Search

CN-122008382-A - Multi-scale inorganic structure and printing manufacturing method thereof

CN122008382ACN 122008382 ACN122008382 ACN 122008382ACN-122008382-A

Abstract

The invention discloses a multi-scale inorganic structure and a printing and manufacturing method thereof, wherein the manufacturing method comprises the following steps: firstly, a cation precursor and an anion precursor are utilized to form a compact liquid phase in the presence of a molecule mediating agent and a solvent, printing fluid is extracted through a physical separation means, a molecule mediating liquid-solid conversion and printing technology is adopted to realize the printing formation of a planar structure and a three-dimensional structure, and then the printing structure is subjected to post-printing treatment to realize the multi-scale inorganic structure forming manufacture. The manufacturing method has wide inorganic salt compatibility, the wide material compatibility enables the design to be more flexible, the most suitable material system can be selected according to specific application requirements, and the multi-scale inorganic structure with excellent performance is further manufactured.

Inventors

  • WANG TIESHENG
  • WU YUEFENG
  • WANG DAZHI

Assignees

  • 大连理工大学

Dates

Publication Date
20260512
Application Date
20260323
Priority Date
20250325

Claims (12)

  1. 1.A method for printing and manufacturing a multi-scale inorganic structure, comprising the steps of: Firstly, mixing a cation precursor, an anion precursor, a molecule mediating agent and a solvent to form a mixed solution containing a compact liquid phase, then, physically separating the mixed solution to obtain printing fluid, printing the printing fluid into a planar structure/three-dimensional structure by a printing technology, solidifying and shaping the planar structure/three-dimensional structure by liquid-solid conversion of the printing fluid under the action of the molecule mediating agent to form a printing structure, and finally, performing post-printing treatment on the printing structure to finish the printing manufacture of the multi-scale inorganic structure.
  2. 2. The method of claim 1, wherein the forming of the dense liquid phase and the liquid-solid conversion of the molecular-mediated dense liquid phase comprise at least one of inorganic ionic polymerization, inorganic ionic crosslinking, and inorganic ionic polymerization crosslinking reactions; The molecular mediating agent can reversibly destroy ionic bonds in the cation precursor and the anion precursor through coordination, promote the cation precursor and the anion precursor to be converted into fluid, remodel the ionic bonds in the fluid after the molecular mediating agent is removed through post treatment, and the fluid is solidified into inorganic solid, so that the molecular mediating agent has the functions of stabilizing the fluid state of the compact liquid phase and regulating and controlling the liquid-solid conversion process in the printing fluid forming process.
  3. 3. The method of claim 1, wherein the cationic element in the cationic precursor is selected from at least one of alkali metal elements, alkaline earth metal elements, transition metal elements, main group metal elements, lanthanoid and actinoid elements, metalloid and non-metal elements, wherein the alkali metal elements comprise Li, na, K, rb, cs, the alkaline earth metal elements comprise Be, mg, ca, sr, ba, the transition metal elements comprise 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, the main group metal elements comprise Al, ga, in, sn, pb, bi, the lanthanoid and actinoid elements comprise La, ce, pr, nd, sm, eu, gd, dy, er, yb, th, U, and the metalloid and non-metal elements comprise B, si, ge, as, sb, te; The anions in the anion precursor are selected from at least one of hydroxide ions, carbonate ions, sulfate ions, carboxylate ions, chlorates ions, bromates ions, iodate ions, selenate ions, telluroates ions, azoxynates ions, arsenoates ions, antimonates ions, silicate ions, germanates ions, stannates ions, plumbates ions and sulfonate ions; The hydroxyl ions comprise OH - , the carbonate ions comprise CO 3 ² - 、HCO 3 - , the sulfate ions comprise SO 4 ² - 、HSO 4 - 、S 2 O 7 ² - 、HS 2 O 7 - 、S 2 O 8 ² - 、HS 2 O 8 - 、SO 3 ² - 、HSO 3 - 、S 2 O 3 ² - 、S 2 O 6 ² - 、HS 2 O 6 - 、S 3 O 6 ² - 、HS 3 O 6 - 、SO 5 ² - 、HSO 5 - ; the carboxylate ions comprise HCOO - 、CH 