CN115970663A - Preparation method and application of super-amphiphobic titanium-based three-dimensional porous material - Google Patents
Preparation method and application of super-amphiphobic titanium-based three-dimensional porous material Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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Abstract
The invention relates to a preparation method and application of a super-amphiphobic titanium-based-three-dimensional porous material. The method comprises the following steps: selecting pure titanium powder with proper particle size, cleaning and drying; (2) A porous structure is designed by adopting a Voronoi-tessellation algorithm, and the pore diameter of the porous model accords with normal distribution; (3) And (4) adjusting the angle of the model in the printing process, and changing the quantity of slag on the surface of the porous structure to obtain the pure titanium porous material capable of realizing underwater super-oleophobic and underwater super-hydrophobic property. The printed underwater super oleophobic-oil super hydrophobic pure titanium porous material has the performance of high-efficiency switchable separation of water-in-oil emulsion and oil-in-water emulsion, and excellent mechanical stability and corrosion resistance.
Description
Technical Field
The invention belongs to the field of super-wetting materials, and particularly relates to a preparation method and application of a super-amphiphobic titanium-based three-dimensional porous material.
Background
Due to the increase of oily sewage and the frequent contamination of oil spills, oil-water separation has received worldwide attention. Inspired by nature, the super-wetting material is researched in the aspect of oil-water separation. Generally, oil/water mixtures include immiscible oil/water mixtures and oil/water emulsions (droplet sizes typically less than 20 um). Emulsified mixtures are more difficult to separate than immiscible oil/water mixtures, especially in the presence of surfactants. The implementation of emulsion separation requires smaller pore sizes at the expense of flux. In recent years, a super-hydrophobic filter membrane and an underwater super-oleophobic small-aperture filter membrane are respectively designed for separating a water-in-oil emulsion and an oil-in-water emulsion. The super-hydrophobic/super-oleophilic (oil removing) material is only suitable for separating water-in-oil emulsion, and the super-hydrophilic/underwater super-oleophobic (water removing) material comprises a TiO2 and gamma-Al 2O3 composite membrane, a silicon dioxide nanosphere coating membrane and a graphene oxide coating net, and is suitable for separating oil-in-water emulsion. It is worth noting that only one emulsion (water-in-oil or oil-in-water) can be separated on all the membranes described above. Therefore, it is highly desirable to design smart membranes that are both effective in separating surfactant-stabilized oil-in-water emulsions and efficient in separating water-in-oil emulsions.
Currently, many smart super-wetting materials can switch wettability between super-hydrophobic and super-hydrophilic under pH, electric field, temperature, light and various stimuli, and are used for controllable oil-water separation. However, the manufacturing process to obtain controlled wettability is often complex and unstable. Most of the existing methods for preparing switchable super-wetting porous materials construct a coating with hybrid micro/nano roughness on a treated grid/fabric through various processes such as spraying, solution dipping, surface etching, electro-deposition and the like; synthetic surface structures often require further chemical modification with low surface energy compounds to form switchable super-wetting surfaces. In addition to the complex multi-step processing, these methods have other inherent drawbacks that limit the performance enhancement of the oil water separation porous materials prepared therefrom. For example, during spraying or solution soaking, the mesh pores may be clogged with coating portions (e.g., nanoparticle aggregates), or worse, a coating prepared on a mesh structure by a conventional method is easily delaminated and abraded due to limited interfacial adhesion or poor adhesion of the coating to the mesh structure, thereby losing its super-wetting property. In addition, most porous material substrates with special wettability, such as metal substrate porous materials, which can be used for oil-water separation, can be corroded by acid and alkali; the fabric and fiber substrate porous materials are easy to degrade at high temperature; sponge and foam base porous materials cannot bear high pressure; furthermore, the mesh size of these commercial porous materials cannot be freely designed, they are generally manufactured according to the standard of the market, and the separation performance (e.g., liquid flux and separation efficiency) of the porous materials is limited. Therefore, a solvent-free preparation technology capable of controlling the structure and the pore size of the porous material is urgently needed, and the switchable super-wetting porous material with high wear resistance and high corrosion resistance is developed to improve the oil-water separation performance.
