CN111718507B - Super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing and manufacturing method thereof - Google Patents
Super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing and manufacturing method thereof Download PDFInfo
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Abstract
The invention discloses a super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing and a manufacturing method thereof. According to the super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing, the 3D bionic substrate is designed to be provided with the spine structure in a 3D printing mode. For example, the water collecting structure of the cactus-like or desert-like beetles and the arrangement of the sharp thorn part can further strengthen the water collecting and water transmitting functions of the device. The preparation method of the 3D printing-based super-hydrophobic and super-hydrophilic moisture collection device comprises the steps of sequentially manufacturing a layer of cuprous sulfide nanosheets on a 3D bionic substrate, covering the cuprous sulfide nanosheets with a template with uniform holes, immersing the cuprous sulfide nanosheets into a hydrophobic solution, removing a mask, immersing the cuprous sulfide nanosheets into a hydrophilic solution, or immersing the cuprous sulfide nanosheets into the hydrophilic solution, removing the mask, and immersing the cuprous sulfide nanosheets into the hydrophobic solution to obtain the 3D printing-based super-hydrophobic and super-hydrophilic moisture collection device; the preparation method is simple and easy to operate.
Description
Technical Field
The invention relates to the field of super-hydrophobic and super-hydrophilic materials, in particular to a super-hydrophobic and super-hydrophilic moisture collecting device based on 3D printing and a manufacturing method thereof.
Background
The imprinting effect is an ability to identify objects and to maintain a logical relationship with the objects. The most well known form of imprinting effect is that of young animals, particularly those birds that leave their nests immediately after hatching, acquiring similar behavioural characteristics from their adult animals. With the ability to impress, newborn animals can learn the necessary skills from stimuli that may, if not their parents, help them adapt to the living environment. For example, ducklings follow dogs to learn swimming; geese which are just hatched by hens can take the hens as learning objects; the young wolf starts barking after coming into contact with the dog, etc. Thus, a newborn animal can be said to impress an object, which is a well-known imprinting effect in the animal kingdom.
For some materials inherently possessing the proper affinity, they tend to attract molecules of similar polarity when in contact with the outside world, and on the other hand, they also have a dispersion preference for a particular solution. From this point of view, then, the imprinting ability is possessed by this class of materials, since they can fuse the properties of absorbing different materials by attracting each other.
In addition, most regions on the earth are water-deficient regions, and a large amount of water is stored in the atmosphere in the form of water vapor, so that many animals and plants in nature have the characteristic of collecting water from the atmosphere by utilizing a structure of alternating super-hydrophilic and super-hydrophobic regions, and a relatively well-known example is a beetle living in a nanometer Biya desert, and the shell of the beetle has hydrophilic protrusions and hydrophobic depressions. The water vapor in the atmosphere is liquefied thereon by the hydrophilic protrusions to form water droplets, and then the water droplets are transported to the legs through the hydrophobic regions and then drunk. The surface of the cactus has a pair of conical spines, and researches show that the spines also have the functions of water collection and water transmission. Therefore, it is important to explore whether the non-living inorganic material has the similar imprinting effect, so as to enrich the functions of the single material.
Disclosure of Invention
In order to solve the defects of the prior art, the primary object of the present invention is to provide a super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing, the moisture collection device has an imprinting effect, and has a structure in which super-hydrophobic regions and super-hydrophilic regions are alternated, the super-hydrophilic regions can collect moisture, and the super-hydrophobic regions transmit the collected moisture, so that moisture collection can be achieved. The device has simple structure and convenient use.
The second purpose of the invention is to provide a manufacturing method of the super-hydrophobic and super-hydrophilic moisture collecting device based on 3D printing, and the manufacturing method is simple and easy to operate. According to the manufacturing method, 3D printing is utilized for bionic design, and then the imprinting effect of the cuprous sulfide nano material is utilized to construct a parent-sparse interphase structure so as to collect moisture.
The primary purpose of the invention can be achieved by adopting the following technical scheme:
the utility model provides a super hydrophilic moisture collection device of super hydrophobicity based on 3D prints, includes 3D bionical basement and cuprous sulfide nanosheet, cuprous sulfide nanosheet includes the base plane of thin slice and the border position of thin slice.
Preferably, the 3D biomimetic substrate is a water collecting structure with a spike structure.
Preferably, the 3D bionic substrate is a water collecting structure of cactus-like or desert-like beetles with a spine structure.
