CN111391303B - Preparation method of three-dimensional super-smooth fabric based on microfluidic 3D printing technology - Google Patents
Preparation method of three-dimensional super-smooth fabric based on microfluidic 3D printing technology Download PDFInfo
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- CN111391303B CN111391303B CN202010304461.3A CN202010304461A CN111391303B CN 111391303 B CN111391303 B CN 111391303B CN 202010304461 A CN202010304461 A CN 202010304461A CN 111391303 B CN111391303 B CN 111391303B
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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
- B29C64/10—Processes of additive manufacturing
- B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
- B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
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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
- B33Y10/00—Processes of additive manufacturing
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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
- B33Y70/00—Materials specially adapted for additive manufacturing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
- B29K2105/0058—Liquid or visquous
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/726—Fabrics
Abstract
The invention discloses a preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology, which is characterized by comprising the following steps of: the method comprises the following steps: fully mixing and emulsifying an immiscible lubricating reagent and a high polymer solution to uniformly disperse lubricating reagent micro-droplets in the high polymer solution to obtain a premixed solution; and step two, assembling the microfluidic component, fixing the liquid outlet structure of the microfluidic component on a moving shaft of the 3D printer, controlling the premixed solution to flow into a collecting pool containing collecting liquid through the microfluidic component and the 3D printer, wherein the collecting liquid and the lubricating reagent are immiscible, and the solvent of the high polymer solution is quickly volatilized and solidified to obtain the three-dimensional super-smooth fabric. The method has the advantages of simple operation, low cost, high precision, strong experiment repeatability and the like.
Description
Technical Field
The invention belongs to the field of biological materials, relates to a super-smooth fabric, and particularly relates to a preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology.
Background
Surfaces with special wettability have attracted attention for their wide application in the fields of environment, energy, biomedicine, and the like. Inspired by natural organisms such as lotus leaves, water striders, pitchers and the like, a series of researches for developing various surfaces with special infiltrative functions are proposed. Among these, liquid-imbibing porous smooth surfaces is of great interest because of their stable, defect-free repellency to a variety of liquids and liquid arrays. Based on this advantage, liquid wetting of porous smooth surfaces shows great potential in applications involving droplet operations. Although they have met with great success in various fields, such as catheter drainage and biochemical analysis, existing research aimed at wetting porous smooth surfaces with such liquids is generally based on surfaces that are flat films or large solid masses. This greatly limits their ability to manipulate droplets in complex situations. Therefore, there is an urgent need to develop a new material for droplet transportation at a complex scale.
The microfluidic technology is a novel method for efficiently preparing multifunctional materials, and particularly achieves a lot of outstanding achievements in the aspect of preparing microspheres and microfibers. Because microfluidic technology can precisely integrate and manipulate small volumes of fluid in microchannels, the prepared microspheres and microfibers have highly uniform morphology and controllable size characteristics. In addition, the microfluidic technology is combined with technologies such as photoetching, digital control, 3D printing and the like, so that the preparation mode and the application field of the functional material can be greatly expanded, and the material is endowed with more extensive functional characteristics and application. However, microfluidic technology combined with 3D printing technology has never been applied to the preparation of ultra-smooth materials.
Disclosure of Invention
The invention provides a preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology, and aims to solve the problem that the existing liquid-infiltrated porous smooth surface cannot be applied to the operation and control of complex-dimension liquid.
In order to achieve the above object, the present invention provides a method for preparing a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology, which has the following characteristics: the method comprises the following steps: fully mixing and emulsifying an immiscible lubricating reagent and a high polymer solution to uniformly disperse lubricating reagent micro-droplets in the high polymer solution to obtain a premixed solution; and step two, assembling the microfluidic component, fixing the liquid outlet structure of the microfluidic component on a moving shaft of the 3D printer, controlling the premixed solution to flow into a collecting pool containing collecting liquid through the microfluidic component and the 3D printer, wherein the collecting liquid and the lubricating reagent are immiscible, and the solvent of the high polymer solution is quickly volatilized and solidified to obtain the three-dimensional super-smooth fabric.
Further, the invention provides a preparation method of the three-dimensional super-smooth fabric based on the microfluidic 3D printing technology, and the three-dimensional super-smooth fabric can also have the following characteristics: wherein the lubricating agent is one of liquid paraffin, fluorine-silicon oil or mineral oil.
Further, the invention provides a preparation method of the three-dimensional super-smooth fabric based on the microfluidic 3D printing technology, and the three-dimensional super-smooth fabric can also have the following characteristics: wherein, the solvent of the high polymer solution is one of N, N-dimethylformamide or dimethyl sulfoxide.
