CN115028836A - Nano multi-level structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof - Google Patents
Nano multi-level structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof Download PDFInfo
- Publication number
- CN115028836A CN115028836A CN202210824390.9A CN202210824390A CN115028836A CN 115028836 A CN115028836 A CN 115028836A CN 202210824390 A CN202210824390 A CN 202210824390A CN 115028836 A CN115028836 A CN 115028836A
- Authority
- CN
- China
- Prior art keywords
- ink
- nano
- structured
- direct
- controllable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2289—Oxides; Hydroxides of metals of cobalt
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Structural Engineering (AREA)
- Composite Materials (AREA)
- Civil Engineering (AREA)
- Ceramic Engineering (AREA)
Abstract
The invention relates to a nano multilevel structured 3D direct writing forming ink base material with controllable ink components and a preparation method thereof. The preparation method of the ink base material comprises the following steps: adding a precursor A of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and a precursor B of 3,3',4,4' -benzophenone tetracarboxylic dianhydride into 1-methyl-2-pyrrolidone to obtain a precursor solution; compared with the prior art, the material has the advantages of simple preparation method, high synthesis efficiency, flexible and adjustable ink components, good processability, nano multilevel structure and the like, and has wide application prospect in the fields of aerospace, wireless electronics, building, seawater desalination, electromagnetic protection and the like.
Description
Technical Field
The invention belongs to the field of nano multilevel structured materials and 3D printing, and particularly relates to a nano multilevel structured 3D direct writing forming ink base material with controllable ink components and a preparation method thereof.
Background
The 3D direct-writing forming printing technology can be used for preparing materials with various materials and properties, and the application fields of the technology are very wide, and the technology comprises electromechanics, structural materials, tissue engineering, soft robots and the like. The type of ink used in this technique is many, such as conductive gels, elastomers, and hydrogels, among others. These inks all have rheological properties (e.g., viscoelasticity, shear thinning, yield stress, etc.) that facilitate the implementation of the 3D printing process.
The 3D direct writing forming of the nano multilevel structured ink has the advantages of a nano hierarchical porous structure of aerogel and a customized macro structure of 3D printing, and has good application prospects in the fields of supercapacitors, thermal management, tissue engineering, aerospace and the like. The shear-thinning rheology of the ink and sufficient storage modulus are a prerequisite for 3D direct write modeling. However, the fluidity of the ink decreases with the aging of the ink until the ink cannot be squeezed out during printing.
In order to solve the above problems, it is necessary to reasonably control the aging rate of the ink so that it has a longer extrusion time in the 3D direct write molding process. Meanwhile, the change of the ink composition may affect the fluidity of the ink and may even largely cause the failure of ink formulation. The industry urgently searches for a nano multilevel structured 3D direct writing forming ink base material with controllable ink components.
Disclosure of Invention
The invention aims to overcome at least one of the defects of the prior art and provide a nano multi-level structured 3D direct writing forming ink base material with controllable ink components, which is simple in preparation method and low in cost, and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the basic idea of the invention is to realize the preparation of the nano multilevel structured ink base material which can be used for 3D direct writing forming by accurately regulating and controlling the rheological parameters of the ink precursor solution and reasonably controlling the aging rate of the ink precursor solution. Firstly, synthesizing a precursor solution by using a precursor 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl, 3',4,4' -benzophenone tetracarboxylic dianhydride and an organic solvent, then sequentially adding a cross-linking agent and a dehydrating agent, and carrying out chemical imidization for a certain time at normal temperature to obtain the nano multi-level structured ink base material for 3D direct writing forming, wherein the specific scheme is as follows:
a preparation method of a nano multi-level structured 3D direct writing forming ink base material with controllable ink components comprises the following steps:
adding precursors of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 3,3',4,4' -benzophenone tetracarboxylic dianhydride into a solvent, and stirring to obtain a precursor solution; the solvent may be 1-methyl-2-pyrrolidone.
And adding a cross-linking agent and a dehydrating agent into the precursor solution, stirring, standing at normal temperature, and performing chemical imidization for a certain time to obtain the nano multi-level structured 3D direct-writing formed ink base material with controllable ink components.