Preferably, the base surface of the sheet is covered with a hydrophobic layer, and the edge positions of the sheet are covered with a hydrophilic layer; or the base surface of the sheet is covered with a hydrophilic layer, and the edge position of the sheet is covered with a hydrophobic layer.
The second purpose of the invention can be achieved by adopting the following technical scheme:
a preparation method of a super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing comprises the following steps:
(1) preparing a 3D bionic substrate: selecting a brass base material, and preparing a water collecting structure with a spine structure by adopting a 3D printing method; or an organic polymer substrate is selected, a water collection structure with a spine structure is prepared by a 3D printing method, and a layer of brass film is deposited on the surface of the 3D bionic substrate in an electroplating and vacuum coating mode;
(2) preparing cuprous sulfide nanosheets: etching the 3D bionic substrate in the step (1) by using concentrated acid, and immersing the 3D bionic substrate into polysulfide ion solution after being washed by clean water to obtain cuprous sulfide nanosheets/3D bionic substrate;
(3) preparation of a super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing: and (3) covering a mask with uniform holes on the cuprous sulfide nanosheet/3D bionic substrate in the step (2), immersing the cuprous sulfide nanosheet/3D bionic substrate in a hydrophobic solution, removing the mask, immersing the cuprous sulfide nanosheet/3D bionic substrate in a hydrophilic solution, or immersing the cuprous sulfide nanosheet/3D bionic substrate in the hydrophilic solution, removing the mask, and immersing the cuprous sulfide nanosheet/3D bionic substrate in a hydrophobic solution to obtain the super-hydrophobic and super-hydrophilic moisture collecting device based on 3D printing.
When a cuprous sulfide nanosheet/3D bionic substrate covered with a mask with uniform holes is immersed into a hydrophobic solution firstly and then is immersed into a hydrophilic solution, the exposed position of the mask is covered with the hydrophobic layer and has super-hydrophobic performance, and the position covered by the mask is covered with the hydrophilic layer and has super-hydrophilic performance; when a cuprous sulfide nanosheet/3D bionic substrate covered with a mask with uniform holes is immersed into a hydrophilic solution firstly and then is immersed into a hydrophobic solution, the exposed position of the mask is covered with a hydrophilic layer and has super-hydrophilic performance, and the position covered by the mask is covered with a hydrophobic layer and has super-hydrophobic performance; when the device is immersed into the hydrophilic solution firstly, the super-hydrophobic characteristic of the cuprous sulfide nanosheet/substrate device cannot be damaged, and similarly, when the device is immersed into the hydrophobic solution firstly, the super-hydrophilic characteristic of the cuprous sulfide nanosheet/substrate device cannot be damaged, and the sulfide nanosheet super-hydrophobic super-hydrophilic moisture collecting device with the imprinting effect can be obtained through the steps.
Preferably, the concentrated acid in the step (2) is concentrated hydrochloric acid, and the mass concentration is 15-35%.
Preferably, the diameter of the mask in the step (3) is 1-4 mm.
Preferably, the hydrophilic solution in the step (3) is any one of an aqueous amino acid solution, an aqueous polyvinyl alcohol solution, an aqueous polyacrylic acid solution, and an aqueous sodium polyacrylate solution.
Preferably, the concentration of the hydrophilic solution is 0.1-0.4 mol/L.
Preferably, the hydrophobic solution in the step (3) is an organic solution of long-chain alkane, and the number of carbon atoms of the long-chain alkane is more than or equal to 15; or the hydrophobic solution is an organic solution of long-chain alkane with amino at the end group, and the carbon atom number of the long-chain alkane is more than or equal to 18; or the hydrophobic solution is an organic solution of long-chain alkane with hydroxyl at the end group, and the carbon number of the long-chain alkane is more than or equal to 18.
Preferably, the concentration of the hydrophobic solution is 0.1-0.4 mol/L.
The reason why the cuprous sulfide nanosheets are selected to construct the super-hydrophobic and super-hydrophilic moisture collecting device is that the unique structure of the two-dimensional nano cuprous sulfide is found in research. Two-dimensional cuprous sulfide nanosheets exhibit two major types of surfaces: respectively the base surface of the lamella and the edge position of the lamella. The base surface of the sheet is an inert surface, which is usually most exposed and particularly stable, since it has the least number of dangling bonds distributed and has the least roughness, whereas the edge positions of the sheet have a very high polarity and are not easily exposed. This results in the base surface of the sheet being hydrophobic and the edge locations of the sheet being hydrophilic. The difference in affinity between the basal plane of the lamella and the edge position of the lamella may give the sulphide the ability to bind both low and high polarity species. In other words, the sulfide will therefore have imprinting ability with the potential to learn other material properties.