Further, the invention provides a preparation method of the three-dimensional super-smooth fabric based on the microfluidic 3D printing technology, and the three-dimensional super-smooth fabric can also have the following characteristics: wherein the high polymer is one of polyurethane, polyvinylidene fluoride or polyvinyl alcohol.
Further, the invention provides a preparation method of the three-dimensional super-smooth fabric based on the microfluidic 3D printing technology, and the three-dimensional super-smooth fabric can also have the following characteristics: wherein the collecting solution is one or more mixed reagent of deionized water, ethanol, ethylene glycol or glycerol.
Further, the invention provides a preparation method of the three-dimensional super-smooth fabric based on the microfluidic 3D printing technology, and the three-dimensional super-smooth fabric can also have the following characteristics: wherein, the microfluidic component comprises a syringe, a polyethylene plastic tube, a glass capillary tube and a glass sheet; the specific method of the second step is as follows: the glass capillary tube and the glass sheet are glued and assembled to form the liquid outlet structure microfluidic chip, one end of the glass capillary tube is connected with one end of a polyethylene plastic tube, and the other end of the polyethylene plastic tube is connected with a needle head of an injector; and (3) filling the premixed solution into an injector, fixing the microfluidic chip on a moving shaft of the 3D printer, controlling the flow rate by using the peristaltic pump, starting the 3D printer after the solution forms a stable flowing state, and controlling the motion track of the microfluidic chip by using the 3D printer to enable the premixed solution to flow out according to a printing model.
Further, the invention provides a preparation method of the three-dimensional super-smooth fabric based on the microfluidic 3D printing technology, and the three-dimensional super-smooth fabric can also have the following characteristics: in the first step, the mixing and emulsifying mode of the lubricating reagent and the high polymer solution is a stirring method or an ultrasonic crushing method.
Further, the invention provides a preparation method of the three-dimensional super-smooth fabric based on the microfluidic 3D printing technology, and the three-dimensional super-smooth fabric can also have the following characteristics: wherein the volume ratio of the high polymer to the solvent in the high polymer solution is 1: 5; the volume ratio of the lubricating agent to the high polymer solution is 3: 7.
The invention has the beneficial effects that:
the invention provides a preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology, the three-dimensional super-smooth fabric is prepared by a one-step method of the microfluidic 3D printing technology, high polymer microfibers with super-smooth surfaces are assembled into a three-dimensional structure, the surfaces of the microfibers are of a relatively uniform porous structure, internal holes are communicated with one another, and lubricating oil is filled in the three-dimensional super-smooth fabric, so that the constructed three-dimensional super-smooth fabric can realize lossless and rapid transportation of liquid in a three-dimensional space and complex dimensions, can be used in the field of medical instruments such as wound drainage and the like, can improve the wound drainage efficiency, reduce infection probability and further effectively improve the wound healing efficiency.
And secondly, the three-dimensional fabric with the super-smooth surface is prepared by a one-step method, the preparation method is simple, the subsequent treatment of the fabric is not needed, the cost is lower, the product is stable, the precision is high, and the experimental repeatability is strong.
And thirdly, the three-dimensional super-smooth fabric provided by the invention has a uniform structure and controllable shape and size.
Drawings
FIG. 1 is a schematic illustration of the preparation of a three-dimensional ultra-smooth fabric;
FIG. 2 is a schematic view of a liquid droplet sliding on a three-dimensional ultra-smooth fabric surface;
FIG. 3 is a schematic view of three-dimensional transport of liquid droplets through a solid, ultra-smooth fabric;
FIG. 4 is a light and electron microscope image of the three-dimensional ultra-smooth fabric of example 1;
FIG. 5 is a wettability chart of a three-dimensional ultra-smooth fabric in example 1.
Detailed Description
The present invention is further illustrated by the following specific examples.
Example 1
The embodiment provides a preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology, which comprises the following steps:
step one, preparation of a premixed solution.
Adding 3mL of liquid paraffin and 7mL of polyurethane/N, N-dimethylformamide solution with the volume ratio of 1:5 into a black-mouth bottle, adding a stirrer, wrapping the black-mouth bottle with a sealing film, placing the black-mouth bottle on a stirring table, and stirring at the rotation speed of 1200 rpm and under the heating condition of 60 ℃ for 12 hours to fully mix and emulsify the mixture. Because the density of the liquid paraffin is less than that of the polyurethane solution, the two liquids are easy to stratify in the stirring process. Therefore, during the stirring, it is necessary to reverse the black-necked bottle back and forth so that the liquid paraffin droplets are uniformly dispersed in the polyurethane solution. Finally, a milky premix solution was prepared.