Disclosure of Invention
The invention aims to provide a preparation method and application of a super-amphiphobic titanium-based three-dimensional porous material.
In order to achieve the purpose, the technical scheme of the invention is as follows: a preparation method of a super-amphiphobic titanium-based three-dimensional porous material comprises the following steps:
a) Before printing, respectively cleaning metal powder by using alcohol and deionized water in an ultrasonic machine for 15 minutes, and then drying in a drier at 60 ℃ for 10 hours;
b) By using a parametric modeling method, the division of a space region is realized by controlling the seed points generated by the space, and the contour line of each cell of the Voronoi model is extracted to be used as a skeleton of the porous structure, so that the design of the irregular porous structure is realized;
c) Guiding the model in the step b) into an SLM-Solution125HL metal 3D printer computer control system, fixing a pure titanium substrate on a building platform, leveling, vacuumizing the building chamber, and filling argon; then, scattering metal powder in a) on a pure titanium substrate by adopting an automatic powder scattering system, and printing a model by using laser under the control of a computer control system;
d) After the construction process is finished, redundant powder is immediately removed from the surface of the part by using an air cylinder, and the underwater super oleophobic-oil super hydrophobic porous material capable of switching and separating the water-in-oil emulsion and the oil-in-water emulsion is prepared.
In one embodiment of the present invention, the metal powder includes: tool steel, martensitic steel, stainless steel, pure titanium and titanium alloy, aluminum alloy, nickel-based alloy, copper-based alloy, cobalt-chromium alloy; the diameter ranges from 10 to 100 um.
In one embodiment of the invention, the porous structure is a model of all shapes and sizes generated using a Voronoi model.
In one embodiment of the invention, the thickness of the metal powder is 10-30 um, the laser power is 100-400W, the laser spot is 70-100um, and the scanning speed is 200-600mm/s.
In an embodiment of the present invention, in the step (c), an angle between the upper surface of the mold and the substrate during printing is 40 to 70 °.
The invention also provides an application of the super-amphiphobic titanium-based three-dimensional porous material, and the underwater super-oleophobic-oil-bottom super-hydrophobic porous material for switchable separation of the water-in-oil emulsion and the oil-in-water emulsion, which is prepared by the preparation method, is applied to the switchable separation of the water-in-oil emulsion and the oil-in-water emulsion.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through reasonably designing printing parameters and adopting a metastable state theory in a solid-oil-water system, thermodynamic contradiction is avoided, and SLM-3DTi shows the oil super-hydrophobicity and the water super-oleophobicity. Under the condition of no continuous external stimulation, only alternate drying and washing are needed, the SLM-3DTi wettability can be reversibly switched between underwater super-oleophobic property and underwater super-hydrophobic property, so that switchable oil-water separation is realized, the separation efficiency is up to 99.8%, and the flux is more than 2000L/m 2 h. In addition, the pure titanium microspheres are firmly distributed on the SLM-3DTi surface through laser melting and resolidification, and the connection mode is stronger than that of any adhesive and has extremely strong mechanical stability. More importantly, no chemical reagent is used in the printing process, no chemical reaction occurs, and the SLM-3DTi still has the excellent corrosion resistance of pure titanium. Therefore, the SLM-3DTi has wide practical application prospect in switchable oil-water emulsion separation.
Drawings
FIG. 1 is an electron microscope image of the pure titanium powder of the present embodiment 1.
Fig. 2 shows the establishment of a three-dimensional model in embodiment 1 of the present invention.
Fig. 3 shows the principle of SLM forming in embodiment 1 of this embodiment.