Compared with the prior art, the invention has the following beneficial effects:
1. the super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing has a bionic structure between parent and hydrophobic phases and has an imprinting effect similar to the characteristic and capability of a newborn animal to learn and simulate the surrounding environment; the device is placed in an atmospheric environment with certain humidity, the super-hydrophilic area is utilized to condense and collect moisture in the air, and the super-hydrophobic area is utilized to transmit the collected moisture. The device can also be applied to the fields of agricultural irrigation and seawater desalination.
2. According to the super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing, the 3D bionic substrate is designed to be provided with the spine structure in a 3D printing mode. For example, the water collecting structure of the cactus-like or desert-like beetles and the arrangement of the sharp thorn part can further strengthen the water collecting and water transmitting functions of the device.
3. The preparation method of the 3D printing-based super-hydrophobic and super-hydrophilic moisture collection device comprises the steps of sequentially manufacturing a layer of cuprous sulfide nanosheets on a 3D bionic substrate, covering the cuprous sulfide nanosheets with a template with uniform holes, immersing the cuprous sulfide nanosheets into a hydrophobic solution, removing a mask, immersing the cuprous sulfide nanosheets into a hydrophilic solution, or immersing the cuprous sulfide nanosheets into the hydrophilic solution, removing the mask, and immersing the cuprous sulfide nanosheets into the hydrophobic solution to obtain the 3D printing-based super-hydrophobic and super-hydrophilic moisture collection device; the preparation method is simple and easy to operate.
Drawings
Fig. 1 is a 3D printed organic polymer substrate biomimetic substrate of embodiment 1 of the present disclosure.
Fig. 2 is an SEM image of cuprous sulfide nanosheets prepared in example 1 of the present invention.
Fig. 3 is an XRD pattern of cuprous sulfide nanosheet prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1:
as shown in fig. 1, the method for manufacturing the super-hydrophobic and super-hydrophilic moisture collecting device based on 3D printing according to the embodiment includes the following steps:
(1) preparing a 3D bionic substrate: selecting high molecular polymer acrylonitrile-butadiene-styrene (ABS) as a base material, and preparing a water collection structure of the desert-like beetles by adopting a 3D printing method, wherein the specific structure is shown in figure 1;
(2) preparing a cuprous sulfide nanosheet/3D bionic substrate: depositing a layer of brass film (with Zn content of 30%) on the 3D bionic substrate in the step (1) in a vacuum evaporation mode, wherein the vacuum degree of the deposition is 10-2Pa, the evaporation temperature is 350 ℃, and the deposition time is 15 minutes; soaking the obtained 3D bionic substrate sample covered with brass in concentrated hydrochloric acid with the mass concentration of 15% for 10 minutes, taking out, placing in a polysulfide ion solution, and soaking at normal temperature for 5 minutes to obtain a cuprous sulfide nanosheet/3D bionic substrate, wherein FIG. 2 is a SEM (scanning electron microscope) image of the cuprous sulfide nanosheet, and FIG. 3 is an XRD (X-ray diffraction) image of the obtained cuprous sulfide nanosheet; the polysulfide ion solution is composed of 5 wt% of Na2S and 2 percent of sulfur solution by mass;
(3) preparation of a super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing: and (3) covering a mask with uniform holes of 2mm in diameter on the cuprous sulfide nanosheet/3D bionic substrate in the step (2), immersing the cuprous sulfide nanosheet/3D bionic substrate in 0.1mol/L of hydrophobic solution (petroleum ether solution of octadecane), removing the mask, and immersing the cuprous sulfide nanosheet/3D bionic substrate in 0.1mol/L of hydrophilic solution (amino acid aqueous solution) to obtain the super-hydrophobic and super-hydrophilic moisture collecting device based on 3D printing. At this time, the exposed positions of the mask are superhydrophobic, and the masked positions of the mask are superhydrophilic.
Of course, in the step (3), the cuprous sulfide nanosheet/3D biomimetic substrate in the step (2) can be covered with a mask with uniform holes, the mask is immersed in a hydrophilic solution (amino acid aqueous solution), the mask is removed, and the mask is immersed in a hydrophobic solution (petroleum ether solution of octadecane), wherein the exposed positions of the mask are superhydrophilic, and the covered positions of the mask are superhydrophobic.
Preferably, the 3D printing substrate in step (1) may also be an organic polymer such as polylactic acid (PLA), or a brass substrate, and if the brass substrate is directly selected, the plating process may not be performed.