Furthermore, functional nano materials are added before the dehydrating agent is added.
Further, the molar ratio of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl to 3,3',4,4' -benzophenone tetracarboxylic dianhydride was (90-110): (90-110).
Further, the total mass fraction of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 3,3',4,4' -benzophenone tetracarboxylic dianhydride in the precursor solution is 8-12%.
Further, the cross-linking agent is 1,3, 5-tri (4-aminophenyl) benzene, and the molar ratio of the cross-linking agent to the 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl is 1 (90-110).
Further, the dehydrating agent is a mixture of acetic anhydride and pyridine, wherein the molar ratio of the acetic anhydride to the pyridine to the 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl is (2-4):1 (2-4).
The molar ratio of acetic anhydride, pyridine and 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl is m: m: 1, wherein m is 4, 3, 2, including but not limited to the above ratio.
Further, the functional nano material includes, but is not limited to, carbon nanotubes or nano cobalt oxide, and is added in an amount of 0-11% of the total mass of the precursors of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 3,3',4,4' -benzophenone tetracarboxylic dianhydride.
Further, the rheological parameters of the system meet the following conditions after being regulated and controlled: the storage modulus is controlled to be 10 3 -10 5 Pa, the ink satisfies shear-thinning non-newtonian fluid behavior.
Compared with the prior art, the invention has the following advantages:
the invention has the characteristics of simple preparation method, lower cost, easily obtained raw materials, flexible and adjustable ink components, simple experimental operation, short reaction period, good machinability and the like. On one hand, the diamine monomer 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and the dianhydride monomer 3,3',4,4' -benzophenone tetracarboxylic dianhydride which are easy to obtain and low in cost are used, the aging process of the precursor solution is slowed down by reducing the use proportion of the dehydrating agent, and the printable time of the ink is properly prolonged.
Other multifunctional nanomaterials have a dominant effect on the relevant needs of a particular field. Meanwhile, a 3D structure with a nano multistage structure is printed by combining a 3D direct writing forming technology, customized structuralization, customized density, customized material and customized functional novel 3D structure materials can be obtained, and the printing ink has wide application prospects in the fields of spaceflight requiring light high-temperature resistant materials, wireless electronics requiring low dielectric constant materials, building requiring heat insulation and preservation materials, seawater desalination requiring high evaporators, electromagnetic protection requiring electromagnetic shielding materials and the like. Due to the outstanding characteristics and advantages, the invention has better application prospect.
Drawings
FIG. 1 is a photograph of a nano-multilevel structured 3D direct-write ink substrate prepared according to the present invention;
FIG. 2 is the rheological properties of the nano-multilevel structured 3D direct write ink substrate of examples 1-3, wherein (a) is the viscosity change curve at different shear rates, and (b) is the storage modulus and loss modulus change curves at different shear stresses;
FIG. 3 is a diagram of a 3D direct writing molded object of the nano-multilevel structured ink substrate in example 2;
FIG. 4 is a scanning electron micrograph of a 3D direct write patterning structure of the nano-multilevel structured ink substrate of example 2;
FIG. 5 is a scanning electron microscope photomicrograph of the 3D direct-write molded structure of the nano-multilevel structured ink substrate of example 2;
fig. 6 is a nitrogen adsorption/desorption curve and an aperture distribution diagram of the nano multi-level structured 3D direct writing molded structure in example 2;
FIG. 7 is a graph of the change in modulus with time during imidization for the inks of examples 1-3;
FIG. 8 is a photo of a functional ink prepared by the present invention and using a nano-scale structured 3D direct writing forming ink as a substrate and additionally introducing carbon nanotubes;
fig. 9 is a rheological property of a functional ink additionally incorporating carbon nanotubes, using a nano-multi-structured 3D direct writing ink as a substrate in example 4, wherein (a) is a viscosity change curve at different shear rates, and (b) is a storage modulus and a loss modulus change curve at different shear stresses;
FIG. 10 is a diagram of a 3D direct writing formed object of the functional ink additionally introduced with carbon nanotubes using the nano multi-level structured 3D direct writing formed ink as a substrate in example 4;
fig. 11 is a scanning electron microscope photograph of a 3D direct writing formed structure of a functional ink additionally introduced with carbon nanotubes using the nano-scale structured 3D direct writing formed ink as a base material in example 4;
fig. 12 is a scanning electron microscope photomicrograph of a 3D direct writing formed structure of a functional ink additionally introduced with carbon nanotubes using a nano multi-level structured 3D direct writing formed ink as a substrate in example 4;
fig. 13 is a nitrogen adsorption/desorption curve and a pore size distribution diagram of the nano multi-level structured 3D direct writing molded structure in example 4.
