High-atomic-number nano-porous ceramic 3D direct writing forming ink base material as well as preparation method and application of high-atomic-number nano-porous ceramic 3D direct writing forming ink base material

Abstract

The invention relates to the field of nano multi-stage structured materials and 3D printing, in particular to a high-atomic-number nano porous ceramic 3D direct writing forming ink base material and a preparation method and application of the high-atomic-number nano porous ceramic 3D direct writing forming ink base material. The preparation method comprises the following steps: adding a stabilizer and water into a tetrabutyl zirconate-absolute ethyl alcohol solution to obtain a first precursor solution; adding a hydrochloric acid-absolute ethyl alcohol-water solution into a tetraethyl orthosilicate-ethyl alcohol-water solution, and heating to obtain a second precursor solution; adding the second precursor solution into the first precursor solution, and stirring until the second precursor solution and the first precursor solution are uniformly mixed to obtain a precursor mixed solution; and adding a gel accelerator into the precursor mixed solution, and heating to enable the precursor mixed solution to spontaneously perform a sol-gel process to obtain the zirconium oxide / silicon oxide ceramic-based nano-structure 3D direct-writing forming ink base material, namely the nano-composite multilevel structure 3D direct-writing forming ink base material. Compared with the prior art, the invention has the advantages of simple preparation, good stability and printability and the like.

Description

Technical Field

[0001] The present invention relates to the field of nano multi-level structured materials and 3D printing, and in particular to a high atomic number nano porous ceramic 3D direct writing ink substrate and a preparation method and application thereof. Background Art

[0002] 3D direct writing printing technology can be used to prepare materials of various materials and properties. Its application fields are very wide, including motor science, structural materials, tissue engineering, and soft robotics. There are many types of inks used in this technology, such as conductive glue, elastomer, and hydrogel. These inks have rheological properties (such as viscoelasticity, shear thinning, yield stress, etc.), which are helpful for the implementation of the 3D printing process.

[0003] At present, the research on 3D printing inks for ceramic materials has become a hot topic in the field of scientific research. There are many types of 3D printing technologies that can prepare dense structure ceramic materials, including extrusion molding, photopolymerization molding, powder bonding molding and powder sintering molding. However, despite the variety of printing methods, the density of printed materials is difficult to control, especially 3D printing of high atomic number ceramic materials at low density is very difficult. The main reason is that the formability of 3D printed parts of low-density ceramic materials is relatively poor, and shrinkage will occur during the formation of the pore structure. In addition, in order to achieve pore formation, the stability and printability of the ink are often poor, so it is urgent to develop 3D printing inks that can be used to prepare low-density ceramic materials.

[0004] In addition, metal oxides with high atomic numbers tend to have high activity, and how to introduce nanoporous structures is a difficult problem. This is mainly because the commonly used self-sacrificial template method requires post-processing processes such as heat treatment, and metal oxides with high atomic numbers often cause the pore structure to disappear due to high temperatures. The present invention aims to prepare sol-gel direct writing inks through a simple process, and nanoporous materials with complex three-dimensional shapes can be prepared without complex post-processing processes.

[0005] Patent publication number CN115028836A discloses a nano multi-level structured 3D direct writing ink substrate with controllable ink composition and a preparation method thereof, the method comprising the following steps: adding precursors 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl and 3,3',4,4'-benzophenone tetracarboxylic dianhydride to a solvent, stirring to obtain a precursor solution; adding a cross-linking agent and a dehydrating agent to the precursor solution, stirring, and then standing to obtain a nano multi-level structured 3D direct writing ink substrate with controllable ink composition. However, the raw materials involved in the preparation method have certain toxicity and their temperature resistance is relatively poor. Summary of the invention

[0006] The purpose of the present invention is to overcome the defects of the above-mentioned prior art and provide a high atomic number nanoporous ceramic 3D direct writing ink substrate with simple preparation, good stability and printability, and its preparation method and application.