Preferably, the hydrophilic solution used in this embodiment is an aqueous solution of amino acid, and through our experiments, the hydrophilic solution can be selected from any one of aqueous solutions of polyvinyl alcohol, polyacrylic acid, and sodium polyacrylate.
The hydrophobic solution adopted in the embodiment is petroleum ether solution of octadecane, and in addition, other materials with better hydrophobicity are tried, and the result shows that alkane with carbon atom number more than or equal to 15, organic amine with amino group at carbon atom number more than or equal to 18 terminal group, and alcohol with hydroxyl group at carbon atom number more than or equal to 18 terminal group can enable the sample to have good hydrophobicity.
Comparative example 1:
preparing a desert insect bionic substrate taking ABS as a base material according to the preparation method recorded in the step (1) in the embodiment 1, depositing a brass film according to the content of the step (2), omitting the subsequent imprinting step, and respectively immersing the desert insect bionic substrate into a hydrophobic solution and a hydrophilic solution according to the content of the step (3) to obtain the moisture collection device taking ABS as the base material.
Comparative example 2:
the desert insect bionic substrate using the ABS as the base material is prepared according to the preparation method described in the step (1) in the example 1, the step (2) is omitted, and the moisture collecting device using the brass-covered ABS as the base material is obtained by directly immersing the substrate into the hydrophobic solution and the hydrophilic solution respectively according to the content of the step (3).
Example 2:
for comparative illustration of the super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing manufactured in this example 1, which can improve moisture collection efficiency, accelerated moisture collection tests were performed on the super-hydrophobic and super-hydrophilic moisture collection device manufactured in this example 1, the super-hydrophobic and super-hydrophilic moisture collection device manufactured in comparative example 1, and the specific test results are shown in table 1, in a manner shown in fig. 3:
TABLE 1
The result shows that the water collecting efficiency of the super-hydrophobic and super-hydrophilic water collecting device based on 3D printing prepared by the embodiment can reach 10g/cm2h. The cuprous sulfide device with the imprinting effect based on 3D printing has obvious technical advantages in the aspect of moisture collection.
Example 3
According to the preparation method of the embodiment 1, cuprous sulfide is prepared and matched with different hydrophobic and hydrophilic materials, the moisture collection efficiency is tested, and the moisture collection efficiency result (g/h-cm) is obtained2) As in table 2.
TABLE 2
| Polyacrylamide sodium salt | Amino acids | Polyacrylic acid | Polyvinyl alcohol | |
| Alkane(s) | 15.5-16.6 | 14.8-15.5 | 12.3-13.5 | 9.1-10.8 |
| Organic amine | 14.5-15.0 | 11.2-12.7 | 9.5-9.9 | 7.8-8.9 |
| Alcohol(s) | 11.5-12.6 | 10.2-11.3 | 9.1-10.8 | 6.0-7.5 |
As can be seen from Table 2, different hydrophilic solutions have influence on the water collection effect due to the difference of the hydrophilic characteristics, and the experimental results show that under the condition of no change of other conditions, the water collection effect is that sodium polyacrylate > amino acid > polyacrylic acid > polyvinyl alcohol; under the condition of the same carbon chain length, the hydrophobic effect is alkane > organic amine > alcohol.
Example 4
Testing comparative example 1, comparative example 2 and example 1 the moisture collection device was tested for its contact angle with water.
We show that the cuprous sulfide nanosheet material has the imprinting capability through the following experiments that the water collecting devices of comparative example 1, comparative example 2 and example 1 are sequentially placed into the hydrophilic aqueous solution of the solution amino acid and then taken out, the surfaces of the water collecting devices have hydrophilic characteristics, the contact angles of the water collecting devices to water are tested to be respectively that the contact angle of a directly printed ABS substrate to water is less than 85 degrees, the contact angle of the printed ABS substrate covering brass to water is less than 90 degrees, the ABS substrate is printed, and the contact angle of the substrate with the cuprous sulfide nanosheet of a sample with imprinted cuprous sulfide to water is less than 2 degrees.