3 COO - 、C 2 O 4 ² - 、C 6 H 7 O 7 - 、C 6 H 6 O 7 ² - 、C 6 H 5 O 7 ³ - 、C 4 H 5 O 6 - 、C 4 H 4 O 6 ² - ; the chloroxide ions comprise ClO - 、ClO 2 - 、ClO 3 - 、ClO 4 - , the bromate ions comprise BrO - 、BrO 2 - 、BrO 3 - 、BrO 4 - , the iodate ions comprise IO - 、IO 2 - 、IO 3 - 、IO 4 - 、IO 6 5- , the selenate ions comprise SeO 4 2- 、SeO 3 2- , the telluroxide ions comprise TeO 3 2- 、TeO 4 2- , the azoxide ions comprise N 2 O 2 2- 、NO 2 - 、NO 3 - , the arsenoxide ions comprise AsO 3 3- 、AsO 4 3- , the antimonate ions comprise SbO 2 - 、[Sb(OH) 6 ] - , the silicate ions comprise SiO 3 2- 、SiO 4 4- 、Si 2 O 7 6- , the germanate ions comprise GeO 3 2- 、GeO 4 4- , the stannate ions Sn (OH) 6 2- , the plumbate ions comprise PbO 3 2- 、PbO 2 2- , and the sulfonate ions comprise R-SO 3 - ; The cation precursor is an inorganic salt containing the cation element; The anion precursor is selected from at least one of water and molecules generating carbonate ions, molecules generating sulfate ions, molecules generating carboxylate ions, molecules generating chlorate ions, molecules generating bromate ions, molecules generating iodate ions, molecules generating selenate ions, molecules generating telluroate ions, molecules generating azoate ions, molecules generating arsenoate ions, molecules generating antimonoate ions, molecules generating silicate ions, molecules generating germanate ions, molecules generating stannate ions, molecules generating plumbate ions, molecules generating sulfonate ions; The molecules for generating carbonate ions comprise carbonic acid, the molecules for generating the sulfate ions comprise sulfuric acid, the molecules for generating the carboxylate ions comprise formic acid, acetic acid, oxalic acid, citric acid and tartaric acid, the molecules for generating the oxychloride ions comprise hypochlorous acid, chlorous acid, chloric acid, and perchloric acid, the molecules for generating the bromate ions comprise hypobromous acid, bromous acid, and hydrobromic acid, the molecules for generating the iodate ions comprise hypoiodic acid, iodic acid and periodic acid, the molecules for generating the selenate ions comprise selenious acid and selenic acid, the molecules for generating the telluroxide ions comprise telluronium acid and telluronium acid, the molecules for generating the nitroxide ions comprise nitrous acid and nitric acid, the molecules for generating arsenical acid and arsenical acid, the molecules for generating the antimonic acid and antimonic acid, the molecules for generating the silicate ions comprise orthosilicic acid and metasilicic acid, the molecules for generating the iodate ions comprise selenic acid, the molecules for generating the stannic acid ions comprise the stannic acid and the molecules for generating the stannic acid ions.
  4. 4. The method of claim 1, wherein the method of obtaining a printing fluid is one or two of the following methods: The method comprises the steps of physically separating a mixed solution obtained after a dense liquid phase is formed by molecules, separating gel-like fluid, adding a solvent into the gel-like fluid for dilution and physical separation again, repeatedly diluting and separating for 1-50 times, and centrifugally displacing the fluid obtained after separation by using the solvent and stirring for 0-48 h to obtain printing fluid; the second method comprises the steps of physically separating the mixed solution obtained after the formation of the dense liquid phase by molecular medium, separating out gel-like fluid, centrifugally replacing the fluid obtained after separation by using a solvent, and stirring 0-48 h to obtain printing fluid; in the mixed solution, the concentration of the anion precursor and the cation precursor is 0.1M-1M, and the concentration of the molecular mediating agent is 0.1-M-10M; The viscosity of the printing fluid is 1-100000000 cp, and the mass fraction of the gel-like substance in the printing fluid is 30-99%.