[0007] The purpose of the present invention can be achieved by the following technical solutions:

[0008] One of the technical solutions of the present invention is to provide a method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate, comprising the following steps:

[0009] Adding a stabilizer and water to a tetrabutyl zirconate-anhydrous ethanol solution to obtain a first precursor solution;

[0010] Adding hydrochloric acid-anhydrous ethanol-water solution to tetraethyl orthosilicate-ethanol-water solution, and heating to obtain a second precursor solution;

[0011] Adding the second precursor solution to the first precursor solution and stirring until the mixture is uniformly mixed to obtain a precursor mixed solution;

[0012] A gel accelerator is added to the precursor mixed solution, and the solution is heated to spontaneously undergo a sol-gel process to obtain a zirconium oxide / silicon oxide ceramic-based nanostructured 3D direct writing ink substrate, namely, a nanocomposite multi-level structured 3D direct writing ink substrate.

[0013] Preferably, the stabilizer is concentrated nitric acid, with a mass fraction of 65% to 70%.

[0014] Preferably, in the first precursor solution, the volume ratio of tetrabutyl zirconate-anhydrous ethanol solution, stabilizer, and water is 10-20:3-7:1, and more preferably 13-16:3-4:1;

[0015] The mass fraction of tetrabutyl zirconate in the tetrabutyl zirconate-anhydrous ethanol solution is 40% to 60%, and more preferably 45% to 50%.

[0016] Preferably, in the second precursor solution, the mass molar ratio of tetraethyl orthosilicate in the tetraethyl orthosilicate-ethanol-water solution to hydrochloric acid in the hydrochloric acid-anhydrous ethanol-water solution is 50-100 g:1 mmol, more preferably 60-80 g:1 mmol, and even more preferably 70 g:1 mmol;

[0017] The mass volume ratio of tetraethyl orthosilicate, ethanol and water in the tetraethyl orthosilicate-ethanol-water solution is 1-5 g: 5-20 mL: 1 mL, more preferably 2-3 g: 8-12 mL: 1 mL, and even more preferably 2.5 g: 10 mL: 1 mL;

[0018] The hydrochloric acid-anhydrous ethanol-water solution includes 0.2-2 mol / L hydrochloric acid solution and anhydrous ethanol, wherein the volume ratio of the hydrochloric acid solution to the anhydrous ethanol is 1:30-50, and more preferably 0.5-1.5 mil / L hydrochloric acid solution and anhydrous ethanol, wherein the volume ratio of the hydrochloric acid solution to the anhydrous ethanol is 1:35-45, and more preferably 1 mol / L hydrochloric acid solution and anhydrous ethanol, wherein the volume ratio of the hydrochloric acid solution to the anhydrous ethanol is 1:40.

[0019] Preferably, in the precursor mixed solution, the total mass fraction of tetrabutyl zirconate and tetraethyl orthosilicate is 20% to 40%, more preferably 29.6% to 33.5%; the molar ratio of tetrabutyl zirconate to tetraethyl orthosilicate is 1:0.5 to 1.5, more preferably 1:0.56 to 1.3.

[0020] Preferably, the gel accelerator is an aqueous ammonia solution, wherein the solvent is water, and the volume ratio of the aqueous ammonia to water is 1:100-150, more preferably 1:100-110.

[0021] Preferably, the volume ratio of the gel accelerator, the first precursor solution, and the second precursor solution is 10:40-60:20-75, and more preferably 10:45-50:30-60.

[0022] Preferably, the heating temperature of the second precursor solution obtained after heating is 40-60°C, and the heating time is 0.5-2h, and more preferably the heating temperature is 45-55°C.

[0023] Preferably, the heating temperature for spontaneously performing the sol-gel process is 50-70°C, and the heating time is 0.5-1.5 h, and more preferably the heating temperature is 55-65°C.

[0024] The second technical solution of the present invention is to provide a high atomic number nanoporous ceramic 3D direct writing ink substrate, which is prepared by the preparation method.

[0025] The third technical solution of the present invention is to provide a high atomic number nanoporous ceramic 3D direct writing ink substrate for use in the field of 3D direct writing technology.

[0026] Preferably, the rheological parameters of the 3D direct writing ink substrate meet the following conditions: the storage modulus is controlled within (10 3 -10 5 )Pa, the ink satisfies the shear-thinning non-Newtonian fluid behavior.

[0027] Further preferably, under low shear (<100Pa), the storage modulus is controlled within (10 3 -10 5)Pa.