And step two, preparing the three-dimensional super-smooth fabric.
Assembling the microfluidic assembly. The microfluidic component comprises a syringe, a polyethylene plastic pipe, a glass capillary tube and a glass sheet. And (3) gluing and assembling the glass capillary tube and the glass sheet to form the liquid outlet structure microfluidic chip, wherein one end of the glass capillary tube is connected with one end of a polyethylene plastic tube, and the other end of the polyethylene plastic tube is connected with a needle head of the injector.
And (3) filling the premixed solution into an injector, setting the speed of a peristaltic pump to be 0.8mL/h, setting the parameters of a 3D printer, setting the shape of a model to be square, and setting the printing time to be 30 minutes. A plastic capsule serving as a collecting tank is placed on a platform of the 3D printer, and a mixed solution of ethanol and deionized water in a volume ratio of 3: 1 serving as a collecting liquid is filled in the collecting tank and is loaded to a position 3/4 so as to provide enough printing height. And fixing the microfluidic chip on a moving shaft of the 3D printer, and adjusting the height of the microfluidic chip to be 1 mm away from the bottom of the cuvette. The peristaltic pump is started first to enable the premixed solution to form stable fluid in the polyethylene plastic pipe, then the 3D printer is started, and the three-dimensional super-smooth fabric can be prepared in a one-step method due to the fact that the liquid paraffin and the ethanol are not mutually soluble. The preparation process is shown in figure 1.
Wherein, the glass capillary in the microfluidic chip can be selected with different inner diameters, so that microfibers (constituent units of ultra-smooth fabrics) with different diameters can be obtained. The preparation of the three-dimensional super-smooth fabric with any shape, size and structural arrangement can be realized by changing the model shape presetting program and the printing speed of the 3D printer.
The prepared three-dimensional fabric has super-smooth performance, the schematic drawing of the sliding of the liquid drops on the surface of the three-dimensional super-smooth fabric is shown in figure 2, and the schematic drawing of the three-dimensional transportation of the liquid drops through the three-dimensional super-smooth fabric is shown in figure 3.
The fabric was characterized by an optical microscope and a scanning electron microscope, and the results are shown in fig. 4, where a and d are optical microscope images of the plane and cross section of the fabric, respectively, b and e are electron microscope images of the surface and cross section of the super-smooth fiber constituting the fabric, respectively, and c and f are magnified images corresponding to b and e, respectively. The lubricating oil is uniformly distributed on the surfaces of the microfibers due to the characteristics of low surface energy and insolubility in a collecting liquid during the solvent dispersion process of a polymer solution, and is filled in the microfibers during the preparation process. As can be seen from the characterization chart, after the lubricant oil micro-droplets are removed, it can be seen that the surface and the inside of the fiber both present a porous structure. Meanwhile, the fibers forming the fabric are well connected, the surface of the fabric has a uniform porous structure, and the inner holes are communicated with each other. Therefore, the three-dimensional ultra-smooth fabric has a huge application prospect in the field of droplet control.
The results of the wettability correlation experiments on the three-dimensional ultra-smooth fabric are shown in fig. 5, wherein a is a representation image of the static contact angle and the rolling angle of the ultra-smooth fabric (i) and the common porous fabric (ii), and b is a representation of the liquid drop transportation of the ultra-smooth fabric in the two-dimensional plane (i) and the three-dimensional space (ii).
First, the static contact angles of the ultra-smooth fabric and the general porous fabric were measured, respectively, and the results are shown as a in fig. 5. Then, the ultra-smooth fabric and the general porous fabric were inclined at a certain angle, respectively, and liquids were dropped to detect the rolling angles, and the results are shown in a of fig. 5. And it can be seen that the droplets quickly slide off the surface of the ultra-smooth fabric without significant pause and residue, as shown in b (i) of fig. 5.
In addition, the feasibility of the application of the ultra-smooth fabric in the three-dimensional conveying of the liquid drops is also verified. The ultra-smooth fabric is covered on a negative pressure device, liquid drops are dripped, and then the device is opened to form negative pressure. Under the action of the negative pressure suction, one large droplet rapidly passes through the fabric without any residue, as shown in fig. 5 b (ii).