Fig. 14 is a drawing of nano-multilevel structured 3D direct-write modeling ink of other functional materials in example 5.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
In the following examples, the raw materials were all commercially available materials, and the purity was chemically pure or analytically pure.
Example 1
A nano multilevel structured 3D direct writing forming ink base material with controllable ink components comprises the following specific steps:
(1) sequentially adding 1.815g of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 2.754g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride into 40mL of 1-methyl-2-pyrrolidone, and respectively stirring at normal temperature for 30min to obtain precursor solutions;
(2) adding 0.034g of cross-linking agent into the precursor mixed solution obtained in the step (1), and stirring for 30min at room temperature;
(3) adding a dehydrating agent (a mixed solution of 3.23ml of acetic anhydride and 2.75ml of pyridine with the m value of 4) into the precursor mixed solution obtained in the step (2), and stirring for 10min at room temperature;
(4) and (4) placing the precursor mixed solution obtained in the step (3) at room temperature for about 2 hours, and carrying out a chemical imidization process under the catalysis of a dehydrating agent to obtain the nano multi-structured 3D direct writing forming ink base material.
The nano multi-level structured 3D direct-writing ink substrate prepared in this example is shown in fig. 1, and the ink is a yellow quasi-solid non-newtonian fluid.
As shown in the figure2, the nano multi-level structured 3D direct-writing ink substrate (named 4: 1) obtained in example 1 shows obvious shear thinning non-newtonian fluid behavior, thereby facilitating smooth extrusion in the 3D direct-writing forming process; meanwhile, the ink has certain viscoelastic property, and the storage modulus is larger than the loss modulus and is larger than 10 in the range of less than yield stress 3 Pa, indicating that it has better shape retention after extrusion.
Example 2
A nano multilevel structured 3D direct writing forming ink base material with controllable ink components comprises the following specific steps:
(1) sequentially adding 1.815g of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 2.754g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride into 40mL of 1-methyl-2-pyrrolidone, and respectively stirring at normal temperature for 30min to obtain precursor solutions;
(2) adding 0.034g of cross-linking agent into the precursor mixed solution obtained in the step (1), and stirring for 30min at room temperature;
(3) adding a dehydrating agent (a mixed solution of 2.42ml of acetic anhydride and 2.07ml of pyridine with the m value of 3) into the precursor mixed solution obtained in the step (2), and stirring for 10min at room temperature;
(4) and (4) placing the precursor mixed solution obtained in the step (3) at room temperature for about 4 hours, and carrying out a chemical imidization process under the catalysis of a dehydrating agent to obtain the nano multi-level structured 3D direct writing forming ink base material.
As shown in fig. 2, the nano-scale structured 3D direct-writing ink substrate (named 3: 1) obtained in example 2 shows obvious shear-thinning non-newtonian fluid behavior, thereby facilitating smooth extrusion during 3D direct-writing forming process; meanwhile, the ink has certain viscoelastic property, and the storage modulus is larger than the loss modulus and is larger than 10 in the range of less than yield stress 3 Pa, indicating that it has better shape retention after extrusion.
As shown in fig. 3, when the nano multi-level structured 3D direct writing forming ink base material obtained in example 2 is used to perform a 3D direct writing forming experiment, the printed 3D structure has better fidelity and customization, and further diversified 3D structures can be obtained.
As shown in fig. 4 and 5, with the nano-scale structured 3D direct-writing ink substrate obtained in example 2, after the printed 3D structure is subjected to supercritical drying, a significant structure of extruded fiber stack can be observed under an electron microscope, and a large number of micro-to-nano-scale pore structures are included, which is beneficial to low density.