[0028] Compared with the prior art, the present invention has the following advantages:

[0029] (1) The present invention has the characteristics of simple preparation method, low cost, easy to obtain raw materials, flexible and adjustable ink composition, simple experimental operation, short reaction cycle, good processability, etc. Zirconium is a metal with a high atomic number. Due to the presence of nanoporous structure, the density of the printed part is less than 300 mg / cc. The present invention uses tetraethyl orthosilicate, which is easy to obtain and low in cost, as the first precursor, tetrabutyl zirconate with high reaction activity as the second precursor (zirconium source), concentrated nitric acid as a stabilizer, and ammonia solution as a gel accelerator. Concentrated nitric acid reduces the polymerization rate, slows down the aging process of the precursor solution, and appropriately prolongs the printable time of the ink. After adding tetraethyl orthosilicate, silicon oxide is modified on the surface of the zirconium oxide nanoskeleton through hydrolysis and condensation reaction, which enhances the formability of the material and the stability of the pore structure. Ethanol is a cheap and common solvent, and deionized water promotes the hydrolysis and condensation reaction of the sol. Compared with similar materials, the thermal stability and chemical stability of high atomic number oxides are very high, and the biocompatibility and surface potential are very high, so it can be used as a catalyst and drug carrier.

[0030] (2) The present invention combines 3D direct writing technology to print 3D structures with nano-multilevel structures, and can obtain customized structure, customized density, customized material, and customized functional new 3D structural materials, which have broad application prospects in the aerospace field requiring lightweight and high-temperature resistant materials, in the wastewater treatment field requiring high specific surface area, etc. It is precisely because of the above outstanding characteristics and advantages that the present invention has a good application prospect. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 The ink substrates prepared in Example 1, Comparative Example 2 and Comparative Example 3 are (a) Comparative Example 2, (b) Example 1, and (c) Comparative Example 3;

[0032] Figure 2 The rheological properties of the nano multi-level structured 3D direct writing ink substrate in Examples 1 to 3, wherein Figure (a) is a viscosity change curve at different shear rates, and Figure (b) is a storage modulus and loss modulus change curve at different shear stresses;

[0033] Figure 3Model diagram, actual diagram and printed grid structure of 3D direct writing of ceramic-based nano multi-level structured ink substrate, (a) badge model diagram, (b) actual diagram of badge printed in Example 1, (c) gear model diagram, (d) actual diagram of gear printed in Example 1, (e) grid structure printed in Example 1 (supercritically dried), (f) grid structure printed in Example 2 (supercritically dried);

[0034] Figure 4 This is a scanning electron microscope photograph of the 3D direct writing structure of the ceramic-based nano multi-level structured ink substrate in Example 2;

[0035] Figure 5 This is a high-magnification scanning electron microscope photograph of the 3D direct writing structure of the ceramic-based nano multi-level structured ink substrate in Example 2;

[0036] Figure 6 The nitrogen adsorption / desorption curves and pore size distribution diagrams of the nano multi-level structured 3D direct writing ink substrates in Examples 1 to 3;

[0037] Figure 7 The optical microscope photos of the fibers obtained after ZSA-40.3 in Example 3 was extruded using needles of different diameters, (a) the needle diameter used was 200 μm, (b) the needle diameter was 250 μm, (c) the needle diameter was 500 μm, and (d) the needle diameter was 600 μm;

[0038] Figure 8 Comparison diagram of the grid structures printed by comparative example 1 and example 3, (a) the state of the grid printed by comparative example 1 during the aging process, (b) the state of the grid printed by example 3 during the aging process, (c) the state of the grid of comparative example 1 after supercritical drying, (d) the state of the grid printed by example 3 after supercritical drying. DETAILED DESCRIPTION

[0039] The present invention is described in detail below in conjunction with the accompanying drawings and specific embodiments. This embodiment is implemented based on the technical solution of the present invention, and a detailed implementation method and a specific operation process are given, but the protection scope of the present invention is not limited to the following embodiments. Based on the given embodiments, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of this application.

[0040] Unless otherwise specified, the reagents, methods, instruments and equipment used in the present invention are conventional reagents, methods, instruments and equipment in the art.