Example 2
The embodiment provides a preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology, which comprises the following steps:
step one, preparation of a premixed solution.
Adding 3mL of fluorosilicone oil and 7mL of polyvinyl alcohol/dimethyl sulfoxide solution with the volume ratio of 1:5 into a blackmouth bottle, adding a stirrer, wrapping the blackmouth bottle with a sealing film, placing the blackmouth bottle on a stirring table, and stirring at the rotation speed of 1200 rpm for 12 hours under the condition of heating at 60 ℃ to fully mix and emulsify the mixture. Because the density of the fluorosilicone oil is greater than that of the polyvinyl alcohol solution, the two liquids are easy to stratify in the stirring process. Therefore, during the stirring process, the black-mouth bottle needs to be turned upside down to uniformly disperse the droplets of fluorosilicone oil in the polyvinyl alcohol solution. Finally, a milky premix solution was prepared.
And step two, preparing the three-dimensional super-smooth fabric.
Assembling the microfluidic assembly. The microfluidic component comprises a syringe, a polyethylene plastic pipe, a glass capillary tube and a glass sheet. And (3) gluing and assembling the glass capillary tube and the glass sheet to form the liquid outlet structure microfluidic chip, wherein one end of the glass capillary tube is connected with one end of a polyethylene plastic tube, and the other end of the polyethylene plastic tube is connected with a needle head of the injector.
And (3) filling the premixed solution into an injector, setting the speed of a peristaltic pump to be 0.8mL/h, setting parameters of a 3D printer, setting the shape of a model to be circular, and setting the printing time to be 30 minutes. A plastic capsule serving as a collecting tank is placed on a platform of the 3D printer, and a mixed solution of ethanol and deionized water in a volume ratio of 3: 1 serving as a collecting liquid is filled in the collecting tank and is loaded to a position 3/4 so as to provide enough printing height. And fixing the microfluidic chip on a moving shaft of the 3D printer, and adjusting the height of the microfluidic chip to be 1 mm away from the bottom of the cuvette. The peristaltic pump is started first to enable the premixed solution to form stable fluid in the polyethylene plastic pipe, then the 3D printer is started, and the three-dimensional super-smooth fabric can be prepared in a one-step method due to the fact that the fluorosilicone oil and the ethanol are not mutually soluble.
Example 3
The embodiment provides a preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology, which comprises the following steps:
step one, preparation of a premixed solution.
Adding 3mL of mineral oil and 7mL of polyvinylidene fluoride/N, N-dimethylformamide solution with the volume ratio of 1:5 into a black-mouth bottle, adding a stirrer, wrapping the black-mouth bottle with a sealing film, placing the bottle on a stirring table, and stirring at the rotation speed of 1200 rpm and under the heating condition of 60 ℃ for 12 hours to fully mix and emulsify the mixture. Because the density of the mineral oil is less than that of the polyvinylidene fluoride solution, the two liquids are easy to delaminate in the stirring process. Therefore, during the stirring process, the black-mouth bottle needs to be inverted back and forth so that the droplets of the mineral oil are uniformly dispersed in the polyurethane solution. Finally, a milky premix solution was prepared.
And step two, preparing the three-dimensional super-smooth fabric.
Assembling the microfluidic assembly. The microfluidic component comprises a syringe, a polyethylene plastic pipe, a glass capillary tube and a glass sheet. And (3) gluing and assembling the glass capillary tube and the glass sheet to form the liquid outlet structure microfluidic chip, wherein one end of the glass capillary tube is connected with one end of a polyethylene plastic tube, and the other end of the polyethylene plastic tube is connected with a needle head of the injector.
And (3) filling the premixed solution into an injector, setting the speed of a peristaltic pump to be 0.8mL/h, setting the parameters of a 3D printer, setting the shape of a model to be square, and setting the printing time to be 30 minutes. A plastic capsule serving as a collecting tank is placed on a platform of the 3D printer, and a mixed solution of ethanol and deionized water in a volume ratio of 3: 1 serving as a collecting liquid is filled in the collecting tank and is loaded to a position 3/4 so as to provide enough printing height. And fixing the microfluidic chip on a moving shaft of the 3D printer, and adjusting the height of the microfluidic chip to be 1 mm away from the bottom of the cuvette. The peristaltic pump is started first to enable the premixed solution to form stable fluid in the polyethylene plastic pipe, then the 3D printer is started, and the three-dimensional super-smooth fabric can be prepared in a one-step method due to the fact that the liquid paraffin and the ethanol are not mutually soluble.