  5. 5. The method according to claim 4, wherein the molecular mediator is at least one selected from the group consisting of aliphatic amines, nitrogen-containing heterocyclic substances, aromatic and aromatic ester mixed amines, amides, sulfoxides, phosphorus-containing ligands, carboxylic acids and polycarboxylic acid salts, wherein the aliphatic amines include diethylamine and triethylamine, the nitrogen-containing heterocyclic substances include pyrrole, pyridine, piperidine, pyrazine and piperazine, the aromatic and aromatic ester mixed amines include aniline, N-benzyl-N-ethylaniline, N-methylaniline and N, N-dimethylaniline, the amides include formamide, acetamide and benzamide, the sulfoxides include dimethyl sulfoxide, methyl phenyl sulfoxide, the phosphorus-containing ligands include trioctylphosphine oxide and triphenylphosphine, and the carboxylic acids and polycarboxylic acid salts include polyacrylic acid, sodium oleate, aspartic acid and glutamic acid; The solvent is selected from at least one of water, alcohols, alkanes, alkenes, alkynes, ethers, ketones, esters, halogenated hydrocarbons, aromatic hydrocarbons, nitriles, amides and sulfoxides; The alcohols comprise methanol, ethanol, N-propanol, isopropanol, glycerol, N-butanol and ethylene glycol, the alkanes comprise cyclohexane, N-hexane, N-pentane and N-heptane, the alkenes comprise styrene and cyclohexane, the alkynes comprise 1-butyne and 1-pentyne, the ethers comprise tetrahydrofuran and diethyl ether, the ketones comprise acetone, the esters comprise ethyl acetate, the halohydrocarbons comprise dichloromethane, chloroform and carbon tetrachloride, the aromatics comprise benzene, toluene and xylene, the nitriles comprise acetonitrile, the amides comprise N, N-dimethylformamide and the sulfoxides comprise dimethyl sulfoxide.
  6. 6. The method of claim 4, further comprising the step of adding a solvent to the printing fluid to control the viscosity of the printing fluid.
  7. 7. The method of claim 1, wherein the printing technique comprises electrofluidic jet printing, direct write printing, aerosol jet printing.
  8. 8. The printing manufacturing method of the multi-scale inorganic structure according to claim 7, wherein when the multi-scale inorganic structure is manufactured by adopting electrofluid jet printing, the printing fluid is used as a material, electrofluid jet printing is carried out by adopting electrofluid jet printing equipment, the parameters are that the electric field intensity is 0.5 kV/cm-3 kV/cm, the diameter of a spray head is 100-800 mu m, the distance between the spray head and a printing substrate is 0.1-5 mm, the temperature of a workbench is 20-300 ℃, the jet printing flow is 1-5 mu L/min, the speeds of X axis, Y axis and Z axis of three motion platforms of the electrofluid jet printing equipment are 0.1-20 mm/s, the jet printing environment temperature is 20-40 ℃, and the relative humidity is 40-60%; When the multi-scale inorganic structure is manufactured by adopting direct-writing printing, the printing fluid is used as a material, direct-writing printing is carried out by utilizing direct-writing printing equipment, the parameters are that the diameter of a printing nozzle is 100-800 mu m, the distance between the nozzle and a printing substrate is 0.1-2 mm, the temperature of a workbench is 20-300 ℃, the printing air pressure is 5-200 kPa, the movement speeds of an X axis, a Y axis and a Z axis of the direct-writing printing equipment are 0.1-20 mm/s, the temperature of a printing environment is 10-40 ℃, and the relative humidity is 40-60%; When the multi-scale inorganic structure is manufactured by aerosol jet printing, the printing fluid is used as a material, aerosol jet printing is performed by aerosol jet printing equipment, and the parameters are that the droplet size is 1-20 mu m, the nozzle diameter is 100-5000 mu m, the sheath air flow is 20-1000 sccm, the carrier gas flow is 10-500 sccm, the distance between a spray head and a printing substrate is 1-5 mm, the temperature of the printing substrate is 10-100 ℃, the printing speed is 0.1-50 mm/s, and the printing fluid viscosity is 1-1000 cp.
  9. 9. The method for manufacturing the multi-scale inorganic structure according to claim 4, further comprising the step of performing room temperature drying in the shade on the printing structure formed by the printing fluid before the post-treatment, wherein the drying in the shade is performed under the conditions that the printing structure is left to stand for 0 h to 7 days at room temperature and is subjected to the post-treatment after being dried in the shade sufficiently; The printing structure formed by the printing fluid obtained by the printing fluid method II comprises the following treatment steps of heat treatment and soaking treatment, wherein the heat treatment conditions are that the temperature is 50-1500 ℃, the temperature rising and falling speed is 1-30 ℃ per minute, the temperature control precision is 1 ℃, the heat treatment atmosphere is at least one of air, inert gas, oxidizing gas and reducing gas, and the soaking treatment conditions are that the inorganic structure after the heat treatment is soaked in water for 0-h days.