FIG. 4 is a structural comparison between the SLM-3DTi design model and the printed material object in embodiment 1 of the present invention. (a) 10 × 10 model magnification, (e) (i) (m) 10 × 10 sem; (b) (iv) 5 × 5 model magnifications, (f) (g) (n) 5 × 5 sem pictures; (c) (ii) 3.5 × 3.5 model magnification, (g) (k) (o) 3.5 × 3.5 sem; (d) The 2 × 2 model magnifications, (h) (i) (p) are 2 × 2 sem pictures.
FIG. 5 is the effect of print angle on surface topography and contact angle; the printing method comprises the following steps of (a) printing a surface topography corresponding to an angle of 30 degrees and a contact angle of water in air, a contact angle of oil in water and a contact angle of water in oil, (b) printing a surface topography corresponding to an angle of 60 degrees and a contact angle of water in air, a contact angle of oil in water and a contact angle of water in oil, (c) printing a surface topography corresponding to an angle of 90 degrees and a contact angle of water in air, a contact angle of oil in water and a contact angle of water in oil, (d) printing a surface topography corresponding to an angle of 180 degrees and a contact angle of water in air, a contact angle of oil in water and a contact angle of water in oil.
FIG. 6 shows the wetting prevalence of SLM-3DTi in example 1 of this embodiment. The wetting behavior of the oil in the SLM-3DTi under the air environment, (b) the wetting behavior of the oil in the SLM-3DTi under the air environment, (c) the wetting behavior of the water in the SLM-3DTi under the oil environment (n-hexane, petroleum ether, hexadecane and dichloroethane), (d) the wetting behavior of the oil in the SLM-3DTi under the water environment (n-hexane, petroleum ether, hexadecane and dichloroethane).
FIG. 7 shows the emulsion separation performance test in example 1 of this embodiment. (a) Particle size distribution before and after oil-in-water emulsion separation and optical microscopy (SS-H-in-W, SS-P-in-W, SS-B-in-W, SS-D-in-W), (B) particle size distribution before and after water-in-oil emulsion separation and optical microscopy (SS-W-in-H, SS-W-in-P, SS-W-in-B, SS-W-in-D).
FIG. 8 emulsion separation efficiency and throughput. Efficiency and flux of (a) separation of oil-in-water emulsions, (b) efficiency and flux of separation of water-in-oil emulsions, (c) variation in flux and efficiency of continuous separation of oil-in-water emulsions of 250ml, (d) variation in flux and efficiency of continuous separation of oil-in-water emulsions of 100ml, (e) variation in flux of alternating separation of water-in-oil emulsions and oil-in-water emulsions, (f) variation in efficiency of alternating separation of water-in-oil emulsions and oil-in-water emulsions.
Fig. 9 is a corrosion resistance test in example 1 of the present embodiment, (a) tafel curve of SLM-3DTi in acid-base salt solution, (b) influence of the immersion time of SLM-3DTi in acid-base salt and aqua regia on the underwater oil contact angle and the water-in-oil contact angle, and (c) surface morphology and the underwater oil contact angle and the water-in-oil contact angle after SLM-3DTi is immersed for 15 days.
FIG. 10 shows the durability test of example 1 of this embodiment (a) the abrasion pattern and (b) the change in underwater superoleophobic-oily superhydrophobicity with abrasion distance.
Detailed Description
The technical solutions in the embodiments of the present invention will be described clearly and completely with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive step based on the embodiments of the present invention, are within the scope of protection of the present invention.
Example 1
(1) Commercially pure titanium powder from SLM-Solution was purchased and observed using a Scanning Electron Microscope (SEM) for powder, as shown in FIG. 1, which has a high sphericity of about 20 to 50 um in diameter. Before the experiment, the powder was washed with alcohol and deionized water in an ultrasonic machine for 15 minutes, and then dried in a 60 ℃ desiccator for 10 hours.
(2) By utilizing a parametric modeling method, the division of space regions is realized by controlling the seed points generated by the space, the regions conform to normal distribution, the contour line of each cell of the Voronoi model is extracted to be used as a skeleton of the porous structure, the design of the irregular porous structure is realized, and the modeling process is shown in figure 2.
