhomboid, elliptical, quadrilateral, regular polygon, irregular polygon, sector, ring, arc, crescent, star, heart, and composite shapes composed of any of the above shapes; The three-dimensional morphology includes amorphous bodies, sheet-like bodies, cubes, spheres, ellipsoids, hollow spheres, cylinders, cones, frustums, polyhedra, curved surfaces, spindles, needle-like shapes, granular shapes, flower-like shapes, ring-like shapes, spiral shapes, leaf-like shapes, tenon-like shapes, and composite shapes composed of any of the above shapes.

12. The multi-scale inorganic structure according to claim 10, characterized in that, The atomic spatial arrangement of the multi-scale inorganic structure is either long-range ordered or long-range disordered. The internal microstructure of the multi-scale inorganic structure is one or more of the following: single crystal, polycrystalline, and long-range disordered structure. Both the single crystal and the polycrystalline structure are one or more of the following crystal systems: isometric, tetragonal, trigonal, hexagonal, orthorhombic, and monoclinic.

Images