  10. 10. A multi-scale inorganic structure produced by the print production method of a multi-scale inorganic structure according to claim 1, wherein the composition of the multi-scale inorganic structure comprises at least one of alkali metal elements, alkaline earth metal elements, transition metal elements, main group metal elements, lanthanoid and actinoid elements, metalloid elements and non-metal elements, wherein the alkali metal elements comprise Li, na, K, rb, cs, the alkaline earth metal elements comprise Be, mg, ca, sr, ba, the transition metal elements comprise 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, the main group metal elements comprise Al, ga, in, sn, pb, bi, the lanthanoid and actinoid elements comprise La, ce, pr, nd, sm, eu, gd, dy, er, yb, th, U, the metalloid elements comprise B, si, ge, as, sb, te; The multi-scale inorganic structure is any one of oxide, hydroxide, carbonate substance, thioxoate substance, carboxylate substance, chloroxoate substance, bromate substance, iodate substance, selenate substance, telluroate substance, azoxyate substance, arsenoate substance, antimonoate substance, silicate substance, germanate substance, stannate substance, plumbate substance or sulfonate substance; The carbonate substances comprise carbonates and bicarbonates, the thioxoates comprise sulfates, bisulfate, pyrosulfate, peroxodisulfate, sulfite, bisulfite, thiosulfate, dithionite, trimellitate, peroxymonosulfate and hyposulfite, the carboxylates comprise formates, acetates, oxalates, citrates and tartrates, the chlorooxoates comprise hypochlorites, chlorites, chlorates and perchlorates, the bromoxonates comprise hypobromites, bromites, bromates and perbromites, the ioxoates comprise hypoiodites, iodites, iodides and periodates, the selenate comprises selenates and selenites, the telluronates comprise telluronates and telluronates, the azoxyates comprise hypo-nitrate, nitrite and nitrate, the arsenoates comprise arsenite and arsenate, the antimonates comprise antimonates and antimonates, the silicate substances comprise metasilicates, the silicate salts comprise metagermanate, the germanate and the germanate; The components of the multi-scale inorganic structure comprise at least one of ions contained in halogen ions, carbon-containing ions, sulfur-containing ions and nitrogen-containing ions; The halogen ion comprises F - 、Cl - 、Br - 、I - , the carbon-containing ion comprises CO 3 2- , the sulfur-containing ion comprises SO 4 2- , and the nitrogen-containing ion comprises NO 3 - .
  11. 11. The multi-scale inorganic structure of claim 10, wherein the multi-scale inorganic structure comprises a multi-scale structure having a three-dimensional morphology and a planar structure having a size in the range of 50 nm to 10 cm; The shape of the plane structure comprises an amorphous shape, a linear shape, a dot shape, a round shape, a triangle shape, a square shape, a rectangle shape, a diamond shape, an oval shape, a quadrilateral shape, a regular polygon shape, an irregular polygon shape, a fan shape, an annular shape, an arc shape, a crescent shape, a star shape, a heart shape and a composite shape formed by any of the above shapes; The three-dimensional morphology comprises an amorphous body, a sheet-shaped body, a cube, a sphere, an ellipsoid, a hollow sphere, a cylinder, a cone, a table body, a polyhedron, a curved surface body, a spindle body, a needle-shaped body, a granular body, a flower-shaped body, a ring-shaped body, a thread-shaped body, a leaf-shaped body, a mortise-tenon-shaped body and a composite shape formed by any of the above shapes.
  12. 12. The multi-scale inorganic structure of claim 10, wherein the atomic spatial arrangement of the multi-scale inorganic structure is long range order or long range disorder; The internal microstructure of the multi-scale inorganic structure is one or more of single crystal, polycrystal and long-range disordered structure; The single crystal and the polycrystalline structure are one or more of equiaxed crystal system, tetragonal crystal system, trigonal crystal system, hexagonal crystal system, orthorhombic crystal system and monoclinic crystal system.