(3) Introducing the model into a computer control system of an SLM-Solution125HL metal 3D printer produced by Germany, fixing a pure titanium substrate with the thickness of 15mm on a building platform, leveling, vacuumizing the building chamber, and filling argon; and then, spraying industrial pure titanium powder on a pure titanium substrate by adopting an automatic powder spraying system, wherein the thickness of each layer is 25 um, the laser power is 200W, the scanning speed is 400 mm/s, and a three-dimensional porous structure (SLM-3 DTi) of the pure titanium is printed. Figure 3 shows a schematic view of SLM processing with an alternating X-Y direction laser scanning strategy. After the construction process is completed, the excess powder is removed from the surface of the part immediately by means of an air duct. Furthermore, the sample surface was kept in a rough as-built condition without any post-treatment. We guaranteed that the structure of the model was unchanged and printed four sizes of 10 x 10, 5 x 5, 3.5 x 3.5, 2 x 2 mm samples whose structure size is shown in fig. 4.
(4) And (4) testing wettability. To verify that SLM-3DTi has both underwater superoleophobicity and underwater superhydrophobicity, four relatively common oils (n-hexane, petroleum ether, hexadecane, and dichloroethane) were selected for wettability testing. The underwater super-oleophobic property test method comprises the following steps: soaking the SLM-3DTi in water, and measuring the contact angle (UWOCA) of n-hexane, petroleum ether, hexadecane and dichloroethane dropped on the surface of the SLM-3DTi by using a contact angle measuring instrument; method for testing the superhydrophobicity of oil: the SLM-3DTi was soaked in various oils (n-hexane, petroleum ether, hexadecane and dichloroethane) and then the contact angle of a water drop on the surface of the SLM-3DTi (UOWCA) was measured using a contact angle measuring instrument, and the results are shown in FIG. 5. Fig. 5 (a) prints the surface topography corresponding to an angle of 30 ° and the contact angle of water in air, the contact angle of oil in water, the contact angle of water in oil, fig. 5 (b) prints the surface topography corresponding to an angle of 60 ° and the contact angle of water in air, the contact angle of oil in water, the contact angle of water in oil, fig. 5 (c) prints the surface topography corresponding to an angle of 90 ° and the contact angle of water in air, the contact angle of oil in water, the contact angle of water in oil, fig. 5 (d) prints the surface topography corresponding to an angle of 180 ° and the contact angle of water in air, the contact angle of oil in water, the contact angle of water in oil.
FIG. 6 shows the wetting prevalence of SLM-3DTi in example 1 of this embodiment. FIG. 6 (a) wetting behavior of water at SLM-3DTi in air environment, FIG. 6 (b) wetting behavior of oil at SLM-3DTi in air environment, FIG. 6 (c) wetting behavior of water at SLM-3DTi in oil (n-hexane, petroleum ether, hexadecane and dichloroethane) in water environment, and FIG. 6 (d) wetting behavior of oil (n-hexane, petroleum ether, hexadecane and dichloroethane) in water environment.
(5) And (4) emulsion separation testing. First, 80mg of Tween 80 and 1ml of oil (n-hexane, petroleum ether, xylene (1,4-dimethyl-benzene) and dichloroethane) were added to 99 ml deionized water and stirred vigorously on a magnetic stirrer for 3 hours, followed by sonication at 40 kHz for 3 hours to prepare a surfactant-stabilized oil-in-water emulsion (SSE (o/w)). These emulsions were designated SS-H-in-W, SS-P-in-W, SS-B-in-W and SS-D-in-W, respectively. Then, 80mg of Span 80 and 1ml of water were added to 99 ml oil (n-hexane, petroleum ether, dichloromethane and dichloroethane) and vigorously stirred on a magnetic stirrer for 3 hours, followed by ultrasonication at 40 kHz for 3 hours to prepare a surfactant-stabilized water-in-oil emulsion (SSE (w/o)). These emulsions were designated SS-W-in-H, SS-W-in-P, SS-W-in-B and SS-W-in-D, respectively. All surfactant-stabilized oil-water emulsions remained highly stable over 24 hours. Finally, the prepared SLM-3DTi sample is placed and sealed in the middle of a self-made filtering device system, and the poured oil-water emulsion is separated under the pressure of 0.04 mPa. Flux was determined by calculating the filtrate volume per unit time, flux F = V/St, where V is the filtrate volume, S is the membrane area, and t is the test time. Testing the Chemical Oxygen Demand (COD) in the filtrate of the oil-in-water emulsion with a COD detector and converting to the separation efficiency of the oil-in-water emulsion; the separation efficiency of the water-in-oil emulsion was calculated by testing the water content of the filtrate of the water-in-oil emulsion with a KF coulometer.
To further understand the separation process, we recorded the size and distribution of the droplets in the emulsion before and after separation using Dynamic Light Scattering (DLS) technique and optical microscopy. The first column in FIG. 7 (a) is a particle size distribution diagram before SSE (o/W) separation (no signal is received after separation and is not shown), and the second column is an optical micrograph before and after separation and a real comparison diagram (1. SS-H-in-W, 2.SS-P-in-W, 3.SS-B-in-W, 4. SS-D-in-W). Before filtration, the size distribution range of SSE (o/w) droplets is observed to be 0.1 to 10 mu m, most of the SSE droplets are within 1 to 10 mu m, and a large number of droplets are uniformly distributed in an optical microscope picture, but after filtration, a filtrate can be seen to be quite clear from a physical comparison picture, a DLS instrument does not receive an acquired filtrate signal, and water droplets are not found in the optical microscope picture, so that the SLM-3DTi has excellent oil-in-water emulsion separation performance. The SLM-3DTi was then dried and then wetted with oil for a water-in-oil emulsion separation test. Experimental procedures as above, the isolated video is shown as V3. The size and distribution of the droplets in the water-in-oil emulsion before and after the separation were recorded by the same method, as shown in FIG. 7 (B) (5. SS-W-in-H, 6.SS-W-in-P, 7.SS-W-in-B, 8. SS-W-in-D), the separation phenomenon was similar to that of the oil-in-water emulsion. This confirms that SLM-3DTi still has excellent water-in-oil emulsion separation performance.
The separation flux and separation efficiency of the oil-in-water emulsion were calculated as shown in fig. 8 (a). SS-H-in-W, SS-P-in-W, SS-B-in-W, SS-D-in-W has separation efficiencies of 2298, 2540, 2019, and 2111, respectively; the efficiency is more than 99%. The separation throughput and separation efficiency of the water-in-oil emulsion are shown in FIG. 8 (b). The separation efficiency of SS-W-in-H, SS-W-in-P, SS-W-in-B, SS-W-in-D is 5093, 6634, 5590 and 4585 respectively; the calculated separation purity was also about 99%. The results show that FGPA has a fast and efficient separation capacity for water in oil emulsions, where the separation throughput of water-in-oil emulsions is faster because SLM-3DTi itself has super lipophilicity and the osmotic resistance of oil during separation is much lower than water.
The samples were then subjected to successive emulsion separations, each time 25ml, without washing, 10 times in succession, the oil-in-water emulsion being n-hexane-in-water and the water-in-oil emulsion being water-in-dichloromethane, and the separation time was recorded and the separation efficiency and the separation purity were calculated. FIG. 8 (c) shows the separation efficiency and purity of a continuous n-hexane-in-water emulsion, wherein the flux gradually decreases and then stabilizes at about 1200 deg.C, because the SLM-3DTi pores are blocked by the intercepted oil droplets as the separation emulsion increases, and the flux gradually decreases, and when the blockage reaches a peak, because the SLM-3DTi is in an underwater superoleophobic state, water has a lower breakthrough pressure than oil and can penetrate through the oil droplets which block the pores under the action of surface tension, and therefore when the blockage occurs at a maximum, the flux stabilizes at a constant value; the efficiency is always stabilized at about 99.9 percent. Fig. 8 (d) shows the separation efficiency and separation purity of continuous separation of water-in-dichloromethane emulsion, and the flux phenomenon is the same as that of n-hexane-in-water emulsion, and the efficiency is slowly increased because oil droplets with smaller particle size are intercepted after blockage, which is equivalent to the reduction of the SLM-3DTi pore size. Next, alternate cycle separation experiments of oil-in-water and water-in-oil emulsions were performed, where the samples were washed and dried, 25ml each, 10 cycles before the alternate experiments. The separation flux for the alternate separation experiment is shown in fig. 8 (e) and the separation efficiency is shown in fig. 8 (f), and it can be seen that the flux and efficiency remain substantially unchanged after each alternate. Through a series of experimental tests, SLM-3DTi has switchable, continuous, quick and efficient emulsion separation capacity and shows excellent multiple applicability in treating various complex oil-water emulsions.
(6) And (5) performing corrosion resistance test. The electrochemical workstation works at room temperature by adopting a three-electrode system, namely a platinum plate is taken as a counter electrode, a CHI150 Saturated Calomel Electrode (SCE) is taken as a reference electrode, and the exposed surface area is 4 cm 2 The SLM-3DTi of (1) is a working electrode. The polarization curve versus open circuit potential (Eocp) was measured in HCl (pH = 2), 3.5 wt% NaCl and KOH (pH = 13) solutions at a scan speed of 5 mV/s in the range 300 mV to 300 mV. And calculating parameters of corrosion potential (Ecorr) and corrosion current density (Icorr) by a Tafel extrapolation method, and evaluating the corrosion resistance of the surface of the tested sample. And the surface wettability and surface morphology of SLM-3DTi after etching in HCl (pH = 2), 3.5 wt% NaCl, KOH (pH = 13) solution, and most corrosive aqua regia were determined. Four groups of samples were soaked in 50mL equivalents of HCl (pH = 2), 3.5 wt% NaCl, KOH (pH = 13) solution, and most corrosive aqua regia, respectively, and contact angles were recorded every other day. Finally, the block was closed at 20 ℃ for 15 days and the corresponding contact angle and surface topography were measured.
The dynamic potential polarization curve is shown in FIG. 9 (a), and it is seen that the corrosion potential is already as small as 10 -6 The corrosion resistance is very difficult to be corroded, and the corrosion resistance is very strong in acid-base salt solution. Changes of UOWCA and UWOCA (n-hexane) of SLM-3DTi along with soaking time are shown in fig. 9 (b), changes of underwater oil contact angle and water contact angle value along with time are very stable, and the changes do not have large fluctuation and are both more than 150Degree. To make the experiment more convincing, the soak time was extended to 15 days and the corresponding WCA and surface topography were measured as shown in fig. 9 (c). The sample still keeps underwater super-oleophobic property and oil super-hydrophobic property, and the appearance is not changed, which shows that SLM-3DTi has higher corrosion resistance.
(7) And (5) testing the wear resistance. The mechanical durability of the SLM-3DTi was evaluated by an abrasion test under load on sandpaper. The SLM-3DTi was loaded with heavy objects and moved in one direction over the SiC sandpaper, keeping the same speed as possible. Here, we selected 400 mesh SiC paper and 200g different loads for the experiments. As shown in fig. 10 (a), the prepared SLM-3DTi was placed on a sandpaper under the weight of a load and then moved forcibly in one direction at a speed as constant as possible. Meanwhile, during the abrasion test, for each 40cm movement, the underwater oil contact angle and the underwater oil contact angle were measured and recorded. However, the relationship between the underwater oil contact angle and the oil-water contact angle and the wear distance shows a fluctuation state, and the original surface topography of the SLM-3DTi and the surface topography after wear of 240cm are illustrated (FIG. 10 (b)). The overall trend of the test is that as the abrasion distance increases, the underwater oil contact angle slowly increases, while the underwater oil contact angle slowly decreases, which can be attributed to the destruction of the microstructure at the top of the surface topography (as can be demonstrated by the insets), and the SLM-3DTi surface wettability approaches the intrinsic contact angle of pure titanium. But SLM-3DTi surfaces can retain underwater superoleophobic-oil superhydrophobic (9 (b)) within a wear distance of 240cm, which is one of the furthest distances reported so far. In conclusion, the underwater superoleophobic-oil superhydrophobic SLM-3DTi surface demonstrates excellent mechanical durability properties.
The above are preferred embodiments of the present invention, and all changes made according to the technical scheme of the present invention that produce functional effects do not exceed the scope of the technical scheme of the present invention belong to the protection scope of the present invention.
Claims (6)
1. A preparation method of a super-amphiphobic titanium-based three-dimensional porous material is characterized by comprising the following steps:
a) Before printing, respectively cleaning metal powder with alcohol and deionized water in an ultrasonic machine for 15 minutes, and then drying in a dryer at 60 ℃ for 10 hours;
b) By utilizing a parametric modeling method, the division of a space region is realized by controlling the seed points generated by the space, and the contour line of each cell of the Voronoi model is extracted to be used as a skeleton of the porous structure, so that the design of the irregular porous structure is realized;
c) Guiding the middle model in the step b) into an SLM-Solution125HL metal 3D printer computer control system, fixing and leveling a pure titanium substrate on a building platform, vacuumizing the interior of a building, and filling argon; then, scattering metal powder in a) on a pure titanium substrate by adopting an automatic powder scattering system, and printing a model by using laser under the control of a computer control system;
d) After the construction process is finished, redundant powder is immediately removed from the surface of the part by using an air cylinder, and the underwater super oleophobic-oil super hydrophobic porous material capable of switching and separating the water-in-oil emulsion and the oil-in-water emulsion is prepared.
2. The method for preparing the super-amphiphobic titanium-based three-dimensional porous material according to claim 1, wherein the metal powder comprises: tool steel, martensitic steel, stainless steel, pure titanium and titanium alloy, aluminum alloy, nickel-based alloy, copper-based alloy, cobalt-chromium alloy; the diameter ranges from 10 to 100 um.
3. The method for preparing a titanium-based three-dimensional porous material with super-amphiphobic character according to claim 1, wherein the porous structure is a model of all shapes and sizes generated by a Voronoi model.
4. The method for preparing the super-amphiphobic titanium-based three-dimensional porous material according to claim 1, wherein the thickness of the metal powder is 10-30 um, the laser power is 100-400W, the laser spot is 70-100um, and the scanning speed is 200-600mm/s.
5. The method for preparing the titanium-based super-amphiphobic three-dimensional porous material as claimed in claim 1, wherein in the step (c), an included angle between the upper surface of the mold and the substrate in the printing process is 40-70 degrees.
6. The application of the super-amphiphobic titanium-based three-dimensional porous material is characterized in that the underwater super-oleophobic-oil-falling super-hydrophobic porous material for switchable separation of water-in-oil emulsion and oil-in-water emulsion, which is prepared by the preparation method of any one of claims 1 to 5, is applied to the switchable separation of the water-in-oil emulsion and the oil-in-water emulsion.
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| CN114307997A (en) * | 2021-12-28 | 2022-04-12 | 中物院成都科学技术发展中心 | Super-hydrophobic porous material for oil-water separation and preparation method thereof |
| CN115160728A (en) * | 2022-06-23 | 2022-10-11 | 华中科技大学 | Super-hydrophilic and super-oleophobic composite material, 3D printing piece and printing method |
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| US20180243666A1 (en) * | 2017-02-24 | 2018-08-30 | Board Of Trustees Of The University Of Arkansas | Composite for oil-water separation, synthesis methods and applications of same |
| CN109806775A (en) * | 2019-03-08 | 2019-05-28 | 哈尔滨工业大学 | It is a kind of it is underwater it is superoleophobic and oily under super-hydrophobic seperation film and its preparation method and application |
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