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 printing and manufacturing method of the multi-scale inorganic structure comprises the following steps: firstly, carrying out an inorganic polymerization reaction on an inorganic anion precursor and an inorganic cation precursor in the presence of a capping agent and an organic solvent to form an inorganic oligomer fluid; printing forming of a plane structure and a three-dimensional structure of an inorganic oligomer is achieved through a printing technology, then heat treatment is conducted on a printed structure, and further inorganic polymerization preparation is utilized to achieve forming manufacturing of a multi-scale inorganic structure. The internal chemical components of the inorganic structure manufactured by the method are uniformly distributed, the printing and manufacturing resolution can reach below 10 [mu] m, and the manufacturing precision is higher; 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] The present invention relates to the technical field of materials science and technology, and in particular to a multi-scale inorganic structure and a printing manufacturing method thereof. Background Art

[0002] Inorganic compounds, originally referring to compounds unrelated to the organism (a few compounds related to the organism are also inorganic compounds, such as water), corresponding to organic compounds, usually refer to compounds that do not contain carbon elements, but include carbon-containing carbon oxides, carbonates, cyanides, carbides, carboranes, metal carbonyls, alkyl metals, metal organic ligand complexes, etc. carbon-containing species studied in inorganic chemistry, abbreviated as inorganic substances.

[0003] A multi-scale inorganic structure refers to a multi-scale structure formed by using inorganic substances as constituent materials through specific chemical or physical processes. The multi-scale inorganic structure has outstanding thermal stability and chemical stability, high mechanical strength, unique electrical and optical properties, and excellent biocompatibility / biodegradability. It can be used as a dielectric structure for high-end electronic devices such as ceramic dielectric capacitors, field effect transistors, and micro-nano sensors, and can also be applied to fields such as implantable (invasive) medical devices and brain-computer interfaces.

[0004] Currently, the main method for manufacturing multi-scale inorganic structures is laser sintering. The inorganic material powder is mixed with resin and evenly spread on a platform. The laser beam scans along the surface of the powder according to the sliced data preset by the computer and locally heats the powder to melt or sinter it in the laser irradiation area. The sintered powder will fuse into a solid inorganic structure. In addition, the removal of the resin depends on high-temperature sintering, which will cause the structure to shrink and exacerbate the problem of difficult precision control. At the same time, since the temperature of the heat treatment process is often as high as thousands of degrees Celsius, it is difficult to be compatible with materials such as carbonates (such as calcium carbonate decomposes at 900°C) and hydroxyphosphates (such as hydroxyapatite decomposes at 500°C).

[0005] Printing technology is a manufacturing process for constructing planar structures and three-dimensional structures by precisely depositing or layer-by-layer adding materials. This technology relies on digital model guidance and deposits or stacks materials layer by layer according to a preset program to finally realize the complete forming of the pre-designed structure. According to the principle, printing technology can be divided into various process types, including electrohydrodynamic printing (EHD), direct ink writing (DIW), aerosol jet printing (AJP), etc. Printing technology is suitable for both the precise construction of planar structures and the forming 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 and other fields. Printing technology provides a new path for the high-precision manufacturing of multi-scale inorganic structures. Summary of the Invention

[0006] The present invention provides a multi-scale inorganic structure and a printing manufacturing method thereof to solve the above problems.

[0007] To achieve the above object, the technical solution of the present invention is:

[0008] A printing manufacturing method of a multi-scale inorganic structure, comprising the following steps:

[0009] First, an inorganic polymerization reaction occurs between an inorganic anion precursor and an inorganic cation precursor in the presence of a capping agent and an organic solvent to form an inorganic oligomer fluid. The planar and three-dimensional structures of the inorganic oligomer are printed and formed by using printing technology. After that, the printed structure is heat-treated, and further inorganic polymerization is used to realize the forming and manufacturing of the multi-scale inorganic structure.

[0010] Further, the inorganic polymerization is an inorganic ion polymerization reaction or an inorganic ion polymerization reaction accompanied by an inorganic ion cross-linking reaction.

[0011] Further, the inorganic cation element in the inorganic oligomer fluid is selected from any one 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;

[0012] The inorganic anion in the inorganic oligomer fluid is selected from OH - , CO3 2- , 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- , H2PO4 - , P2O7 4- , P3O 10 5- , H2PO3 - , HPO3 2-, H2PO3 - , H2PO2 - , (PO3)3 3- , (PO3)4 4- , (PO3)6 6- , P2O6 4- , PO5 3- Any one of the above or any combination of the above anions;

[0013] The inorganic cation precursor is an inorganic salt containing the inorganic cation element;

[0014] The inorganic anion precursor is carbon dioxide, sulfur dioxide, sulfur trioxide, phosphoric acid, sulfuric acid or water and any combination of the above substances.

[0015] Furthermore, the steps for preparing the inorganic oligomer fluid are: centrifuging the inorganic oligomer mixture obtained after the inorganic polymerization reaction, separating the gel-like inorganic oligomer after centrifugation, and then adding an organic solvent to prepare the inorganic oligomer fluid;

[0016] In the inorganic oligomer mixture, the concentrations of the inorganic anion precursor and the inorganic cation precursor are both 1 mM to 10 M, and the concentration of the capping agent is 1 mM to 100 M;

[0017] The viscosity of the inorganic oligomer fluid is 1 to 1,000,000 cp, and the mass fraction of the gel-like substance in the inorganic oligomer fluid is 1% to 99%.

[0018] Furthermore, the capping agent is diethylamine, triethylamine, pyrrole, pyridine, piperidine, pyrazine or piperazine;

[0019] 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;

[0020] Furthermore, the heat treatment conditions are: temperature range 50 - 1500 °C, heating and cooling rate 0.1 - 50 °C / min, temperature control accuracy 1 °C, and heat treatment atmosphere is air, nitrogen, argon, ammonia, hydrogen sulfide, hydrogen, oxygen or a mixture of the above gases.