As shown in FIG. 6, after the printed 3D structure is subjected to supercritical drying by using the nano multi-level structured 3D direct writing formed ink substrate obtained in example 2, a typical IV-class curve is shown in a nitrogen adsorption and desorption curve, and a pore size distribution diagram shows the material characteristics (the center is 27.2nm) of mesopores and the specific surface area is 561.7m 2 /g。
Example 3
A nano multilevel structured 3D direct writing forming ink base material with controllable ink components comprises the following specific steps:
(1) sequentially adding 1.815g of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 2.754g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride into 40mL of 1-methyl-2-pyrrolidone, and respectively stirring for 30min at normal temperature to obtain precursor solution;
(2) adding 0.034g of cross-linking agent into the precursor mixed solution obtained in the step (1), and stirring for 30min at room temperature;
(3) adding a dehydrating agent (the m value is 2, namely the mixed solution of 1.62ml of acetic anhydride and 1.38ml of pyridine) into the precursor mixed solution obtained in the step (2), and stirring for 10min at room temperature;
(4) and (4) placing the precursor mixed solution obtained in the step (3) at room temperature for about 16 hours, and carrying out a chemical imidization process under the catalysis of a dehydrating agent to obtain the nano multi-level structured 3D direct writing forming ink base material.
As shown in fig. 2, the nano-scale structured 3D direct-write ink substrate (named 2: 1) obtained in example 3 shows obvious shear-thinning non-newtonian fluid behavior, thereby facilitating smooth extrusion during 3D direct-write formation; meanwhile, the ink has certain viscoelastic property, and the storage modulus is larger than the loss modulus and larger than the loss modulus in the range of less than yield stress10 3 Pa, indicating that it has better shape retention after extrusion.
In the preparation process of the ink, the dehydrating agent has the function of facilitating the polyamic acid to carry out chemical imidization reaction (namely, dehydrating carboxyl and peptide bonds connected on benzene rings in the polyamic acid chain to finally form five-membered rings), and similar to the function of a catalyst, the molecular chains in a reaction system are increased and connected with each other. The viscosity of the ink may be related to the amount of molecular chains in the reaction system and the degree of entanglement.
As shown in fig. 7, as the imidization process proceeds, the system modulus gradually increases, and the initial solution state with the loss modulus higher than the storage modulus is changed into the quasi-gel state with the storage modulus higher than the loss modulus; the reduction of the dehydrating agent can slow down the aging process of the ink, but the subsequent possibility of consuming longer imidization reaction time is needed; the more dehydrating agents, the faster the reaction, but the more accelerated the ink aging process, eventually leading to a shorter printable time. For the comprehensive factors such as the extrudability and the shape retention of the ink, the dosage of the dehydrating agent and the reaction time need to be strictly controlled to obtain the proper rheological property of the ink, and finally the ink meeting the printing requirement is obtained (the ink can be well extruded in the required printing time, and the good shape retention of the ink can be maintained after the extrusion). This is also true for the conditions of modulus requirements for print conformality obtained in examples 1-3, which are different in the time required for different ratios.
Example 4
A3D direct-writing forming ink base material with controllable ink components and nano multilevel structure (such as short hydroxylated multi-wall carbon nano-tubes, the inner diameter is 3-5nm, the outer diameter is 8-15nm, and the length is 0.5-2 μm) comprises the following specific steps:
(1) sequentially adding 1.815g of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 2.754g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride into 40mL of 1-methyl-2-pyrrolidone, and respectively stirring at normal temperature for 30min to obtain precursor solutions;
(2) adding 0.034g of cross-linking agent into the precursor mixed solution obtained in the step (1), and stirring for 30min at room temperature;
(3) adding 0.25g or 0.5g of carbon nano tube into the precursor mixed solution obtained in the step (2), stirring for 1h at room temperature, then adding a dehydrating agent (2.42ml of acetic anhydride and 2.07ml of pyridine mixed solution), and stirring for 10min at room temperature;
(4) and (3) placing the precursor mixed solution obtained in the step (3) at room temperature for about 6 hours, and spontaneously carrying out a chemical imidization process under the catalysis of a dehydrating agent to obtain the nano multi-stage structured 3D direct-writing formed carbon nanotube-containing ink (respectively named as PA/CNT-5.5% (0.25g) and PA/CNT-11% (0.5g) according to the amount of the added carbon nanotubes).