[0041] Example 1

[0042] A method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate comprises the following steps:

[0043] (1) 12 g of tetrabutyl zirconate (TCI Shanghai Chemical Industry Development Co., Ltd., product code Z0016) and 11.5 g of anhydrous ethanol were fully mixed to obtain a tetrabutyl zirconate-anhydrous ethanol solution, and then 4.84 g of concentrated nitric acid (Sinopharm Chemical Reagent Co., Ltd., mass fraction 68%) and 1.8 g of deionized water were added in sequence, and the mixture was stirred at room temperature for 30 min to obtain a first precursor solution;

[0044] (2) 35 g of tetraethyl orthosilicate (Sinopharm Chemical Reagent Co., Ltd., product code 80124118) was added to 140 mL of anhydrous ethanol and 12 mL of deionized water to obtain a tetraethyl orthosilicate-ethanol-water solution, 0.5 mL of 1 mol / L hydrochloric acid was diluted with 20 mL of anhydrous ethanol to obtain a hydrochloric acid-anhydrous ethanol-water solution, the hydrochloric acid-anhydrous ethanol-water solution was added to the tetraethyl orthosilicate-ethanol-water solution, the mixture was stirred and mixed evenly, and the mixture was placed in a 50° C. oven for 60 min to obtain a second precursor solution;

[0045] (3) adding 17.3 mL of the obtained second precursor solution to 30 mL of the first precursor solution, stirring the mixture sufficiently to obtain a precursor mixed solution;

[0046] (4) Add 8 mL of an ammonia solution to the precursor mixed solution, wherein the solvent in the ammonia solution is water, and the volume ratio of ammonia solution (Sinopharm Chemical Reagent Co., Ltd., product code XW011336216024) to water is 1:100. After stirring evenly, place the mixture at 60° C. for 1 hour to allow the precursor mixed solution to spontaneously undergo a sol-gel process under the action of dilute ammonia solution to obtain a zirconium oxide / silicon oxide ceramic-based nanostructured 3D direct writing ink substrate, i.e., a nanocomposite multi-level structured 3D direct writing ink substrate, named ZSA-17.3.

[0047] Example 2

[0048] A method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate comprises the following steps:

[0049] (1) 12 g of tetrabutyl zirconate and 11.5 g of anhydrous ethanol were fully mixed to obtain a tetrabutyl zirconate-anhydrous ethanol solution, and then 4.84 g of concentrated nitric acid (mass fraction 68%) and 1.8 g of deionized water were added in sequence, and the mixture was stirred at room temperature for 30 min to obtain a first precursor solution;

[0050] (2) adding 35 g of tetraethyl orthosilicate to 140 mL of anhydrous ethanol and 12 mL of deionized water to obtain a tetraethyl orthosilicate-ethanol-water solution, diluting 0.5 mL of 1 mol / L hydrochloric acid with 20 mL of anhydrous ethanol to obtain a hydrochloric acid-anhydrous ethanol-water solution, adding the hydrochloric acid-anhydrous ethanol-water solution to the tetraethyl orthosilicate-ethanol-water solution, stirring and mixing, and placing the solution in a 50° C. oven for 60 min to obtain a second precursor solution;

[0051] (3) adding 28.8 mL of the second precursor solution to 30 mL of the first precursor solution, stirring the mixture to obtain a precursor mixed solution;

[0052] (4) Add 8 mL of an ammonia solution to the precursor mixed solution, wherein the solvent in the ammonia solution is water, and the volume ratio of ammonia solution to water is 1:121.5. After stirring evenly, place the mixture at 60°C for 1 hour to allow the precursor mixed solution to spontaneously undergo a sol-gel process under the action of dilute ammonia solution to obtain a zirconium oxide / silicon oxide ceramic-based nanostructured 3D direct writing ink substrate, i.e., a nanocomposite multi-level structured 3D direct writing ink substrate, named ZSA-28.8.

[0053] Example 3

[0054] A method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate comprises the following steps:

[0055] (1) 12 g of tetrabutyl zirconate and 11.5 g of anhydrous ethanol were fully mixed to obtain a tetrabutyl zirconate-anhydrous ethanol solution, and then 4.84 g of concentrated nitric acid (mass fraction 68%) and 1.8 g of deionized water were added in sequence, and the mixture was stirred at room temperature for 30 min to obtain a first precursor solution;

[0056] (2) adding 35 g of tetraethyl orthosilicate to 140 mL of anhydrous ethanol and 12 mL of deionized water to obtain a tetraethyl orthosilicate-ethanol-water solution, diluting 0.5 mL of 1 mol / L hydrochloric acid with 20 mL of anhydrous ethanol to obtain a hydrochloric acid-anhydrous ethanol-water solution, adding the hydrochloric acid-anhydrous ethanol-water solution to the tetraethyl orthosilicate-ethanol-water solution, stirring and mixing, and placing the solution in a 50° C. oven for 60 min to obtain a second precursor solution;

