3D printing ink and preparation method and application thereof
Technical Field
The invention relates to the technical field of three-dimensional structure forming, in particular to 3D printing ink and a preparation method and application thereof.
Background
In order to meet the potential demands of the consumer electronics and the internet of things for miniaturization and customization of electronic devices, the ability to implement functional oxide patterning and integration is increasingly important. However, the current micro-nano processing technology can only generally realize simple geometric figure processing through cyclic and reciprocating deposition, masking, etching and other processes, and is accompanied by a large amount of energy consumption and time cost, so that the process is difficult to expand to the customized consumption field. For this reason, a new material processing technology, i.e., 3D direct writing technology, has received extensive attention from researchers in recent years.
The concept of direct write molding was first proposed by Joseph Cesarano, national laboratory of Sandia, usa. The printing method firstly designs the required three-dimensional structure pattern by means of computer assistance, and then automatically controls a suspension conveying device which is arranged on the Z axis and consists of a needle cylinder and a needle nozzle by means of a computer. The suspension in the needle cylinder is extruded into linear fluid with accurate size from the needle mouth through pneumatic or screw pressure, meanwhile, the X-Y axis moves according to a programmed track, and the linear fluid is deposited on a motion platform, so that a first layer structure is obtained. After the formation of the first layer structure, the Z-axis motor drives the suspension conveyor to move precisely upwards to a height determined by the structural scheme, and the second layer formation is to be carried out on the first layer structure. Subsequently, a complex three-dimensional periodic structure which cannot be prepared by the traditional molding process is obtained by a layer-by-layer superposition mode. The 3D direct-writing forming technology has been shown to have an unparalleled integration capability in the field of customized electronics, especially in the fields of miniature batteries, wearable optoelectronic devices, terahertz electromagnetic structures, conformal antennas, stress-strain sensors, soft robots, and the like, by virtue of its extrusion-type deposition process characteristics, abundant material choices, and negligible substrate limitations.
Functional oxides, which are a functional material having a wide variety of classes and excellent photoelectric properties, have been widely used for producing high-performance functional electronic devices. In order to be able to achieve complex, high-density structural integration within a limited spatial scale, high precision deposition of functional oxides is necessary. Therefore, there is an urgent need to develop various types of functional oxide inks so that the inks have excellent rheological properties such as shear thinning, high elastic modulus, etc., to achieve stable extrusion flow properties of the inks over a long period of time and high-precision printability. Based on current research reports, the preparation schemes of functional oxidized inks can be largely divided into two types: sol-gel inks and colloidal suspension inks. The sol-gel ink generally contains a specific metal alkoxide, an organic solvent, a polymer stress-releasing agent, and the like. During the preparation process, the metal alkoxide can spontaneously react with water molecules through hydrolysis. Then, the hydrolyzed alkoxide is dehydrated and polycondensed under the action of a catalyst, so that chain-shaped organic-inorganic hybrid polymer gel is formed. And printing the polymer gel with a three-dimensional structure by a direct writing forming technology. In the high-temperature annealing treatment, the polymer blank is promoted to be cracked, and then the corresponding metal oxide is obtained. The method has been used for preparing titanium dioxide photonic crystals and tin doped indium oxide transparent electrodes, and the structural accuracy can reach 250nm. Nevertheless, the inks of this method are all composed of precursor polymers corresponding to the functional oxides. Therefore, in order to achieve a transition from organic to inorganic, an ablative treatment at high temperature (above 500 ℃) is unavoidable, which however would lead to an unpredictable severe shrinkage of the green body and to a severe deviation of the product structure from the design dimensions and even to failure of the electronic system at high temperatures. Another ink design strategy is based on a high solids colloidal suspension system to reduce shrinkage of the body during post-processing. Reversible fluid-gel transition is achieved by modulating the interaction forces between the particles so that the ink can successfully extrude out of the needle and maintain a three-dimensional shape thereafter. To date, this approach has been widely used for printing of various functional oxides, such as dielectric, piezoelectric, optical, conductive, magnetic, and superconductive functional oxides. However, the feature sizes of the above functional oxides are all in the hundreds of microns range. The highest printing accuracy of nano-functional oxide inks prepared by this method has heretofore been only tens of microns. For example, li et al realized direct-write printing of two-dimensional structures with an accuracy of 30 μm by preparing high-concentration barium titanate nanoparticle ink. Sun et al realize direct-writing printing of three-dimensional micro batteries by designing lithium titanate and lithium iron phosphate nanoparticle ink, and the printing precision is 30 mu m. These limitations in printing accuracy not only reduce the possibility of further fabricating high integration density functional devices, but also reduce the gain of the micro three-dimensional structure to the intrinsic physical properties of the functional oxide, which together result in very limited improvement in device performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides 3D printing ink, a preparation method and application thereof, and tin oxide nano particles are used as main components of the ink, so that high-precision direct-writing printing with colloid suspension as system ink is realized.