The nano multi-level structured 3D direct writing forming ink containing carbon nanotubes prepared in this example is shown in fig. 8, and the ink appears as a black quasi-solid non-newtonian fluid.
As shown in fig. 9, the nano multi-level structured 3D direct-writing forming ink containing carbon nanotubes obtained in example 4 has similar rheological properties to those of the inks of examples 1 to 3, and also shows obvious shear-thinning non-newtonian fluid behavior characteristics and appropriate viscoelastic properties, thereby facilitating smooth extrusion during 3D direct-writing forming and having better shape retention after extrusion.
As shown in fig. 10, when the nano multi-level structured 3D direct writing forming ink containing carbon nanotubes obtained in example 4 is used to perform a 3D direct writing forming experiment, the printed 3D structure has better fidelity and customization, and further diversified nano multi-level 3D structures containing carbon nanotubes can be obtained.
As shown in fig. 11 and 12, with the nano multi-level structured 3D direct writing forming ink containing carbon nanotubes obtained in example 4, after the printed 3D structure is subjected to supercritical drying, a significant structure of extruded fiber stack can be observed under an electron microscope, and a large number of multi-level pore structures from micrometer to nanometer are included, which is beneficial to low density.
As shown in fig. 13, after the printed 3D structure is subjected to supercritical drying, the nitrogen adsorption-desorption curve of the nano multi-level structured 3D direct-write forming ink containing the carbon nanotubes obtained in example 4 shows a typical iv-type curve, and the pore size distribution diagram shows the material characteristics of the mesopores (the center is 29.6nm (PA/CNT-5.5%), and 30.9nm (PA | r)CNT-11%)) and a specific surface area of 553.7m respectively 2 /g(PA/CNT-5.5％)、545.1m 2 /g(PA/CNT-11％)。
Example 5
A flexible nano multi-level structured 3D direct-writing forming ink base material (other functional materials are introduced, such as titanium nitride, nano cobalt oxide and the like) comprises the following specific steps:
(1) sequentially adding 1.815g of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 2.754g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride into 40mL of 1-methyl-2-pyrrolidone, and respectively stirring at normal temperature for 30min to obtain precursor solutions;
(2) adding 0.034g of cross-linking agent into the precursor mixed solution obtained in the step (1), and stirring for 30min at room temperature;
(3) adding 0.5g of titanium nitride (Ti) into the precursor mixed solution obtained in the step (2) 3 N 4 ) Or nano cobalt oxide (Co) 3 O 4 ) Stirring for 1h at room temperature, adding dehydrating agent (2.42ml acetic anhydride and 2.07ml pyridine mixed solution), and stirring for 10min at room temperature;
(4) and (4) placing the precursor mixed solution obtained in the step (3) at room temperature for about 6 hours, and carrying out a chemical imidization process under the catalysis of a dehydrating agent to obtain the nano multi-level structured 3D direct-writing formed titanium nitride or nano cobalt oxide-containing ink.
The nano multilevel structured 3D direct writing modeling ink containing titanium nitride or nano cobalt oxide prepared in this embodiment is shown in fig. 14, and the ink can be successfully converted into quasi-solid non-newtonian fluid; and other additive materials, e.g. iron oxide (Fe) 3 O 4 ) And Graphene Oxide (GO), etc., make the ink unsuccessfully transformed into quasi-solid non-newtonian fluids. Therefore, it is presumed that the obtained nano-multilevel structured 3D direct write modeling ink containing titanium nitride or nano-cobalt oxide can realize 3D direct write modeling.