[0021] Furthermore, the specific steps for preparing the multi-scale inorganic structure include:

[0022] 1) Prepare the inorganic oligomer fluid:

[0023] 1.1) Add the inorganic cation precursor M to the organic solvent a to obtain solution A; M is a metal cation salt such as calcium chloride, calcium chloride dihydrate, magnesium chloride, copper chloride or aluminum chloride; the organic solvent a is selected from any one of methanol, ethanol, n-propanol, isopropanol, 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; in solution A, the concentration of M is 1 mM to 10 M;

[0024] 1.2) Add the capping agent N to solution A to obtain solution B; the capping agent N is diethylamine, triethylamine, pyrrole, pyridine, piperidine, pyrazine or piperazine; in solution B, the concentration of the capping agent N is 1 mM to 100 M; in this step, N is dispersed in A and N has not reacted with M yet;

[0025] 1.3) Add the inorganic anion precursor O to the organic solvent a to obtain solution C; O is carbon dioxide, phosphoric acid, sulfuric acid or water; in solution C, the concentration of the inorganic anion reactant O is 1 mM to 10 M;

[0026] 1.4) Slowly add solution B to solution C (or omit step 1.3 and directly introduce the corresponding reaction gas into solution B obtained in step 1.2, the reaction gas is carbon dioxide, sulfur dioxide or sulfur trioxide), stir magnetically at room temperature for 30 to 90 min to obtain suspension D, that is, an ionic oligomer mixture is prepared;

[0027] 1.5) Centrifuge the ionic oligomer mixture. After centrifugation, discard the supernatant and take the gel-like substance; the rotation speed of the centrifugation is 1000 to 20000 rpm, and the centrifugation time is 2 to 60 min;

[0028] 1.6) Disperse the obtained gel-like substance in the organic solvent a to prepare an inorganic oligomer fluid, and obtain an inorganic oligomer fluid with adjustable viscosity and surface tension by adjusting the addition amount of the solvent a as a printing material; the solvent a includes 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. The mass fraction of the solid in the inorganic oligomer fluid is 1% to 90%;

[0029] 2) Multi-scale inorganic structure deposition construction and heat treatment

[0030] Using the inorganic oligomeric fluid prepared in the above step 1) as a printing material, printing and manufacturing are carried out by a printing method, and the printing method includes electrohydrodynamic printing, direct writing printing, and aerosol jet printing. The specific steps of each printing method are as follows:

[0031] 2.1) Steps for constructing a multi-scale inorganic structure by electrohydrodynamic deposition of a multi-scale inorganic structure:

[0032] Position the substrate on a levelled and heatable workbench, and use electrohydrodynamic printing equipment for structure deposition and construction. The specific operation is as follows: Fill the inorganic oligomeric fluid into a syringe, and fix the syringe on a bracket through a syringe clamp. This bracket is installed on the Z-axis of the motor; Connect a DC or AC high-voltage power supply to the syringe to provide a high-voltage electric field, and an air pump provides a stable air pressure to the syringe through a pneumatic control cabinet; Under the control of a computer, drive the power supply to adjust the movement of the Z-axis, X-axis, and Y-axis of the motor; Under the action of the high-voltage electric field between the syringe and the substrate, the inorganic oligomeric fluid is refined into a conical jet and gradually ejected. The computer controls the movement of the motor to deposit and construct a multi-scale inorganic structure on the substrate; The electrohydrodynamic printing equipment parameters are adjusted as follows: The electric field strength is 0.5 kV / cm to 3 kV / cm, the nozzle diameter is 30 to 5000 μm, the distance between the nozzle and the substrate is 0.01 to 5 mm, the workbench temperature is -40 to 300 °C, the printing flow rate is 0.1 to 10 μL / min, and the printing resolution is 50 nm to 10 μm; The speed ranges of the three moving platforms on the X, Y, and Z axes are 0.01 to 50 mm / s, the temperature of the printing environment is -40 to 100 °C, and the relative humidity is 40% to 60% to prevent the solvent from evaporating too quickly and keep the solution properties stable; Monitor the relative position between the syringe and the substrate and the obtained inorganic structure through an observation camera to ensure the smooth completion of the process.

[0033] 2.2) Steps for constructing a multi-scale inorganic structure by direct writing deposition of a multi-scale inorganic structure:

[0034] Position the substrate on a levelled and heatable workbench, and use direct writing printing equipment to deposit and construct the structure. The specific operation is as follows: Load the inorganic oligomer fluid into a syringe, and fix the syringe on a bracket through a syringe clamp. The bracket is installed on the Z-axis of the motor; under the control of a computer, the drive power regulates the movement of the Z-axis, X-axis, and Y-axis of the motor; the syringe is connected to a pneumatic controller and an air pump through an air pipe. Under the action of the stable air pressure provided by the air pump, the fluid is extruded at a stable flow rate; the computer controls the movement of the motor to deposit and construct a multi-scale inorganic structure on the substrate. The parameters of the direct writing printing equipment are adjusted as follows: the diameter of the printing nozzle is 25 - 1000 μm, the distance between the nozzle and the substrate is 0.01 - 5 mm, the temperature of the workbench is -40 - 300 °C, the printing air pressure is 5 - 100 kPa, the fluid flow rate is 0.01 - 10 μL / min, and the printing resolution is 10 μm - 50 μm; the speed range of the X, Y, and Z axes is 0.01 - 50 mm / s, the temperature of the printing environment is -40 - 100 °C, and the relative humidity is 40% - 60%. Monitor the relative position between the syringe and the substrate and the obtained inorganic structure through an observation camera to ensure the smooth completion of the process;

[0035] 2.3) Steps for aerosol jet deposition of multi-scale inorganic structures The steps for aerosol jet deposition of multi-scale inorganic structures are as follows:

[0036] Position the substrate on a levelled and heatable workbench, and use aerosol jet printing equipment to deposit and construct the structure. The specific operation is as follows: Use a high-frequency (MHz level) ultrasonic nebulizer to convert the inorganic oligomer fluid into micron-sized droplets. The micro-droplets enter the carrier gas to form an aerosol and are 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 ejected at high speed and deposited on the substrate surface; under the control of a computer, the drive power regulates the movement of the Z-axis, X-axis, and Y-axis of the motor to achieve the deposition and construction of multi-scale inorganic structures. The parameters of the aerosol jet printing equipment are adjusted as follows: the size of the micro-droplets is 2 - 20 μm; the nozzle diameter is 100 μm - 5000 μm; the sheath gas flow rate is 20 - 1000 sccm, and the carrier gas flow rate is 10 - 100 sccm; the distance between the nozzle and the printed structure is 0.01 - 5 mm; the printing resolution is 10 μm - 50 μm; the printing temperature is -40 - 500 °C; the ambient relative humidity is 40% - 60%; the gas flow rate is 1 L / min - 10 L / min; the printing air pressure is 5 - 100 kPa; the speed range of the X, Y, and Z axes is 0.01 - 50 mm / s; monitor the relative position between the syringe and the substrate and the obtained inorganic structure through an observation camera to ensure the smooth completion of the process;

[0037] 2.4) After the multi-scale inorganic structure is constructed, it is heat-treated using a heat treatment device to polymerize / crosslink the inorganic ions, followed by curing to finally obtain the multi-scale inorganic structure. The heating parameters are set as follows: the temperature range is 50 - 1500 °C, the heating and cooling rate is 0.1 - 50 °C / min, the temperature control accuracy is 1 °C, and the heat treatment atmosphere is air, nitrogen, argon, ammonia, hydrogen sulfide, hydrogen, oxygen, or a mixture of the above gases.

[0038] The present invention also provides a multi-scale inorganic structure manufactured by this method. The multi-scale inorganic structure includes metal elements and metalloid elements. 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;

[0039] The multi-scale inorganic structure is an oxide, hydroxide, carbonate, bicarbonate, sulfate, bisulfate, pyrosulfate, persulfate, sulfite, bisulfite, thiosulfate, dithionate, trithionate, permonosulfate, hyposulfite, phosphate, hydrogen phosphate, dihydrogen phosphate, pyrophosphate, tripolyphosphate, phosphite, hydrogen phosphite, hypophosphite, metaphosphate, diphosphate, or perphosphate.

[0040] Further, the multi-scale inorganic structure includes a multi-scale structure with a three-dimensional morphology and a planar structure, and its size range is 50 nm - 10 cm;

[0041] The morphology of the planar structure includes amorphous, linear, dot-shaped, circular, triangular, square, rectangular, rhombic, elliptical, quadrilateral, regular polygon, irregular polygon, fan-shaped, annular, bow-shaped, crescent-shaped, star-shaped, heart-shaped, and composite shapes composed of any of the above shapes;

[0042] The three-dimensional morphology includes amorphous body, sheet-like body, cube, sphere, ellipsoid, hollow sphere, cylinder, cone, frustum, polyhedron, curved surface body, spindle, needle-shaped, granular, flower-shaped, annular, spiral, blade-shaped, mortise-and-tenon-shaped, and composite shapes composed of any of the above shapes.

[0043] Further, the atomic spatial arrangement of the multi-scale inorganic structure is long-range ordered or long-range disordered;

[0044] The internal microstructure of the multi-scale inorganic structure includes single crystals, polycrystals, long-range disordered structures, and combinations of the above three;

[0045] Both the single crystal and the polycrystalline structure are of cubic, tetragonal, trigonal, hexagonal, orthorhombic, monoclinic, and triclinic systems, or combinations of any several of the above crystal systems.

[0046] The beneficial effects of the present invention are as follows:

[0047] (1) In the method for printing and manufacturing the multi-scale inorganic structure disclosed in the present invention, compared with the traditional laser sintering method, the internal chemical composition of the inorganic structure manufactured by this method is evenly distributed, and the printing and manufacturing resolution can reach below 10 μm, with higher manufacturing precision;

[0048] (2) The manufacturing method provided by the present invention has broad compatibility with inorganic salts: compared with the traditional method, the present invention shows high compatibility with a variety of inorganic materials. This broad material compatibility makes the design more flexible, enabling the selection of the most suitable material system according to specific application requirements, and then preparing multi-scale inorganic structures with excellent performance. 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 use in 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 the manufacturing principle diagram of the multi-scale inorganic structure of the present invention;

[0051] Figure 2 It is the flowchart of electrohydrodynamic printing of inorganic structures of the present invention;

[0052] Figure 3 It is the flowchart of direct writing printing of inorganic structures of the present invention;

[0053] Figure 4 It is the photo of calcium carbonate oligomer fluid in Example 1 of the present invention;

[0054] Figure 5 It is the photo of calcium phosphate oligomer fluid in Example 4 of the present invention;

[0055] Figure 6 It is the photo of calcium hydroxyphosphate oligomer fluid in Example 7 of the present invention;

[0056] Figure 7 It is the photo of the heat-treated solid of calcium phosphate in Example 4 of the present invention;

[0057] Figure 8 Photograph of the solid after heat treatment of calcium carbonate in Example 1 of the present invention;

[0058] Figure 9 Photograph of the solid after heat treatment of calcium carbonate in Example 2 of the present invention;

[0059] Figure 10 Photograph of the solid after heat treatment of calcium hydroxyphosphate in Example 7 of the present invention;

[0060] Figure 11 XRD image of the calcium phosphate solid sample in Example 4 of the present invention;

[0061] Figure 12 XRD image of the calcium carbonate solid sample in Example 1 of the present invention;

[0062] Figure 13 XRD image of the calcium carbonate solid sample in Example 2 of the present invention;

[0063] Figure 14 Photograph of the electrohydrodynamic printing equipment;

[0064] Figure 15 Photograph of the direct writing printing equipment. Detailed implementation manners

[0065] 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.

[0066] Principle of the present application:

[0067] The present invention provides a method for fabricating a multi-scale inorganic structure, and fabricates a multi-scale inorganic structure through the above method. As Figure 2 、 Figure 3 shown is a schematic diagram of the manufacturing process of the multi-scale inorganic structure of the present invention. During the manufacturing process, first, an inorganic material precursor undergoes an inorganic polymerization reaction under a capping agent and an organic solvent to form an inorganic oligomer fluid. The inorganic oligomer is deposited on a substrate through a printing technique. In the printing process, a precisely controlled motor is used to extrude the inorganic oligomer fluid through a fine nozzle to form an inorganic structure in the shape of "H" shown in the figure. After that, the printed inorganic structure is heat-treated, and further inorganic polymerization is used to achieve curing and forming, forming a high-precision multi-scale inorganic structure with uniform composition and dense structure. The schematic diagram of the manufacturing principle of the multi-scale inorganic structure is as Figure 1as shown

[0068] Example 1:

[0069] Ca 2+ and CO3 2- Manufacturing of oligomer fluid and its multi-scale inorganic structure direct writing printing, the steps include:

[0070] In the first step, take Ca 2+ and CO3 2- oligomer fluid, and use it as the printing material. The mass fraction of the gel-like substance is 50%, and the viscosity is 5000 cp. The specific steps include:

[0071] 1.1) Take 3.675 g of calcium chloride dihydrate and add it to 50 mL of ethanol to obtain solution A, where the concentration of calcium chloride dihydrate is 0.5 M;

[0072] 1.2) Add 2.52 g of triethylamine to solution A to obtain solution B, where the concentration of diethylamine is 0.5 M;

[0073] 1.3) Pass carbon dioxide gas into solution A and stir magnetically at room temperature. The gas flow rate is 80 mL / min, and the ventilation and stirring time is 30 min to obtain suspension D as the ionic oligomer solution;

[0074] 1.4) Centrifuge the oligomer solution at a rotation speed of 5000 rpm for 15 min to separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0075] 1.5) Disperse the obtained gel-like substance in 10 mL of glycerol to prepare Ca 2+ and CO3 2- oligomer fluid. The prepared calcium carbonate oligomer fluid is as Figure 4 shown;

[0076] In the second step, position the substrate on a leveled and heatable workbench. Inject the inorganic oligomer fluid into a syringe and perform structure printing using the direct writing printing equipment as Figure 15 shown. Input the relevant printing program into the printing device, and set the device parameters as follows: the diameter of the extrusion nozzle is 30 μm, the distance between the nozzle and the substrate / printed structure is 1 mm, and the workbench temperature is 80 °C; the printing air pressure is 10 kPa, the fluid flow rate is 5 μL / min, and the speeds of the X, Y, and Z axes are 0.01 mm / s; the temperature of the printing environment is 20 °C, and the relative humidity is 45%. Monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process;

[0077] In the third step, the obtained structure is heat-treated. The heat treatment atmosphere is air, the temperature is set at 120 °C, the heating and cooling rate is 2 °C / min, and the holding time is 2 h to form the expected structure. The solid product after heat treatment is as Figure 8 shown.