In this embodiment, in the step one, the lubricating agent and the high polymer solution may be mixed and emulsified by an ultrasonic crushing method; in the second step, the collecting solution may be one or a mixture of more than two of deionized water, ethanol, ethylene glycol or glycerol.
Claims (8)
1. A preparation method of a three-dimensional super-smooth fabric based on a microfluidic 3D printing technology is characterized by comprising the following steps of:
the method comprises the following steps:
fully mixing and emulsifying an immiscible lubricating reagent and a high polymer solution to uniformly disperse lubricating reagent micro-droplets in the high polymer solution to obtain a premixed solution;
and step two, assembling the microfluidic component, fixing the liquid outlet structure of the microfluidic component on a moving shaft of the 3D printer, controlling the premixed solution to flow into a collecting pool containing collecting liquid through the microfluidic component and the 3D printer, wherein the collecting liquid and the lubricating reagent are immiscible, and the solvent of the high polymer solution is quickly volatilized and solidified to obtain the three-dimensional super-smooth fabric.
2. The method for preparing the three-dimensional ultra-smooth fabric based on the microfluidic 3D printing technology according to claim 1, wherein the method comprises the following steps:
wherein, the lubricating agent is one of liquid paraffin, fluorine silicon oil or mineral oil.
3. The method for preparing the three-dimensional ultra-smooth fabric based on the microfluidic 3D printing technology according to claim 1, wherein the method comprises the following steps:
wherein the solvent of the high polymer solution is one of N, N-dimethylformamide or dimethyl sulfoxide.
4. The method for preparing the three-dimensional ultra-smooth fabric based on the microfluidic 3D printing technology according to claim 1, wherein the method comprises the following steps:
wherein the high polymer is one of polyurethane, polyvinylidene fluoride or polyvinyl alcohol.
5. The method for preparing the three-dimensional ultra-smooth fabric based on the microfluidic 3D printing technology according to claim 1, wherein the method comprises the following steps:
wherein the collecting liquid is one or more mixed reagent of deionized water, ethanol, ethylene glycol or glycerol.
6. The method for preparing the three-dimensional ultra-smooth fabric based on the microfluidic 3D printing technology according to claim 1, wherein the method comprises the following steps:
wherein, the microfluidic component comprises a syringe, a polyethylene plastic tube, a glass capillary tube and a glass sheet;
the specific method of the second step is as follows: the glass capillary tube and the glass sheet are glued and assembled to form the liquid outlet structure microfluidic chip, one end of the glass capillary tube is connected with one end of a polyethylene plastic tube, and the other end of the polyethylene plastic tube is connected with a needle head of an injector;
and (3) filling the premixed solution into an injector, fixing the microfluidic chip on a moving shaft of the 3D printer, controlling the flow rate by using the peristaltic pump, starting the 3D printer after the solution forms a stable flowing state, and controlling the motion track of the microfluidic chip by using the 3D printer so that the premixed solution flows out according to a printing model.
7. The method for preparing the three-dimensional ultra-smooth fabric based on the microfluidic 3D printing technology according to claim 1, wherein the method comprises the following steps:
in the first step, the mixing and emulsifying mode of the lubricating reagent and the high polymer solution is a stirring method or an ultrasonic crushing method.
8. The method for preparing the three-dimensional ultra-smooth fabric based on the microfluidic 3D printing technology according to claim 1, wherein the method comprises the following steps:
wherein the volume ratio of the polymer to the solvent in the polymer solution is 1: 5;
the volume ratio of the lubricating agent to the high polymer solution is 3: 7.
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| CN104769049A (en) * | 2012-07-13 | 2015-07-08 | 哈佛学院 | Multifunctional repellent materials |
| CN107740196A (en) * | 2017-10-12 | 2018-02-27 | 南京科技职业学院 | A kind of preparation method based on micro-fluidic doughnut |
| CN108367488A (en) * | 2015-11-09 | 2018-08-03 | 爱尔兰国立都柏林大学 | Method, system and equipment for three-dimensional increasing material manufacturing in liquid phase |
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| CN104769049A (en) * | 2012-07-13 | 2015-07-08 | 哈佛学院 | Multifunctional repellent materials |
| CN108367488A (en) * | 2015-11-09 | 2018-08-03 | 爱尔兰国立都柏林大学 | Method, system and equipment for three-dimensional increasing material manufacturing in liquid phase |
| CN107740196A (en) * | 2017-10-12 | 2018-02-27 | 南京科技职业学院 | A kind of preparation method based on micro-fluidic doughnut |
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