The invention has the characteristics of simple preparation method, lower cost, easily obtained raw materials, flexible and adjustable ink components, simple experimental operation, short reaction period, good processability and the like. By reducing the use proportion of the dehydrating agent, the aging process of the precursor solution is slowed down, and the printable time of the ink is properly increased; meanwhile, the nano multi-level structured 3D direct writing forming ink is used as a base material, and a multifunctional nano material is additionally introduced into the ink, so that the ink has a leading effect on related requirements of a specific field. Therefore, the novel 3D structural material with customized structure, customized density and customized function can be obtained, and the novel 3D structural material has wide application prospect in the aerospace field needing light high-temperature resistant materials, the wireless electronic field needing low dielectric constant materials, the building field needing heat insulation materials, the seawater desalination field needing high-efficiency evaporators, the electromagnetic protection field needing electromagnetic shielding materials and the like.
The above-described embodiments are only for illustrating the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to implement the same. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. All equivalent changes and modifications made within the spirit of the disclosure are also covered by the protection scope of the present invention.
Claims (10)
1. A preparation method of a nano multi-level structured 3D direct writing forming ink base material with controllable ink components is characterized by comprising the following steps:
adding precursors of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 3,3',4,4' -benzophenone tetracarboxylic dianhydride into a solvent, and stirring to obtain a precursor solution;
and adding a cross-linking agent and a dehydrating agent into the precursor solution, stirring, and standing to obtain the nano multilevel structured 3D direct writing forming ink base material with controllable ink components.
2. The method for preparing the nano multilevel structured 3D direct writing forming ink base material with the controllable ink components as claimed in claim 1, wherein the functional nano material is added before the dehydrating agent is added.
3. The method for preparing a nano multi-level structured 3D direct write ink substrate with controllable ink composition as claimed in claim 1, wherein the molar ratio of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl to 3,3',4,4' -benzophenone tetracarboxylic dianhydride is (90-110): (90-110).
4. The method for preparing a nano-multilevel structured 3D direct writing ink substrate with controllable ink components according to claim 1, wherein the total mass fraction of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 3,3',4,4' -benzophenone tetracarboxylic dianhydride in the precursor solution is 8-12%.
5. The method for preparing a nano-multilevel structured 3D direct-write ink substrate according to claim 1, wherein the cross-linking agent is 1,3, 5-tris (4-aminophenyl) benzene.
6. The method for preparing the nano-multilevel structured 3D direct writing ink substrate with the controllable ink components according to claim 1, wherein the molar ratio of the crosslinking agent to the 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl is 1 (90-110).
7. The method for preparing a nano multi-stage structured 3D direct writing ink base material with controllable ink components as claimed in claim 1, wherein the dehydrating agent is a mixture of acetic anhydride and pyridine, wherein the molar ratio of acetic anhydride, pyridine and 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl is (2-4): 1.
8. The method for preparing the nano multilevel structured 3D direct writing ink substrate with controllable ink components according to claim 2, wherein the functional nano material includes but is not limited to carbon nanotubes or nano cobalt oxide.
9. The method for preparing a nano multi-level structured 3D direct writing ink base material with controllable ink components according to claim 8, wherein the functional nano material is added in an amount of 0-11% of the total mass of the precursors of 4,4' -diamino-2, 2' -dimethyl-1, 1' -biphenyl and 3,3',4,4' -benzophenone tetracarboxylic dianhydride.