In a first aspect, the present invention provides a 3D printing ink comprising a tin oxide suspension;
the tin oxide suspension comprises tin oxide nano particles, and the particle size range is 50-70 nm.
Further, the tin oxide suspension also includes a solvent and a dispersant;
the solvent is deionized water, and the mass of the solvent accounts for 10% -30% of the tin oxide suspension; and/or the dispersing agent is water-soluble cationic polyelectrolyte, and the mass of the dispersing agent is 1-10% of that of the tin oxide nano particles.
Further, the dispersant is branched polyethyleneimine, and the number average molecular weight range is 600-70000 g/mol.
Further, the method further comprises the following steps: a binder, a rheology modifier, and a humectant;
the adhesive is a water-soluble linear high molecular polymer,
the rheology modifier is concentrated nitric acid or concentrated ammonia water;
the humectant is glycol or glycerol.
Further, the mass of the binder is 0.001% -0.1% of the mass of the tin oxide nano particles;
the mass of the rheological modifier is 0.1-1% of the mass of the tin oxide suspension;
the mass of the humectant is 1-3% of the mass of the tin oxide suspension.
In a second aspect, the present invention provides a method for preparing the 3D printing ink, including:
mixing a dispersing agent and tin oxide nano particles, and performing ball milling treatment to obtain a primary suspension;
and filtering the primary suspension to remove aggregates, centrifugally collecting solids, and dispersing in deionized water to obtain a tin oxide suspension.
Further, the ball milling treatment is as follows:
ball milling is carried out for 1-10 min at the rotating speed of more than 500 rpm.
Further, zirconia ball milling seeds with the diameter of 0.1-0.2 mm are adopted for ball milling, and the mass ratio of the ball milling seeds to the dispersing agent is 2-5:2-5.
Further, the filtering is:
filtering with 5-20 μm filter tip;
the centrifugation is as follows:
centrifuging for 30-60 min at a rotation speed of 5000-10000 rpm;
the tin oxide suspension liquid obtained by dispersing in deionized water is as follows:
dispersing in deionized water to obtain tin oxide suspension with solid content of 70-90%.
The invention further provides application of the 3D printing ink in printing integrated components.
Further, the integrated component is one or more of a bracket structure, a fence structure, a concentric cylinder structure or a three-dimensional gas sensor structure.
Further, after preparing the tin oxide suspension, the method further comprises the following steps:
adding a rheology modifier, and adjusting the viscosity and modulus of the tin dioxide suspension to meet the direct writing molding requirement; then adding humectant and adhesive, homogenizing the tin dioxide suspension for 10-40 min under the action of a autorotation mixer with the rotating speed of 1000-2000 rpm.
The invention further provides a 3D printing method based on the 3D printing ink, which comprises the following steps:
the 3D printing ink is filled into a syringe, and a glass needle with the diameter of 3-20 mu m is fixed on the head of the syringe. The piston is installed at the tail of the needle cylinder, and the cavity at the tail of the needle cylinder is communicated with the air pressure control device. The syringe is then fixed on the Z-axis of the printing platform. The computer controls the printing platform to move, and the air pressure controller controls the air pressure controller to apply 20-80 PSI pressure to the needle cylinder to push ink to flow out from the glass needle. The first layer structure deposition is realized at a printing rate of 0.1-1 mm/s (the general deposition substrate is selected from silicon wafer, glass sheet or special electronic components). After the first layer structure is obtained, the Z-axis is moved precisely upwards to the height determined by the structural scheme, and the printing of the second layer will take place on the first layer structure. And then preparing the complex miniature three-dimensional structure by a layer-by-layer superposition deposition mode.
In addition, the ink can be directly printed on a commercial microelectrode element, so that the three-dimensional patterning processing of the tin dioxide gas sensor is realized.
The invention has the following beneficial effects:
the invention provides tin dioxide colloid suspension ink for high-precision 3D printing, which is characterized in that tin dioxide suspension is subjected to high-energy ball milling to realize the adsorption of a dispersing agent on the surface of nano particles, printing ink with optimal viscoelasticity is obtained by high-speed centrifugation and addition of a rheology modifying reagent, integration with different electronic elements is realized by 3D direct writing, and then organic additives are removed by annealing treatment at 100-300 ℃, so that the integration of a three-dimensional tin dioxide structure in a commercial electronic element is finally realized.
The nano particles are used as the main component of the ink, so that subsequent high-temperature ablation treatment is not needed, and the damage to integrated electronic elements is reduced; secondly, the invention has higher solid content, so that the shrinkage of the blank body in the drying process can be reduced, and the consistency of the printing structure and the preset model is ensured.
In addition, the preparation scheme of the micron-sized tin dioxide 3D printing ink is provided for the first time, the material selection range of the direct-writing forming functional oxide is widened, and the printing precision of direct-writing forming is further improved. The ink formula realizes high-precision direct-writing printing with the colloid suspension liquid as system ink below 10 mu m for the first time.
Drawings
Fig. 1 is a schematic diagram of a 3D printed 16-layer three-dimensional tin dioxide support provided in example 1 of the present invention.
Fig. 2 is an enlarged cross-sectional view of a 3D printed 16-layer three-dimensional tin dioxide stent provided in example 1 of the present invention.
Fig. 3 is a schematic diagram of a two-dimensional tin dioxide fence structure obtained by 3D printing according to embodiment 2 of the present invention.
Fig. 4 is a schematic diagram of a three-dimensional tin dioxide concentric cylinder structure obtained by 3D printing according to embodiment 3 of the present invention.
Fig. 5 is a partial enlarged view of a three-dimensional tin dioxide concentric cylinder structure obtained by 3D printing according to embodiment 3 of the present invention.
Fig. 6 is a schematic diagram of a three-dimensional gas sensor structure printed on a micro-interdigital electrode according to embodiment 4 of the present invention.
FIG. 7 is a graph showing the resistance response data of the printed three-dimensional gas sensor according to example 4 of the present invention at 250℃for acetylene gas at a concentration of 10 ppm.
Fig. 8 is a graph showing the viscosity versus shear rate of the tin dioxide colloidal ink provided in example 4 of the present invention.
Fig. 9 is a graph showing the change of shear modulus with shear stress of the tin dioxide gel ink according to example 4 of the present invention.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Example 1
The present embodiment provides a process for preparing a three-dimensional tin dioxide scaffold having a minimum feature size of 20 μm, comprising:
1. 0.3g of polyethyleneimine having a molecular weight of 600g/mol is added to 30g of deionized water, and stirred at room temperature until the polyethyleneimine is completely dissolved in deionized water. Then 30g of tin dioxide nano particles and 30g of zirconia ball milling seeds with the diameter of 0.1mm are added, and the mixture is subjected to high-energy ball milling for 1min at the rotating speed of 2000rpm, so as to obtain a primary suspension with the mass fraction of 50%.
2. The primary suspension was filtered through a 20 μm filter to remove all agglomerates, and the filtered primary suspension was placed in a centrifuge tube, centrifuged at 5000rpm for 30min at 20 ℃, and the precipitate was collected and redispersed in another portion of deionized water to give a 90% high concentration tin dioxide suspension.
3. Adding 0.06g of strong ammonia water, and adjusting the viscosity and modulus of the tin dioxide suspension to meet the direct writing molding requirement. Finally, adding 0.33g of ethylene glycol and 0.01g of polyvinyl alcohol with the molecular weight of 100000g/mol, and homogenizing the tin dioxide suspension for 10min under the action of a self-rotating mixer with the rotating speed of 2000rpm to obtain the 3D printing tin dioxide colloidal ink.
4. Glass micro needles with the diameter of 20 mu m are arranged at the head part of the needle cylinder, a piston is arranged at the tail part of the needle cylinder, a computer controls a printing platform to move, meanwhile, an air pressure controller controls an air pressure control device to give 80PSI pressure to the needle cylinder, direct writing printing is carried out on a silicon wafer, the printing speed is 1mm/s, and the number of printing layers is 16. And then annealing for 2 hours in an air atmosphere at 100 ℃ to obtain the 16-layer three-dimensional tin dioxide bracket, as shown in fig. 1 and 2.
Example 2
The present embodiment provides a process for preparing a two-dimensional tin dioxide barrier structure having a minimum feature size of 3 μm, comprising:
1. 1g of polyethyleneimine having a molecular weight of 10000g/mol was added to 50g of deionized water, and stirred at room temperature until polyethyleneimine was completely dissolved in deionized water. Then 50g of tin dioxide nano particles and 50g of zirconia ball milling seeds with the diameter of 0.1mm are added, and the mixture is subjected to high-energy ball milling for 10 minutes at the rotating speed of 2000rpm, so as to obtain a primary suspension with the mass fraction of 50%.
2. The primary suspension was filtered through a 5 μm filter to remove all agglomerates, and the filtered primary suspension was placed in a centrifuge tube, centrifuged at 10000rpm for 30min at 20 ℃, and the precipitate was collected and re-dispersed in another portion of deionized water to give a 75% high concentration tin dioxide suspension.
3. And 0.7g of concentrated nitric acid, and adjusting the viscosity and the modulus of the tin dioxide suspension to meet the direct writing forming requirement. Finally adding 1g of glycerol and 0.0005g of cellulose with the molecular weight of 100000g/mol, and homogenizing the suspension for 20min under the action of a autorotation mixer with the rotating speed of 2000rpm to obtain the tin dioxide colloidal ink.
4. Glass micro-needles with the diameter of 3 mu m are arranged at the head of the needle cylinder, a piston is arranged at the tail of the needle cylinder, a computer controls the printing platform to move, meanwhile, the air pressure controller controls the air pressure control device to give 20PSI pressure to the needle cylinder, and direct writing printing is carried out on a silicon wafer, wherein the printing speed is 0.1mm/s. And then annealing at 300 ℃ for 2 hours in an air atmosphere to obtain a two-dimensional tin dioxide fence structure, as shown in fig. 3.
Example 3
This example provides a process for preparing a three-dimensional concentric cylindrical structure of tin dioxide with a minimum feature size of 8 μm, comprising:
1. 1g of polyethylenimine having a molecular weight of 70000g/mol was added to 20g of deionized water and stirred at room temperature until the polyethylenimine was completely dissolved in the deionized water. Then adding 20g of tin dioxide nano particles and 20g of zirconia ball milling seeds with the diameter of 0.1mm, and performing high-energy ball milling for 10min at the rotating speed of 2000rpm to obtain a primary suspension with the mass fraction of 50%.
2. The primary suspension was filtered through a 10 μm filter to remove all agglomerates, and the filtered primary suspension was placed in a centrifuge tube, centrifuged at 8000rpm for 40min at 20 ℃, and the precipitate was collected and redispersed in another portion of deionized water to give a 78% high concentration tin dioxide suspension.
4. 0.13g of concentrated nitric acid is added, and the viscosity and the modulus of the suspension are adjusted to meet the direct writing molding requirement. Finally, adding 0.5g of ethylene glycol and 0.001g of polyethylene glycol with the molecular weight of 200000g/mol, and homogenizing the tin dioxide suspension for 40min under the action of a autorotation mixer with the rotating speed of 1000rpm to obtain the 3D printing tin dioxide colloidal ink.
5. Glass micro needles with the diameter of 8 mu m are arranged at the head of the needle cylinder, a piston is arranged at the tail of the needle cylinder, a computer controls the printing platform to move, meanwhile, the air pressure controller controls the air pressure control device to give 50PSI pressure to the needle cylinder, and direct writing printing is carried out on a silicon wafer, wherein the printing speed is 0.1mm/s. And then annealing for 2 hours in an air atmosphere at 200 ℃ to obtain a three-dimensional tin dioxide concentric cylinder structure, as shown in fig. 4 and 5.
Example 4
The present embodiment provides a process for preparing a three-dimensional gas-sensitive layer sensor structure having a minimum feature size of 5 μm, comprising:
and is integrated with microelectrodes for gas-sensitive detection.
1. 2g of polyethyleneimine having a molecular weight of 10000g/mol are added to 20g of deionized water, and stirred at room temperature until polyethyleneimine is completely dissolved in deionized water. Then adding 20g of tin dioxide nano particles and 20g of zirconia ball milling seeds with the diameter of 0.1mm, and performing high-energy ball milling for 5min at the rotating speed of 2000rpm to obtain a primary suspension with the mass fraction of 50%.
2. The primary suspension was filtered through a 5 μm filter to remove all agglomerates, and the filtered primary suspension was placed in a centrifuge tube, centrifuged at 9000rpm for 60min at 20 ℃, and the precipitate was collected and redispersed in another portion of deionized water to give a high concentration tin dioxide suspension with a solids content of 70%.
3. 0.03g of concentrated nitric acid is added, and the viscosity and the modulus of the suspension are adjusted to meet the direct writing molding requirement. Finally, adding 0.85g of ethylene glycol and 0.02g of polypyrrolidone with molecular weight of 200000g/mol, and homogenizing the suspension for 40min under the action of a self-rotating mixer with rotation speed of 2000rpm to obtain the 3D printing tin dioxide colloidal ink.
4. Glass micro needles with the diameter of 5 mu m are arranged at the head part of the needle cylinder, a piston is arranged at the tail part of the needle cylinder, a computer controls the printing platform to move, meanwhile, the air pressure controller controls the air pressure control device to give 30PSI pressure to the needle cylinder, and direct writing printing is carried out on the micro interdigital electrode, wherein the printing speed is 0.5mm/s. And then annealed in an air atmosphere at 300 c for 2 hours to obtain a three-dimensional gas sensor structure, as shown in fig. 6. The resistance response data of the three-dimensional gas sensor to the acetylene gas with the concentration of 10ppm at 250 ℃ is shown in fig. 7, and the resistance of the three-dimensional gas sensor is obviously reduced under the action of the acetylene gas, which shows that the three-dimensional gas sensor has obvious response characteristic to the acetylene gas.
The data curve of the viscosity change along with the shear rate of the 3D printing tin dioxide colloidal ink obtained in the step 3 of the embodiment is shown in fig. 8, and the viscosity gradually decreases along with the increase of the shear rate, which indicates that the ink has remarkable shear thinning characteristics and has the capability of being smoothly extruded under high shear stress. The data curve of the shear modulus of the tin dioxide colloid ink obtained in this embodiment along with the change of the shear stress is shown in fig. 9, and it can be seen that the yield stress of the ink is about 200Pa, and when the shear stress is lower than 200Pa, the elastic modulus of the ink is far higher than the loss modulus, which indicates that the ink has remarkable self-supporting property after extrusion, and can maintain a complex three-dimensional structure without collapse.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.