[0057] (3) adding 40.3 mL of the obtained second precursor solution to 30 mL of the first precursor solution, stirring the mixture sufficiently to obtain a precursor mixed solution;

[0058] (4) Add 8 mL of an ammonia solution to the precursor mixed solution, wherein the solvent in the ammonia solution is water, and the volume ratio of ammonia solution to water is 1:121.5. After stirring evenly, place the mixture at 60°C for 1 hour to allow the precursor mixed solution to spontaneously undergo a sol-gel process under the action of dilute ammonia solution to obtain a zirconium oxide / silicon oxide ceramic-based nanostructured 3D direct writing molding ink substrate, i.e., a nanocomposite multi-level structured 3D direct writing molding ink substrate, named ZSA-40.3.

[0059] Comparative Example 1:

[0060] Compared with Example 3, most of the steps are the same except that ethyl orthosilicate is not added.

[0061] Comparative Example 2

[0062] Compared with Example 1, most of the steps are the same, except that no heating is performed after adding ammonia water in step (4).

[0063] Comparative Example 3

[0064] Compared with Example 1, most of the steps are the same except that step (4) is heated at 60°C for 2h.

[0065] The ink substrates prepared in Example 1, Comparative Example 2 and Comparative Example 3 are as follows Figure 1 As shown, Figure 1 (a) The ink substrate obtained in Comparative Example 2 is in a sol state and cannot be used for 3D direct writing; Figure 1 (b) is the ink substrate obtained in Example 1, which is in a semi-gel state, and the ink appears as a milky quasi-solid non-Newtonian fluid; Figure 1 (c) is the ink substrate obtained in Comparative Example 3, which is in a completely gel state and lacks fluidity, and cannot be used for 3D direct writing.

[0066] Figure 2 The rheological properties of the nano multi-level structured 3D direct writing ink substrate in Examples 1 to 3, wherein Figure 2 (a) is the viscosity change curve at different shear rates. Figure 2 (b) is the storage modulus and loss modulus change curve under different shear stresses, where G' represents the storage modulus and G" represents the loss modulus. Among them, ZSA-17.3, ZSA-28.8, and ZSA-40.3 of Examples 1 to 3 all exhibit obvious shear-thinning non-Newtonian fluid behavior characteristics, which is conducive to smooth extrusion during 3D direct writing molding; at the same time, the ink has certain viscoelastic properties, and its storage modulus is greater than the loss modulus within the range of less than the yield stress, and is greater than 10 3 Pa, indicating that it has good shape retention after extrusion.

[0067] The nano multi-level structured 3D direct writing ink substrate obtained in Example 1 and Example 2 was used to carry out a 3D direct writing experiment. The needle diameter used was 410 μm and the air pressure applied by the air pump was 35 psi. Figure 3 As shown, the printed 3D structure has good fidelity and customization, and further diversified 3D structures can be obtained.

[0068] like Figure 4 , 5 As shown, using the nano multi-level structured 3D direct writing ink substrate obtained in Example 2, after supercritical drying, the printed 3D structure can be observed under an electron microscope to have an obvious extruded fiber structure, and at the same time contains a large number of multi-level pore structures from microns to nanometers, which is conducive to low density.

[0069] like Figure 6 As shown in Figure 1, the nitrogen adsorption-desorption curve of ZSA-17.3 obtained in Example 1 presents a typical type IV curve, and the pore size distribution diagram shows the material characteristics of mesopores (average pore size is 3.8 nm), and the specific surface area is 512.75 m 2 The nitrogen adsorption-desorption curve of ZSA-28.8 in Example 2 presents a typical type IV curve, and the pore size distribution diagram shows the material characteristics of mesopores (average pore size is 4.02 nm), and the specific surface area is 518.76 m 2 The nitrogen adsorption-desorption curve of ZSA-40.3 obtained in Example 3 shows a typical type IV curve, and the pore size distribution diagram shows the mesoporous material characteristics (average pore size is 4.05nm), and the specific surface area is 535.63m 2 / g.

[0070] like Figure 7 As shown, the ZSA-28.8 of Example 3 can print fiber structures of different thicknesses by using needles of different diameters, which proves that the ink obtained in the present invention is suitable for direct writing 3D printing under various precision requirements.

[0071] Figure 8 This is a comparison diagram of the grid structures printed by Comparative Example 1 and Example 3. Figure 8 (a) is the state of the grid aging process printed in comparative example 1, Figure 8 (b) is the state of the grid aging process printed in Example 3, Figure 8 (c) is the state of the grid after supercritical drying in Comparative Example 1, Figure 8(d) is the state of the grid printed in Example 3 after supercritical drying. Without adding tetraethyl orthosilicate precursor solution, the ink can still be directly written at a pressure of 30psi for 3D printing, but the print will swell during gel aging and solvent replacement, and the fragile skeleton will cause the 3D printed structure to be unable to be maintained. After supercritical drying, the print without tetraethyl orthosilicate precursor shrinks severely and the printed structure disappears completely; while the sample printed according to Example 3 maintains a good structure.

[0072] Although the present invention has been described in detail above by means of general description, specific implementation methods and tests, it is obvious to those skilled in the art that some modifications or improvements can be made to the present invention. Therefore, these modifications or improvements made without departing from the spirit of the present invention all fall within the scope of protection claimed by the present invention.

Claims

1. A method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate, characterized in that: The following steps are involved: Adding a stabilizer and water to a tetrabutyl zirconate-anhydrous ethanol solution to obtain a first precursor solution; Adding hydrochloric acid-anhydrous ethanol-water solution to tetraethyl orthosilicate-ethanol-water solution, and heating to obtain a second precursor solution; Adding the second precursor solution to the first precursor solution and stirring until the mixture is uniformly mixed to obtain a precursor mixed solution; A gel accelerator is added to the precursor mixed solution, and the solution is heated to spontaneously undergo a sol-gel process to obtain a zirconium oxide / silicon oxide ceramic-based nanostructured 3D direct writing ink substrate, namely, a nanocomposite multi-level structured 3D direct writing ink substrate.

2. The method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate according to claim 1, characterized in that: The stabilizer is concentrated nitric acid.

3. The method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate according to claim 1, characterized in that: In the first precursor solution, the volume ratio of tetrabutyl zirconate-anhydrous ethanol solution, stabilizer, and water is 10-20:3-7:1; The mass fraction of tetrabutyl zirconate in the tetrabutyl zirconate-anhydrous ethanol solution is 40% to 60%.

4. The method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate according to claim 1, characterized in that: In the second precursor solution, the mass molar ratio of tetraethyl orthosilicate in the tetraethyl orthosilicate-ethanol-water solution to hydrochloric acid in the hydrochloric acid-anhydrous ethanol-water solution is 50-100 g:1 mmol; The mass volume ratio of tetraethyl orthosilicate, ethanol and water in the tetraethyl orthosilicate-ethanol-water solution is 1-5 g: 5-20 mL: 1 mL; The hydrochloric acid-anhydrous ethanol-water solution comprises 0.2-2 mol / L hydrochloric acid solution and anhydrous ethanol, wherein the volume ratio of the hydrochloric acid solution to the anhydrous ethanol is 1:30-50.

5. The method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate according to claim 1, characterized in that: In the precursor mixed solution, the total mass fraction of tetrabutyl zirconate and tetraethyl orthosilicate is 20% to 40%, and the molar ratio of tetrabutyl zirconate to tetraethyl orthosilicate is 1:0.5 to 1.

5.

6. The method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate according to claim 1, characterized in that: The gel accelerator is an ammonia solution, wherein the solvent is water, and the volume ratio of the ammonia solution to water is 1:100-150.

7. The method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate according to claim 1, characterized in that: The volume ratio of the gel accelerator, the first precursor solution and the second precursor solution is 10:40 to 60:20 to 75.

8. The method for preparing a high atomic number nanoporous ceramic 3D direct writing ink substrate according to claim 1, characterized in that: The heating temperature of the second precursor solution obtained after heating is 40 to 60° C.; The heating temperature for spontaneously undergoing the sol-gel process is 50 to 70°C.

9. A high atomic number nanoporous ceramic 3D direct writing ink substrate, which is prepared by the preparation method according to any one of claims 1 to 8.

10. Application of a high atomic number nanoporous ceramic 3D direct writing ink substrate as claimed in claim 9 in the field of 3D direct writing technology.

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