Description

Multi-scale inorganic structure and printing manufacturing method thereof Technical Field The invention relates to the technical field of material science, in particular to a multi-scale inorganic structure and a printing manufacturing method thereof. Background Inorganic compounds are defined as compounds not related to the body (a few of which are also inorganic compounds such as water), and generally refer to compounds that do not contain carbon elements, corresponding to organic compounds, but include carbon-containing carbon oxides, carbonates, cyanides, carbides, carboranes, metal carbonyls, alkyl metals, organic ligand complexes of metals, and the like, carbon-containing species studied in inorganic chemistry, simply referred to as inorganic substances. The multi-scale inorganic structure refers to a multi-scale structure formed by a specific chemical or physical process using an inorganic substance as a constituent material. The multi-scale inorganic structure has outstanding thermal stability and chemical stability, higher mechanical strength, unique electrical and optical properties and excellent biocompatibility/biodegradability, can be used as a dielectric structure of high-end electronic devices such as ceramic dielectric capacitors, field effect transistors, micro-nano sensors and the like, and can also be applied to the fields of implantable (invasive) medical instruments, brain-computer interfaces and the like. Printing technology is a manufacturing process for constructing planar structures and three-dimensional structures by precisely depositing or adding materials layer by layer. The technology relies on a digital model to guide, materials are deposited or stacked layer by layer according to a preset program, and finally the complete molding of the prefetching structure is realized. Printing techniques can be categorized into a variety of process types according to principles, including electrohydrodynamic inkjet printing (EHD), direct write printing (DIW), aerosol Jet Printing (AJP), photo-curing printing, and the like. The printing technology is suitable for precise construction of a planar structure, can realize forming and manufacturing of a three-dimensional structure, and is widely applied to the fields of high-end manufacturing, biomedical, electronic devices, aerospace, artistic design and the like at present due to unique customization advantages and small-batch production capacity. The printing technology provides a new path for high-precision manufacturing of multi-scale inorganic structures. The current method for manufacturing the multi-scale inorganic structure mainly comprises the steps of photo-curing and printing, mixing inorganic material powder and resin into slurry, placing the slurry in a material pool, irradiating projection light spots on the surface of the slurry according to slice data preset by a computer, curing the slurry, and sintering the cured structure to remove the resin in the cured structure to obtain the required inorganic structure. However, currently, there are still technical bottlenecks that are difficult to overcome by this mainstream method. Firstly, the traditional method (such as photo-curing printing combined sintering treatment) generally relies on high molecular resin as a binder or a photosensitive matrix, organic components are required to be removed through high-temperature heat treatment (generally >1000 ℃) after printing and molding, the process is easy to cause remarkable shrinkage and cracking of the structure, the molding precision and the molding quality of the structure are limited, and meanwhile, the high molecular resin is used as the binder or the photosensitive matrix, the organic components in the structure cannot be completely removed after the high-temperature heat treatment, so that the segregation of the structural components is caused, and the uniformity of the structure is reduced. Second, the prior art materials have limited flexibility. Because the interior particles of the green body are loose, the pores are more and the density is low after the traditional ceramic is printed and molded, the particles are required to be densified by high-temperature sintering, the temperature of the traditional heat treatment process is often up to thousands of DEG C, so that heat-sensitive functional materials such as carbonate (e.g. calcium carbonate for 900 ℃ decomposition) cannot be compatible with the prior art, and the material limitation causes that the requirements of different application scenes on the composition diversity of inorganic structural materials are difficult to meet. Disclosure of Invention The invention provides a multi-scale inorganic structure and a printing and manufacturing method thereof, which are a multi-scale inorganic structure printing and manufacturing method based on formation of a dense liquid phase and liquid-solid conversion caused by molecular medium, and aim to solve the problems of high forming