Secondly, printing an ABS substrate, and printing a cuprous sulfide sample, wherein the contact angle of the substrate with the cuprous sulfide nanosheet to water is less than 2 degrees (the sample is marked as A), if the substrate with the cuprous sulfide nanosheet is put into a hydrophobic solution such as a petroleum ether solution of octadecane and then taken out, the surface of the substrate has super-hydrophobic characteristics, the contact angle to water is tested to be more than 150 degrees and can reach 155 degrees (the sample is marked as B). Placing the obtained super-hydrophilic sample A in a hydrophobic solution such as petroleum ether solution of octadecane, and taking out, wherein the sample A is still super-hydrophilic, which shows that the hydrophilicity of the sample A can not be changed after the sample A is printed to be super-hydrophilic; similarly, if the obtained super-hydrophobic B sample is placed in a hydrophilic solution such as an amino acid aqueous solution and then taken out, the B sample still has super-hydrophobic property, which indicates that the lyophilic and hydrophobic properties of the B sample will not be changed after the B sample is printed to be super-hydrophobic. We refer to the above-mentioned properties of a material as the imprinting effect of the material.
The above description is only for the preferred embodiments of the present invention, but the protection scope of the present invention is not limited thereto, and any person skilled in the art can substitute or change the technical solution and the inventive concept of the present invention within the scope of the present invention.
Claims (8)
1. The super-hydrophobic and super-hydrophilic moisture collecting device based on 3D printing is characterized by comprising a 3D bionic substrate and cuprous sulfide nanosheets, wherein the cuprous sulfide nanosheets comprise base surfaces of slices and edge positions of the slices;
the preparation method of the 3D printing-based super-hydrophobic and super-hydrophilic moisture collection device comprises the following steps:
(1) preparing a 3D bionic substrate: selecting a brass base material, and preparing a water collecting structure with a spine structure by adopting a 3D printing method; or an organic polymer substrate is selected, a water collection structure with a spine structure is prepared by a 3D printing method, and a layer of brass film is deposited on the surface of the 3D bionic substrate in an electroplating and vacuum coating mode;
(2) preparing cuprous sulfide nanosheets: etching the 3D bionic substrate in the step (1) by using concentrated acid, and immersing the 3D bionic substrate into polysulfide ion solution after being washed by clean water to obtain cuprous sulfide nanosheets/3D bionic substrate;
(3) preparation of a super-hydrophobic and super-hydrophilic moisture collection device based on 3D printing: and (3) covering a mask with uniform holes on the cuprous sulfide nanosheet/3D bionic substrate in the step (2), immersing the cuprous sulfide nanosheet/3D bionic substrate in a hydrophobic solution, removing the mask, immersing the cuprous sulfide nanosheet/3D bionic substrate in a hydrophilic solution, or immersing the cuprous sulfide nanosheet/3D bionic substrate in the hydrophilic solution, removing the mask, and immersing the cuprous sulfide nanosheet/3D bionic substrate in a hydrophobic solution to obtain the super-hydrophobic and super-hydrophilic moisture collecting device based on 3D printing.
2. The 3D printing-based superhydrophobic and superhydrophilic moisture collection device according to claim 1, wherein the 3D biomimetic substrate is a water collecting structure with a pointed spine structure.
3. The 3D printing-based superhydrophobic and superhydrophilic moisture collection device according to claim 2, wherein the 3D biomimetic substrate is a water-collecting structure of cactus-like or desert-like beetles having a spike structure.
4. The 3D printing-based superhydrophobic and superhydrophilic moisture collection device according to claim 1, wherein a base surface of the sheet is covered with a hydrophobic layer and an edge position of the sheet is covered with a hydrophilic layer; or the base surface of the sheet is covered with a hydrophilic layer, and the edge position of the sheet is covered with a hydrophobic layer.
5. The 3D printing-based superhydrophobic and superhydrophilic moisture collection device according to claim 1, wherein the hydrophilic solution in step (3) is any one of an aqueous amino acid solution, an aqueous polyvinyl alcohol solution, an aqueous polyacrylic acid solution, and an aqueous sodium polyacrylate solution.
6. The 3D printing-based superhydrophobic and superhydrophilic moisture collection device according to claim 1, wherein the concentration of the hydrophilic solution in the step (3) is 0.1-0.4 mol/L.
7. The 3D printing-based superhydrophobic and superhydrophilic moisture collection device according to claim 1, wherein the hydrophobic solution in the step (3) is an organic solution of long-chain alkane, and the number of carbon atoms of the long-chain alkane is not less than 15; or the hydrophobic solution is an organic solution of long-chain alkane with amino at the end group, and the carbon atom number of the long-chain alkane is more than or equal to 18; or the hydrophobic solution is an organic solution of long-chain alkane with hydroxyl at the end group, and the carbon number of the long-chain alkane is more than or equal to 18.
8. The 3D printing-based superhydrophobic and superhydrophilic moisture collection device according to claim 1, wherein the concentration of the hydrophobic solution in the step (3) is 0.1-0.4 mol/L.
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