[0078] Through the above steps, an inorganic linear structure with a line width of about 100 μm was successfully prepared, and the resolution reached below 10 μm. After verification, the composition of the obtained inorganic linear structure is polycrystalline calcium carbonate, and the crystal forms include trigonal, orthorhombic, and hexagonal crystal systems. These structures show good consistency and repeatability, verifying the effectiveness and feasibility of the technical solution. The XRD image of the prepared calcium carbonate solid sample is as Figure 12 shown.

[0079] Example 2:

[0080] Ca 2+ , CO3 2- Manufacturing of oligomer fluids and their multi-scale inorganic structure aerosol jet printing, the steps include:

[0081] In the first step, take Ca 2+ , CO3 2- oligomer fluid, and use it as the printing material. The mass fraction of the gel-like substance is 80%, and the viscosity is 8000 cp. The specific steps include:

[0082] 1.1) Take 7.35 g of calcium chloride dihydrate and add it to 50 mL of isopropanol to obtain solution A, where the concentration of calcium chloride dihydrate is 1 M;

[0083] 1.2) Add 3 g of diethylamine to solution A to obtain solution B, where the concentration of diethylamine is 1 M;

[0084] 1.3) Pass carbon dioxide gas into solution A and stir magnetically at room temperature. The gas flow rate is 50 mL / min, and the gas passing and stirring time is 30 min to obtain suspension D as the ionic oligomer solution;

[0085] 1.4) Centrifuge the oligomer solution, set the rotation speed at 6000 rpm, and the centrifugation time at 20 min to completely separate the oligomer solution, discard the supernatant, and collect the solid;

[0086] 1.5) Disperse the obtained gel-like substance in 5 mL of isopropanol to prepare Ca 2+ , CO3 2- oligomer fluid;

[0087] In the second step, position the substrate on a levelled and heatable workbench; use a high-frequency (MHz-level) ultrasonic nebulizer to convert the inorganic oligomeric fluid into micron-sized microdroplets. The microdroplets enter the carrier gas to form an aerosol and are transported to the nozzle. Apply a surrounding gas at the nozzle to confine the aerosol into a beam with a diameter of 10 μm, which is ejected at high speed and deposited on the substrate surface. The equipment parameters are adjusted as follows: microdroplet size is 5 μm; nozzle diameter is 100 μm; sheath gas flow rate is 100 sccm, carrier gas flow rate is 40 sccm; distance between the nozzle and the printing structure is 1 mm; printing temperature is 25 °C; ambient relative humidity is 40%; gas flow rate is 1 L / min; the speed range of the X, Y, and Z axes is 0.01 mm / s; monitor the relative position between the syringe and the substrate and the resulting inorganic structure through an observation camera to ensure the smooth completion of the process;

[0088] In the third step, perform heat treatment on the obtained structure. The heat treatment atmosphere is argon, the temperature is set at 300 °C, the heating and cooling rate is 1 °C / min, and the holding time is 2 h to form the desired structure. The solid product formed after heat treatment is as Figure 9 shown.

[0089] Through the above steps, an inorganic linear structure with a wire length of about 20 mm, a wire width of about 2 mm, and a dimensional accuracy of about 50 μm was successfully prepared. After verification, the obtained inorganic linear structure is calcium carbonate, and its internal microstructure is a long-range disordered structure. The inorganic linear structure prepared in this example has excellent uniformity and accuracy. The XRD image of the prepared calcium carbonate solid sample is as Figure 13 shown. The successful preparation of these structures further confirms the applicability and feasibility of the technical solution.

[0090] Example 3:

[0091] Ca 2+ 、CO3 2- Manufacturing of oligomeric fluid and its multi-scale inorganic structure by electrohydrodynamic printing, the steps include:

[0092] In the first step, take Ca 2+ 、CO3 2- oligomeric fluid and use it as the printing material. The mass fraction of the gel-like substance is 80%, and the viscosity is 8000 cp. The specific steps include:

[0093] 1.1) Take 3.675 g of calcium chloride dihydrate and add it to 50 mL of isopropyl alcohol to obtain solution A, where the concentration of calcium chloride dihydrate is 0.5 M;

[0094] 1.2) Add 3 g of diethylamine to solution A to obtain solution B, where the concentration of diethylamine is 1 M;

[0095] 1.3) Carbon dioxide gas is introduced into Solution A and magnetically stirred at room temperature. The gas flow rate is 50 mL / min, and the gas introduction and stirring time is 30 min to obtain Suspension D as an ionic oligomer solution;

[0096] 1.4) The oligomer solution is centrifuged at a rotation speed of 6000 rpm for 20 min to completely separate the oligomer solution. The supernatant is discarded, and the solid is collected;

[0097] 1.5) The obtained gel-like substance is dispersed in 5 mL of isopropanol to prepare a Ca 2+ 、CO3 2- oligomer fluid;

[0098] In the second step, the substrate is positioned on a leveled and heatable workbench; the inorganic oligomer fluid is injected into a syringe, and structure printing is performed using the electrohydrodynamic printing equipment as shown in Figure 14 ; the relevant printing program is input into the printing device, and the device parameters are set as follows: the electric field strength is 2 kV / cm, the nozzle diameter is 50 μm, the distance between the nozzle and the substrate / printed structure is 2 mm, the workbench temperature is 70 °C, the fluid flow rate is 10 μL / min, the speed range of the X, Y, and Z axes is 0.5 mm / s, the temperature of the printing environment is 20 °C, and the relative humidity is 40%. The relative position between the syringe and the substrate and the obtained structure are monitored through an observation camera to ensure the smooth completion of the process;

[0099] In the third step, the obtained structure is heat-treated. The heat treatment atmosphere is argon, the temperature is set at 300 °C, the heating and cooling rate is 1 °C / min, and the heat preservation time is 2 h to form the expected structure.