10. A nano-multilevel structured 3D direct write ink substrate with controllable ink composition prepared by the method of any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210824390.9A CN115028836B (en) | 2022-07-13 | 2022-07-13 | Nanometer multistage structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210824390.9A CN115028836B (en) | 2022-07-13 | 2022-07-13 | Nanometer multistage structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115028836A true CN115028836A (en) | 2022-09-09 |
| CN115028836B CN115028836B (en) | 2023-04-28 |
Family
ID=83129039
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210824390.9A Active CN115028836B (en) | 2022-07-13 | 2022-07-13 | Nanometer multistage structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115028836B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6147374A (en) * | 1997-01-22 | 2000-11-14 | Hitachi, Ltd. | Resin-encapsulated semiconductor apparatus |
| JP2016086158A (en) * | 2014-10-22 | 2016-05-19 | セントラル硝子株式会社 | Laminate for wafer processing, temporary adhesive material for wafer processing and method of manufacturing thin wafer |
| CN107936685A (en) * | 2017-11-17 | 2018-04-20 | 同济大学 | A kind of preparation method of polyimides ink available for 3D printing |
| CN111205458A (en) * | 2020-02-21 | 2020-05-29 | 吉林奥来德光电材料股份有限公司 | Polyimide, polyimide film and preparation method thereof |
-
2022
- 2022-07-13 CN CN202210824390.9A patent/CN115028836B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6147374A (en) * | 1997-01-22 | 2000-11-14 | Hitachi, Ltd. | Resin-encapsulated semiconductor apparatus |
| JP2016086158A (en) * | 2014-10-22 | 2016-05-19 | セントラル硝子株式会社 | Laminate for wafer processing, temporary adhesive material for wafer processing and method of manufacturing thin wafer |
| CN107936685A (en) * | 2017-11-17 | 2018-04-20 | 同济大学 | A kind of preparation method of polyimides ink available for 3D printing |
| CN111205458A (en) * | 2020-02-21 | 2020-05-29 | 吉林奥来德光电材料股份有限公司 | Polyimide, polyimide film and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIANMING YANG等: ""Versatile Direct Writing of Aerogel-Based Sol-Gel Inks"", 《LANGMUIR》 * |
| MARY ANN B. MEADOR等: ""Low Dielectric Polyimide Aerogels As Substrates for Lightweight Patch Antennas"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115028836B (en) | 2023-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111925194B (en) | High-temperature-resistant high-performance aerogel composite material and preparation method thereof | |
| CN101104668B (en) | Method for preparing functional carbon nano-tube and application thereof | |
| KR20170142935A (en) | Producing method of carbon aerogel and carbon aerogel made by the same | |
| Selvi et al. | Optical, thermal, mechanical properties, and non‐isothermal degradation kinetic studies on PVA/CuO nanocomposites | |
| CN108504096B (en) | Preparation method of carbon nano tube/polymer composite material | |
| KR20130019232A (en) | Polydopamine treated graphene oxide and polymer composite containing the same | |
| CN103962074B (en) | A kind of hollow sub-micron, its preparation method and application | |
| CN111603950B (en) | Solvent-resistant bridged polysilsesquioxane nanofiltration composite membrane and preparation method thereof | |
| Rahimi-Razin et al. | Properties of matrix-grafted multi-walled carbon nanotube/poly (methyl methacrylate) nanocomposites synthesized by in situ reversible addition-fragmentation chain transfer polymerization | |
| CN108329689B (en) | Low-dielectric-constant polyimide porous film and preparation method thereof | |
| KR20190127709A (en) | Method for producing surface treated carbon nanostructures | |
| Yin et al. | Synthesis of high-performance one-dimensional polyaniline nanostructures using dodecylbenzene sulfonic acid as soft template | |
| CN111087634B (en) | Nano-composite porous polyimide film and preparation method thereof | |
| CN111943654A (en) | High-temperature-resistant and radiation-resistant aerogel composite material and preparation method thereof | |
| CN114213142A (en) | Preparation method of extruded 3D printed silicon-aluminum oxide ceramic aerogel | |
| CN115028836B (en) | Nanometer multistage structured 3D direct-writing forming ink base material with controllable ink components and preparation method thereof | |
| CN110976907A (en) | Preparation method of silver nanowire with high length-diameter ratio | |
| CN112851938B (en) | One-dimensional organic nanomaterial and preparation method thereof | |
| KR20100083391A (en) | Method of preparing conductive ink composition for printed circuit board and method of producing printed circuit board | |
| CN113818246A (en) | Preparation method of antioxidant PPS fiber | |
| KR102072914B1 (en) | A method for eco-friendly production of oxidized graphite and oxidized graphene using a hydroxylation reaction | |
| CN113637202B (en) | Bio-based polyimide-halloysite nanotube composite film and preparation method thereof | |
| CN114212777B (en) | Graphene nanosphere and preparation method and application thereof | |
| CN108192459B (en) | Heat-conducting composite material and preparation method and application thereof | |
| JP2012052043A (en) | Composite comprising metal particle and electroconductive polymer, and method of manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |