CN109249617B - 3D droplet printer and method for preparing suspension droplets by using same - Google Patents
3D droplet printer and method for preparing suspension droplets by using same Download PDFInfo
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- CN109249617B CN109249617B CN201811168233.7A CN201811168233A CN109249617B CN 109249617 B CN109249617 B CN 109249617B CN 201811168233 A CN201811168233 A CN 201811168233A CN 109249617 B CN109249617 B CN 109249617B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
- B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
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- 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
- B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
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Abstract
The invention discloses a 3D (three-dimensional) droplet printer and a method for preparing suspended droplets by using the same. The invention adopts hydrogel with shear thinning property as water phase, and has supporting effect on oil phase liquid drop suspended in the water phase. The three-dimensional motion of a printer nozzle is accurately controlled through the digital model file by adopting a 3D printing technology based on the digital model file, and meanwhile, the feeding of the oil phase in the three-dimensional space is controlled through an injection pump, so that the position of oil phase liquid drops in the three-dimensional space and the size of the liquid drops are accurately controlled. The oil phase liquid drops are arranged in a specific space mode, so that the proportion of the oil phase and the water phase can be optimized, and meanwhile, a three-dimensional model with a specific shape and formed by the oil phase liquid drops can be printed out, and the method has wide application prospects in various fields.
Description
Technical Field
The invention relates to the field of microemulsion, in particular to a method for preparing suspension droplets by using a 3D droplet printer.
Background
The suspension liquid drop is a microemulsion in which the oily liquid drop is stably suspended in the water phase for a long time, wherein the oil phase can contain various oily components, and the suspension liquid drop can be widely applied to the processing of novel materials, and the development of novel products and the application of the novel products in the fields of cosmetics, medicines, foods and the like. There are several problems with conventional systems of suspended droplets prepared by shearing methods. Firstly, a system prepared by a shearing method cannot accurately control a dispersion process, and is easy to form phase separation, so that the proportion of an oil phase in a water phase is low, and the oil phase is difficult to improve. And secondly, the system prepared by the shearing method has the advantages of non-uniform droplet size, non-uniform dispersion and disordered position, and limits the application of the system in developing new materials and designing new products.
In the present invention, a fused deposition 3D printing technique is utilized to build an object by layer-by-layer printing based on a digital model file. 3D printing techniques can convert complex three-dimensional models into a series of simple two-dimensional fabrications, and thus arbitrarily complex models can be generated without the use of molds.
According to the invention, a consumable feeding mechanism of a traditional fused deposition type 3D printer is changed into a pressure control mechanism for controlling the flow of liquid, such as an injection pump or a peristaltic pump, so that liquid drops with uniform particle size are printed in hydrogel through a printing nozzle. Compared with the method for preparing the suspended micro-droplets by a shearing method, the method for preparing the suspended micro-droplets by the 3D printer can accurately control the positions of the oily droplets in the three-dimensional space, optimize the proportion of an oil phase and a water phase by the specific arrangement of the oily droplets, and print a three-dimensional model with a specific shape by controlling the three-dimensional space position of each droplet, thereby expanding the application of the technology in various fields.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing suspended liquid drops based on a 3D printing technology, which solves the problem that the oil phase ratio is difficult to improve in the traditional suspended liquid drop preparation method by using a microfluidic technology.
To achieve the above object, the present invention provides the following solutions:
the invention discloses a 3D printer for preparing suspension liquid drops, which comprises a three-dimensional moving printing system, wherein the three-dimensional moving printing system comprises a Z-axis lifting platform, an X-axis moving mechanism, a Y-axis moving mechanism and a printing nozzle, and the X-axis moving mechanism and the Y-axis moving mechanism are used for driving the printing nozzle to realize movement in an XY plane; the Z-axis lifting platform is used for adjusting the distance between the area to be printed and the printing nozzle in the Z-axis direction; the 3D printer further comprises a pressure control mechanism and a conduit; the pressure control mechanism is connected with the printing spray head through a guide pipe.
The invention takes a horizontal plane as an XY plane, a Z direction as a direction vertical to the horizontal plane, a horizontal right direction as an X-axis positive direction, a horizontal forward direction as a Y-axis positive direction, and a vertical upward direction as a Z-axis positive direction.
Preferably, the pressure control mechanism is a syringe pump or a peristaltic pump.
Preferably, the 3D printer further comprises a tank for containing the aqueous phase; the box body is arranged on the Z-axis lifting platform, and the height of the box body in the Z-axis direction is adjusted by the Z-axis lifting platform; the box body is positioned below the printing spray head.
The invention also discloses a preparation method of the suspension liquid drop of the 3D printer, which comprises the following steps:
1) dissolving a material with shear thinning into water to obtain transparent hydrogel-like liquid as a water phase, and selecting one or more oily substances to be mixed as an oil phase;
2) placing the water phase on a Z-axis lifting platform, and providing power for a pressure control mechanism to extrude the oil phase out through a printing nozzle;
3) the printing nozzle is driven to move in an XY plane through the X-axis moving mechanism and the Y-axis moving mechanism, and the distance between the area to be printed and the printing nozzle in the Z-axis direction is adjusted through the Z-axis lifting platform, so that the movement track of the printing nozzle on the 3D printer is controlled, the working state of the pressure control mechanism is controlled, and the oil phase is sheared to obtain liquid drops dispersed into the water phase.
Preferably, the shear-thinning material may be carbomer or xanthan gum.
Preferably, the printing nozzle is an elongated hollow cylinder, one end of the elongated hollow cylinder is connected with the guide pipe, and the other end of the elongated hollow cylinder is used as a nozzle.
Preferably, the movement track of the printing nozzle is that the printing nozzle stops when moving to a position in the water phase, then the pressure control mechanism extrudes a certain amount of oil phase volume, and the printing nozzle moves to the next position after waiting for the certain amount of oil phase volume to be completely extruded.
Preferably, the oily substance can be one or a mixture of silk oil, cashmere ester or vitamin E.
The invention also discloses a three-dimensional model of a specific shape formed by micro liquid drops by controlling the moving track of the printing nozzle.
The invention also discloses a 3D liquid drop printer and a suspension liquid drop prepared by the printer, the particle size and the spatial position of the liquid drop can be accurately controlled, and the proportion of the water phase and the oil phase can be optimized to the maximum extent by adopting a specific liquid drop spatial arrangement mode. In addition, a 3D printing technology based on a digital model file is adopted, and a three-dimensional model with a specific shape and composed of liquid drops can be prepared according to requirements.
The invention has the following beneficial effects:
(1) the invention provides a suspended micro-droplet system prepared based on a 3D droplet printer, and the method is simple and easy to implement, uniform and controllable in micro-droplet particle size, and capable of accurately designing and controlling the system.
(2) The invention adopts 3D printing technology, is based on a digital model file, and can prepare a suspended micro-droplet system which is composed of droplets and has a specific three-dimensional shape according to requirements. The traditional system prepared by a shearing method has the defects of non-uniform droplet size, non-uniform dispersion, disordered position and easy phase separation. The 3D droplet printing technology can accurately control the size and the position of droplets, prepare a suspension droplet system with a specific structure, and has wide application prospect in actual production.
(3) The traditional system prepared by a shearing method cannot accurately control the dispersion process, and is easy to form phase separation, so that the proportion of an oil phase in a water phase is low, and the oil phase is difficult to improve. The invention provides a suspended micro-droplet system prepared by 3D printing, the optimal arrangement of droplets is realized by accurately controlling the position of each droplet, and the proportion of an oil phase in the suspended micro-droplet system can be greatly improved to 74% at most.
(4) According to the invention, the size of the micro-droplets can be accurately controlled by adopting 3D droplet printing, the proportion of the oil phase and the water phase is optimized, and a three-dimensional model with a specific shape and formed by the oil phase droplets is printed. Corresponding material products can be developed and designed by selecting corresponding oil phases, for example, the oil phases beneficial to the skin, such as silk oil, and the like, and the cosmetics with visual functions can be developed and designed. And for example, adopting polymerizable oil phase monomers, designing a close-packed structure through 3D droplet printing, polymerizing the oil phase monomers to form particles, and mutually connecting the particles to obtain a material model consisting of the particles.
Drawings
Fig. 1 shows the preparation of suspended micro-droplets using a modified 3D printer.
Figure 2 is a model of preparing droplets consisting of suspended micro-droplets arranged in simple cubes.
In the figure: 1. the device comprises a syringe pump, 2, a conduit, 3, a printing nozzle, 4, a stepping motor, 5, a container, 6, an aqueous phase solution and 7 serial interface lines.
Figure 3 is a model of preparing a spherical and inverted quadrangular pyramid shaped droplet with suspended micro-droplets.
Detailed Description
Referring to the attached figure 1, the preparation steps of the method adopting the invention are as follows:
the invention will be further described with reference to fig. 1 and the following examples.
The invention provides a 3D printer and a method for preparing suspended liquid drops in hydrogel by using the same, wherein the particle size and the spatial position of the liquid drops are controlled by using the 3D printer, as shown in figure 1, the 3D printer is composed of an injection pump 1, a conduit 2, a printing nozzle 3, a stepping motor 4 and a container 5. 3D printing is a technology based on a digital model file, and the propelling quantity of a three-dimensional motion system and a syringe pump of a printer can be controlled through the digital model file. The print head was immersed in the hydrogel. When the printing nozzle moves to a certain position, pausing for a few seconds, feeding a quantitative oil phase volume by the injection pump, forming microspheres in the oil phase at the printing nozzle, waiting for the quantitative oil phase to be completely extruded, moving the printing nozzle, and obtaining liquid drops suspended in the hydrogel under the action of shearing force.
The present invention will be described with reference to examples, but the present invention is not limited to the examples.
Example 1: a cylinder consisting of droplets was prepared.
The method for preparing the suspension liquid drop comprises the following specific steps:
(1) the circuitry controlling the feeding of consumables of a conventional fused deposition 3D printer is connected to the syringe pump control system through a serial interface. Selecting a needle head with the inner diameter of 0.33mm, the outer diameter of 0.63mm and the length of 15mm as a printing spray head, and connecting the printing spray head with an injection pump through a PE pipe to convey oil phase liquid.
(2) Carbomer 940 was dissolved in water and the pH adjusted to 7. A clear hydrogel was obtained as the aqueous phase. Isononyl isononanoate is selected as the oil phase.
(3) The aqueous phase was held in a strain bottle, which was then placed on the Z-axis platform.
(4) And controlling the working process of the 3D printer by compiling a digital model file to obtain a three-dimensional cylinder model consisting of oil phase liquid drops.
Example 2: suspended micro-droplet systems composed of droplets having a specific three-dimensional shape are prepared.
(1) As shown in example 1, a 3D drop printer was set up, oil and water phase materials were prepared, the water phase was placed in a beaker, and the beaker was then placed on a Z-axis platform.
(2) The working process of the 3D printer is controlled by writing a digital model file, and a three-dimensional spherical model and an inverse mapping quadrangular pyramid model (shown in figure 3) which are composed of oil phase liquid drops are obtained.
Claims (7)
1. A3D printer suspension liquid drop preparation method is disclosed, wherein the 3D printer comprises a three-dimensional moving printing system, the three-dimensional moving printing system comprises a Z-axis lifting platform, an X-axis moving mechanism, a Y-axis moving mechanism and a printing nozzle, and the X-axis moving mechanism and the Y-axis moving mechanism are used for driving the printing nozzle to realize movement in an XY plane; the Z-axis lifting platform is used for adjusting the distance between the area to be printed and the printing nozzle in the Z-axis direction; the 3D printer further comprises a pressure control mechanism and a conduit; the pressure control mechanism is connected with the printing nozzle through a guide pipe;
the method is characterized by comprising the following steps:
1) dissolving a material with shear thinning into water to obtain transparent hydrogel-like liquid as a water phase, and selecting one or more oily substances to be mixed as an oil phase;
2) placing the water phase on a Z-axis lifting platform, and providing power for a pressure control mechanism to extrude the oil phase out through a printing nozzle;
3) the printing nozzle is driven to move in an XY plane by the X-axis moving mechanism and the Y-axis moving mechanism, and the distance between the area to be printed and the printing nozzle in the Z-axis direction is adjusted by the Z-axis lifting platform, so that the movement track of the printing nozzle on the 3D printer is controlled, the working state of the pressure control mechanism is controlled, and the oil phase is sheared to obtain liquid drops dispersed into the water phase;
the movement track of the printing spray head is that the printing spray head is stopped when moving to one position in the water phase, then the pressure control mechanism extrudes a certain amount of oil phase volume, and the printing spray head moves to the next position after the certain amount of oil phase volume is completely extruded.
2. The method of claim 1, wherein the pressure control mechanism is a syringe pump or a peristaltic pump.
3. The method of claim 1, further comprising a tank for containing the aqueous phase; the box body is arranged on the Z-axis lifting platform, and the height of the box body in the Z-axis direction is adjusted by the Z-axis lifting platform; the box body is positioned below the printing spray head.
4. The method of claim 1, wherein the shear-thinning material is carbomer or xanthan gum.
5. The method of claim 1, wherein the print head is an elongated hollow cylinder having one end connected to the conduit and the other end serving as a nozzle.
6. The preparation method according to claim 1, wherein the oily substance is one or more of silk oil, cashmere ester or vitamin E.
7. The three-dimensional model prepared by the preparation method according to any one of claims 1 to 6, wherein the three-dimensional model of the specific shape consisting of the micro-droplets is obtained by controlling the movement trajectory of the printing head.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111171341B (en) * | 2019-12-31 | 2021-05-07 | 浙江大学 | Janus liquid drop with structural color based on 3D liquid drop printing and preparation method thereof |
| CN113524674B (en) * | 2021-07-07 | 2022-12-13 | 清华大学深圳国际研究生院 | Device and method for preparing three-dimensional patterned multi-material hydrogel heterostructure |
| CN113524660B (en) * | 2021-08-10 | 2022-12-13 | 烟台液秀生物科技有限公司 | High-throughput array type 3D liquid drop printing method |
| CN115042427B (en) * | 2022-06-23 | 2023-07-11 | 浙江大学 | Method for preparing heavy metal isotope label combination through 3D liquid printing at high flux |
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| CN103635252A (en) * | 2011-03-08 | 2014-03-12 | 卡普苏姆公司 | Method for forming drops of a first phase dispersed in a second phase substantially immiscible with the first phase |
| WO2017081040A1 (en) * | 2015-11-09 | 2017-05-18 | University College Dublin, National University Of Ireland, Dublin | A method, system and device for three dimensional additive manufacturing in a liquid phase |
| WO2017210298A1 (en) * | 2016-05-31 | 2017-12-07 | Northwestern University | Method for the fabrication of three-dimensional objects and apparatus for same |
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