[0100] Through the above steps, an inorganic linear structure with a wire length of about 20 mm, a wire width of about 2 mm, and a dimensional accuracy of about 50 μm is successfully prepared. It is verified that the composition of the obtained inorganic linear structure is polycrystalline calcium carbonate, and the crystal forms include trigonal and orthorhombic systems. The inorganic linear structure prepared in this example has excellent uniformity and accuracy.

[0101] The successful preparation of these structures further confirms the applicability and feasibility of the technical solution.

[0102] Example 4:

[0103] Ca 2+ 、PO4 3- The preparation of an oligomer fluid and its multi-scale inorganic structure by direct writing printing, the steps include:

[0104] In the first step, take Ca 2+ 、PO4 3-An oligomer fluid is used as a printing material. The mass fraction of the gel-like substance is 70% and the viscosity is 5000 cp. The specific steps are as follows:

[0105] 1.1) Take 0.882 g of calcium chloride dihydrate and add it to 30 mL of methanol to obtain solution A, where the concentration of calcium chloride dihydrate is 0.2 M;

[0106] 1.2) Add 1.21 g of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.4 M;

[0107] 1.3) Add 0.392 g of phosphoric acid to 20 mL of methanol to obtain solution C, where the concentration of phosphoric acid is 0.2 M;

[0108] 1.4) Add solution B to solution C and stir magnetically at room temperature for 40 min to obtain suspension D as an ionic oligomer solution;

[0109] 1.5) Centrifuge the oligomer solution at a rotation speed of 8000 rpm for 10 min, separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0110] 1.6) Disperse the obtained gel-like substance in 5 mL of glycerol to prepare a Ca 2+ 、PO4 3- oligomer fluid. The prepared calcium phosphate oligomer fluid is as Figure 5 shown;

[0111] In the second step, position the glass substrate on a levelled and heatable workbench; inject the inorganic oligomer fluid into a syringe and perform structure printing using a direct writing printing device. Input the relevant printing program into the printing device, and set the device parameters as follows: the diameter of the extrusion nozzle is 500 μm, the distance between the nozzle and the substrate / printed structure is 3 mm, the workbench temperature is 80 °C; the printing air pressure is 15 kPa, the fluid flow rate is 8 μL / min, and the speeds of the X, Y, and Z axes are 1 mm / s; the temperature of the printing environment is 20 °C and the relative humidity is 45%; monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process;

[0112] In the third step, perform heat treatment on the obtained structure. The heat treatment atmosphere is argon, the temperature is set at 300 °C, the heating and cooling rate is 1 °C / min, and the holding time is 1 h to form the expected structure. The solid product after heat treatment is as Figure 7 shown. Through the above steps, an inorganic cylinder structure with a diameter of about 0.5 cm, a height of about 1 cm, and a dimensional accuracy of about 50 μm is successfully prepared. After verification, the composition of the obtained inorganic structure is single crystal calcium phosphate. The XRD image of the prepared calcium phosphate solid sample is as Figure 11As shown. The inorganic linear structure prepared in this embodiment has excellent uniformity and accuracy.

[0113] Example 5:

[0114] Ca 2+ 、PO4 3- Manufacturing of oligomer fluid and its multi-scale inorganic structure by electrohydrodynamic printing, the steps include:

[0115] The first step is to take Ca 2+ 、PO4 3- oligomer fluid, which is used as the printing material. The mass fraction of the gel-like substance is 60%, and the viscosity is 4000 cp. The specific steps include:

[0116] 1.1) Take 0.882 g of calcium chloride dihydrate and add it to 30 mL of methanol to obtain solution A, where the concentration of calcium chloride dihydrate is 0.2 M;

[0117] 1.2) Add 1.21 g of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.4 M;

[0118] 1.3) Add 0.392 g of phosphoric acid to 20 mL of methanol to obtain solution C, where the concentration of phosphoric acid is 0.2 M;

[0119] 1.4) Add solution B to solution C and stir magnetically at room temperature for 40 min to obtain suspension D as the ionic oligomer solution;

[0120] 1.5) Centrifuge the oligomer solution at a rotation speed of 8000 rpm for 10 min, separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0121] 1.6) Disperse the obtained gel-like substance in 5 mL of glycerol to prepare Ca 2+ 、PO4 3- oligomer fluid;

[0122] The second step is to position the substrate on a levelled and heatable workbench; inject the inorganic oligomer fluid into a syringe and use electrohydrodynamic printing equipment for structure printing; input the relevant printing program into the printing device, and set the device parameters as follows: the electric field strength is 2 kV / cm, the nozzle diameter is 50 μm, the distance between the nozzle and the substrate / printed structure is 1 mm, the workbench temperature is 70 °C, the fluid flow rate is 10 μL / min, the speed range of the X, Y, and Z axes is 0.5 mm / s, the temperature of the printing environment is 20 °C, and the relative humidity is 40%. Monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process;

[0123] In the third step, the obtained structure is heat-treated. The heat treatment atmosphere is argon, the temperature is set at 300 °C, the heating and cooling rate is 1 °C / min, and the holding time is 1 h to form the expected structure. Through the above steps, an inorganic cylindrical structure with a diameter of about 1 cm, a height of about 1 cm, and a dimensional accuracy of about 50 μm is successfully prepared. After verification, the composition of the obtained inorganic structure is calcium phosphate, and the internal microstructure is long-range disordered. The inorganic linear structure prepared in this example has excellent uniformity and accuracy.

[0124] Example 6:

[0125] Ca 2+ 、SO4 2- Direct writing manufacturing of oligomer fluid and its multi-scale inorganic structure, the steps include:

[0126] In the first step, take Ca 2+ 、PO4 3- oligomer fluid, and use it as the printing material. The mass fraction of the gel-like substance is 60%, and the viscosity is 5000 cp. The specific steps include:

[0127] 1.1) Take 1.47 g of calcium chloride dihydrate and add it to 50 mL of ethanol to obtain solution A, where the concentration of calcium chloride dihydrate is 0.2 M;

[0128] 1.2) Add 2.02 g of triethylamine to solution A to obtain solution B, where the concentration of diethylamine is 0.4 M;

[0129] 1.3) Add 0.98 g of sulfuric acid to 50 mL of ethanol to obtain solution C, where the concentration of sulfuric acid is 0.2 M;

[0130] 1.4) Add solution B to solution C and stir magnetically at room temperature for 40 min to obtain suspension D as the ionic oligomer solution;

[0131] 1.5) Centrifuge the oligomer solution at a rotation speed of 9000 rpm for 10 min, separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0132] 1.6) Disperse the obtained gel-like substance in 5 mL of glycerol to prepare Ca 2+ 、SO4 2- oligomer fluid;

[0133] In the second step, position the glass substrate on the leveled and heatable workbench; inject the inorganic oligomeric fluid into the syringe and perform structure printing using a direct writing printing device; input the relevant printing program into the printing device, and set the device parameters as follows: the diameter of the extrusion nozzle is 0.5 μm, the distance between the nozzle and the substrate / printed structure is 0.01 mm, the workbench temperature is 80 °C; the printing air pressure is 10 kPa, the fluid flow rate is 0.05 μL / min, and the speeds of the X, Y, and Z axes are 0.01 mm / s; the temperature of the printing environment is 20 °C, and the relative humidity is 45%. Monitor the relative position between the syringe and the substrate and the obtained structure through the observation camera to ensure the smooth completion of the process;

[0134] In the third step, perform heat treatment on the obtained structure. The heat treatment atmosphere is air, the temperature is set at 150 °C, the heating and cooling rate is 3 °C / min, and the holding time is 3 h to form the desired structure;

[0135] Through the above steps, rod-shaped inorganic structures with a diameter of approximately 80 μm, a length of approximately 400 μm, and a dimensional accuracy of approximately 10 μm were successfully prepared. After verification, the composition of the obtained inorganic structure is single-crystal calcium sulfate, and the crystal form is orthorhombic system. These structures exhibit good morphological consistency and repeatability, verifying the effectiveness and feasibility of this technical solution.

[0136] Example 7:

[0137] Ca 2+ 、PO4 3- 、OH - Direct writing manufacturing of oligomeric fluid and its multi-scale inorganic structures, the steps include:

[0138] In the first step, take Ca 2+ 、PO4 3- 、OH - oligomeric fluid and use it as the printing material. The mass fraction of the gel-like substance is 40%, and the viscosity is 3000 cp. The specific steps include:

[0139] 1.1) Take 1.47 g of calcium chloride dihydrate and add it to 50 mL of ethanol to obtain solution A, where the concentration of calcium chloride dihydrate is 0.2 M;

[0140] 1.2) Add 3.03 g of triethylamine to solution A to obtain solution B, where the concentration of diethylamine is 0.6 M;

[0141] 1.3) Add 0.58 g of phosphoric acid to 30 mL of ethanol to obtain solution C, where the concentration of phosphoric acid is 0.2 M;

[0142] 1.4) Add Solution B to Solution C, and add 0.36 g of water to Solution C. Stir magnetically at room temperature for 30 min to obtain Suspension D as the ionic oligomer solution;

[0143] 1.5) Centrifuge the oligomer solution at a rotation speed of 8000 rpm for 15 min to separate the oligomer solution. Discard the supernatant and collect the gel-like substance;

[0144] 1.6) Disperse the obtained gel-like substance in 5 mL of glycerol to prepare a Ca 2+ 、PO4 3- 、OH - oligomer fluid. The prepared calcium hydroxyphosphate oligomer fluid is as Figure 6 shown;

[0145] In the second step, position the glass substrate on a levelled and heatable workbench; inject the inorganic oligomer fluid into a syringe and perform structure printing using a direct writing printing device; input the relevant printing program into the printing device, and set the device parameters as follows: the diameter of the extrusion nozzle is 50 μm, the distance between the nozzle and the substrate / printed structure is 0.01 mm, the workbench temperature is 70 °C; the printing air pressure is 15 kPa, the fluid flow rate is 0.05 μL / min, and the speeds of the X, Y, and Z axes are 0.01 mm / s; the temperature of the printing environment is 15 °C and the relative humidity is 50%; monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process.

[0146] In the third step, perform heat treatment on the obtained structure. The heat treatment atmosphere is argon, the temperature is set at 150 °C, the heating and cooling rate is 5 °C / min, and the holding time is 2 h to form the expected structure. The solid product after heat treatment is as Figure 10 shown.

[0147] Through the above steps, an inorganic linear structure with a line width of about 80 μm and a dimensional accuracy of about 20 μm was successfully prepared. After verification, the composition of the obtained inorganic structure is single-crystal calcium hydroxyphosphate, and the crystal form is hexagonal system.

[0148] Example 8:

[0149] Ca 2+ 、OH - oligomer fluid and its multi-scale inorganic structure direct writing manufacturing, the steps include:

[0150] In the first step, take Ca 2+ 、OH-oligomer fluid as the printing material, with the mass fraction of the gel-like substance being 50% and the viscosity being 4000 cp. The specific steps include:

[0151] 1.1) Take 3.675 g of calcium chloride dihydrate and add it to 50 mL of ethanol to obtain solution A, where the concentration of calcium chloride dihydrate is 0.5 M;

[0152] 1.2) Add 5.05 g of triethylamine to solution A to obtain solution B, where the concentration of diethylamine is 1 M;

[0153] 1.3) Add 0.9 g of water to solution B and stir magnetically at room temperature for 40 min to obtain suspension D as the ionic oligomer solution;

[0154] 1.4) Centrifuge the oligomer solution obtained in the first step at a rotation speed of 9000 rpm for 10 min, separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0155] 1.5) Disperse the obtained gel-like substance in 10 mL of glycerol to prepare a Ca 2+ , OH-oligomer fluid;

[0156] In the second step, position the glass substrate on a leveled and heatable workbench; inject the inorganic oligomer fluid into a syringe and perform structure printing using a direct writing printing device; input the relevant printing program into the printing device, and set the device parameters as follows: the diameter of the extrusion nozzle is 50 μm, the distance between the nozzle and the substrate / printed structure is 0.5 mm, the workbench temperature is 60 °C; the printing air pressure is 10 kPa, the fluid flow rate is 0.05 μL / min, and the speeds of the X, Y, and Z axes are 0.05 mm / s; the temperature of the printing environment is 20 °C and the relative humidity is 45%. Monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process;

[0157] In the third step, perform heat treatment on the obtained structure. The heat treatment atmosphere is argon, the temperature is set to 100 °C, the heating and cooling rate is 1 °C / min, and the holding time is 1 h to form the expected structure;

[0158] Through the above steps, an inorganic cantilever beam structure with a length of about 600 μm, a width of about 100 μm, and a dimensional accuracy of about 20 μm was successfully prepared. After verification, the composition of the obtained inorganic structure is calcium hydroxide and the crystal form is hexagonal crystal system.

[0159] Example 9:

[0160] Al 3+ , OH-oligomer fluid and its direct writing manufacturing of multi-scale inorganic structures, the steps include:

[0161] In the first step, take Al 3+, an OH-oligomer fluid, which is used as a printing material, has a mass fraction of the gel-like substance of 80% and a viscosity of 5000 cp. The specific steps include:

[0162] 1.1) Take 1.33 g of aluminum chloride and add it to 50 mL of ethanol to obtain solution A, where the concentration of aluminum chloride is 0.2 M;

[0163] 1.2) Add 2.52 g of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.5 M;

[0164] 1.3) Add 0.54 g of water to the solution and stir magnetically at room temperature for 40 min to obtain suspension D as an ionic oligomer solution;

[0165] 1.4) Centrifuge the oligomer solution at a rotation speed of 7000 rpm for 10 min, separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0166] 1.5) Disperse the obtained gel-like substance in 10 mL of glycerol to prepare Al 3+ 、OH - oligomer fluid b;

[0167] In the second step, position the glass substrate on a leveled and heatable workbench; inject the inorganic oligomer fluid into a syringe and perform structure printing using a direct writing printing device; input the relevant printing program into the printing device, and set the device parameters as follows: the diameter of the extrusion nozzle is 50 μm, the distance between the nozzle and the substrate / printed structure is 1 mm, the workbench temperature is 80 °C; the printing air pressure is 10 kPa, the fluid flow rate is 0.1 μL / min, and the speeds of the X, Y, and Z axes are 0.1 mm / s; the temperature of the printing environment is 25 °C, and the relative humidity is 60%. Monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process;

[0168] In the third step, perform heat treatment on the obtained structure. The heat treatment atmosphere is air, the temperature is set at 500 °C, the heating and cooling rate is 5 °C / min, and the holding time is 2 h to form the expected structure.

[0169] Through the above steps, an inorganic columnar structure with a diameter of about 3 mm, a height of about 5 mm, and a dimensional accuracy of about 20 μm was successfully prepared. After verification, the composition of the obtained inorganic structure is alumina.

[0170] Example 10:

[0171] Al 3+ 、OH-oligomer fluid and its multi-scale inorganic structure electrohydrodynamic printing manufacturing, the steps include:

[0172] Step 1: Take Al 3+ and OH-oligomer fluid, and use it as the printing material. The mass fraction of the gel-like substance is 70%, and the viscosity is 5000 cp. The specific steps are as follows:

[0173] 1.1) Take 1.33 g of aluminum chloride and add it to 50 mL of ethanol to obtain solution A, where the concentration of aluminum chloride is 0.2 M;

[0174] 1.2) Add 2.52 g of triethylamine to solution A to obtain solution B, where the concentration of triethylamine is 0.5 M;

[0175] 1.3) Add 0.54 g of water to the solution and stir magnetically at room temperature for 40 min to obtain suspension D as the ionic oligomer solution;

[0176] 1.4) Centrifuge the oligomer solution at a rotation speed of 7000 rpm for 10 min, separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0177] 1.5) Disperse the obtained gel-like substance in 10 mL of ethanol to prepare Al 3+ and OH-oligomer fluid b;

[0178] Step 2: Position the substrate on a leveled and heatable workbench; inject the inorganic oligomer fluid into the syringe and perform structure printing using an electrohydrodynamic printing device; input the relevant printing program into the printing device, and set the device parameters as follows: the electric field strength is 2 kV / cm, the nozzle diameter is 100 μm, the distance between the nozzle and the substrate / printed structure is 1 mm, the workbench temperature is 70 °C, the fluid flow rate is 10 μL / min, the speed range of the X, Y, and Z axes is 0.5 mm / s, the temperature of the printing environment is 25 °C, and the relative humidity is 40%. Monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process;

[0179] Step 3: Perform heat treatment on the obtained structure. The heat treatment atmosphere is air, the temperature is set at 200 °C, the heating and cooling rate is 5 °C / min, and the holding time is 2 h to form the expected structure;

[0180] Through the above steps, a cylindrical structure with a diameter of about 5 mm, a height of about 1 cm, and a dimensional accuracy of about 30 μm was successfully prepared. After verification, the composition of the obtained inorganic structure is alumina.

[0181] Example 11:

[0182] Cu 2+ and CO3 2- Oligomer fluid and its multi-scale inorganic structure direct writing manufacturing, the steps include:

[0183] Step 1: Take Cu 2+ , CO3 2- oligomer fluid and use it as the printing material. The mass fraction of the gel-like substance is 80%, and the viscosity is 5000 cp. The specific steps are as follows:

[0184] 1.1) Take 3.36 g of copper chloride and add it to 50 mL of ethanol to obtain solution A, where the concentration of copper chloride is 0.5 M;

[0185] 1.2) Add 2.52 g of triethylamine to solution A to obtain solution B, where the concentration of diethylamine is 0.5 M;

[0186] 1.3) Pass carbon dioxide gas into solution A and stir magnetically at room temperature. The gas flow rate is 80 mL / min, and the gas passing and stirring time is 30 min to obtain suspension D as the ionic oligomer solution;

[0187] 1.4) Centrifuge the oligomer solution at a rotation speed of 8000 rpm for 15 min to separate the oligomer solution, discard the supernatant, and take the gel-like substance;

[0188] 1.5) Disperse the obtained gel-like substance in 10 mL of glycerol to prepare Cu 2+ , CO3 2- oligomer fluid;

[0189] Step 2: Position the glass substrate on a levelled and heatable workbench; inject the inorganic oligomer fluid into a syringe and use a direct writing printing device for structure printing; input the relevant printing program into the printing device, and set the device parameters as follows: the diameter of the extrusion nozzle is 50 μm, the distance between the nozzle and the substrate / printed structure is 0.5 mm, the workbench temperature is 80 °C; the printing air pressure is 15 kPa, the fluid flow rate is 1 μL / min, and the speeds of the X, Y, and Z axes are 0.1 mm / s; the temperature of the printing environment is 25 °C, and the relative humidity is 40%. Monitor the relative position between the syringe and the substrate and the obtained structure through an observation camera to ensure the smooth completion of the process;

[0190] Step 3: Perform heat treatment on the obtained structure. The heat treatment atmosphere is argon, the temperature is set at 120 °C, the heating and cooling rate is 1 °C / min, and the holding time is 30 min to form the expected structure;

[0191] Through the above steps, an inorganic linear structure with a length of about 600 μm, a line width of about 50 μm, and a dimensional accuracy of about 20 μm was successfully prepared. After verification, the composition of the obtained inorganic structure is copper carbonate, and the crystal form is monoclinic system.

[0192] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than 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 cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A printing method for manufacturing a multi-scale inorganic structure, characterized in that: The steps include: First, an inorganic anion precursor and an inorganic cation precursor are used to undergo an inorganic polymerization reaction in the presence of a capping agent and an organic solvent to form an inorganic oligomer fluid. Printing technology is used to print the planar and three-dimensional structures of the inorganic oligomers. The printed structure is then heat treated and further inorganic polymerization is used to achieve multi-scale inorganic structure molding and manufacturing.

2. The printing method for manufacturing a multi-scale inorganic structure according to claim 1, characterized in that: The inorganic polymerization is inorganic ion polymerization or inorganic ion polymerization accompanied by inorganic ion crosslinking.

3. The printing and manufacturing method of the multi-scale inorganic structure according to claim 1, characterized in that: The inorganic cationic element in the inorganic oligomer fluid is selected from any one 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, and Te; The inorganic anions in the inorganic oligomer fluid are selected from OH - 、CO3 2- 、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- 、H2PO4 - 、P2O7 4- 、P3O 10 5- 、H2PO3 - 、HPO3 2- 、H2PO3 - 、H2PO2 - 、(PO3)3 3- 、(PO3)4 4- 、(PO3)6 6- 、P2O6 4- PO5 3- Any one of and any combination of the above anions; The inorganic cation precursor is an inorganic salt containing the inorganic cation element; The inorganic anion precursor is carbon dioxide, phosphoric acid, sulfuric acid or water and any combination thereof.

4. The printing and manufacturing method of the multi-scale inorganic structure according to claim 1, characterized in that: The steps of preparing the inorganic oligomer fluid are: centrifuging the inorganic oligomer mixed solution obtained after the inorganic polymerization reaction, separating the gel-like inorganic oligomer after centrifugation, and then adding an organic solvent to prepare the inorganic oligomer fluid; In the inorganic oligomer mixed solution, the concentrations of the inorganic anion precursor and the inorganic cation precursor are both 1mM to 10M, and the concentration of the capping agent is 1mM to 100M; The viscosity of the inorganic oligomer fluid is 1-1,000,000 cp, and the mass fraction of the gel-like substance in the inorganic oligomer fluid is 1%-99%.

5. The printing and manufacturing method of the multi-scale inorganic structure according to claim 1, characterized in that: The capping agent is diethylamine, triethylamine, pyrrole, pyridine, piperidine, pyrazine or piperazine; 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 printing and manufacturing method of the multi-scale inorganic structure according to claim 1, characterized in that: The printing techniques include electrofluidic printing, direct write printing, and aerosol jet printing.

7. The printing method for manufacturing a multi-scale inorganic structure according to claim 6, characterized in that: When electrofluid printing is used to manufacture multi-scale inorganic structures, the inorganic oligomer fluid is used as a printing material, and electrofluid printing is performed using an electrofluid printing device, and the parameters are: the electric field strength is 0.5kV / cm~3kV / cm, the nozzle diameter is 30~5000μm, the distance between the nozzle and the substrate is 0.01~5mm, the workbench temperature is -40~300℃, and the printing flow rate is 0.1~10μL / min; the speed of the three moving platforms X, Y, and Z axes of the electrofluid printing device is 0.01~50mm / s, the temperature of the printing environment is -40~100℃, and the relative humidity is 40%~ 60%; when direct writing printing is used to manufacture multi-scale inorganic structures, the inorganic oligomer fluid is used as the printing material, and direct writing printing equipment is used for direct writing printing, and the parameters are: the diameter of the printing nozzle is 25 to 1000 μm, the distance between the nozzle and the substrate is 0.01 to 5 mm, the table temperature is -40 to 300 ° C, the printing pressure is 5 to 100 kPa, and the printing flow rate is 0.1 to 10 μL / min; the movement speed of the X, Y, and Z axes of the direct writing printing equipment is 0.01 to 50 mm / s, the temperature of the printing environment is -40 to 100 ° C, and the relative humidity is 40% to 60%; When aerosol jet printing is used to manufacture multi-scale inorganic structures, the inorganic oligomer fluid is used as the printing material, and aerosol jet printing is performed using aerosol jet printing equipment, and the parameters are: droplet size is 2 to 20 μm; nozzle diameter is 100 to 5000 μm; sheath gas flow rate is 20 to 1000 sccm, and carrier gas flow rate is 10 to 100 sccm; the distance between the nozzle and the substrate is 2 to 5 mm; the printing temperature is -40 to 500°C; the printing speed is 1 to 50 mm / s, and the printing fluid viscosity is 1 to 1000 cp.

8. The printing and manufacturing method of the multi-scale inorganic structure according to claim 1, characterized in that: The heat treatment conditions are: temperature range 50-1500°C, heating and cooling rate 0.1-50°C / min, temperature control accuracy 1°C, and heat treatment atmosphere is air, nitrogen, argon, ammonia, hydrogen sulfide, hydrogen, oxygen or a mixture of the above gases.

9. A multi-scale inorganic structure manufactured by the printing manufacturing method of the multi-scale inorganic structure according to claim 1, characterized in that: The multi-scale inorganic structure includes metal elements and metalloid elements, wherein 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; The multi-scale inorganic structure is an oxide, hydroxide, carbonate, bicarbonate, sulfate, hydrogen sulfate, pyrosulfate, peroxydisulfate, sulfite, hydrogensulfite, thiosulfate, dithionate, trithionate, permonosulfate, hyposulfate, phosphate, hydrogenphosphate, dihydrogenphosphate, pyrophosphate, tripolyphosphate, phosphite, hydrogenphosphite, hypophosphite, metaphosphate, hypophosphate or superphosphate.

10. The multi-scale inorganic structure according to claim 9, characterized in that: The multi-scale inorganic structure includes a multi-scale structure with a three-dimensional morphology and a planar structure, and its size range is 50nm to 10cm; The morphology of the planar structure includes amorphous, linear, dot-shaped, circular, triangular, square, rectangular, rhombus, ellipse, quadrilateral, regular polygon, irregular polygon, fan-shaped, ring-shaped, arc-shaped, crescent-shaped, star-shaped, heart-shaped and a composite shape composed of any of the above shapes; The three-dimensional morphology includes amorphous bodies, flake bodies, cubes, spheres, ellipsoids, hollow balls, cylinders, cones, tables, polyhedrons, curved bodies, spindles, needles, particles, flowers, rings, spirals, blades, mortise and tenon shapes, and composite shapes composed of any of the above shapes.

11. The multi-scale inorganic structure according to claim 9, characterized in that: The atomic spatial arrangement of the multi-scale inorganic structure is long-range ordered or long-range disordered; The internal microstructure of the multi-scale inorganic structure includes single crystal, polycrystalline, long-range disordered structure and a combination of the above three; The single crystal and the polycrystalline structures are all equiaxed, tetragonal, trigonal, hexagonal, orthorhombic, monoclinic and triclinic, or any combination of the above crystal systems.

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