CN115970663A - Preparation method and application of super amphiphobic titanium-based three-dimensional porous material - Google Patents

Abstract

The invention relates to a preparation method and application of a super-amphiphobic titanium-based three-dimensional porous material. The method includes: (1) selecting pure titanium powder with a suitable particle size, cleaning and drying; (2) designing a porous structure using the Voronoi-tessellation algorithm, and the pore size of the porous model conforms to a normal distribution; (3) using selective laser cladding (SLM) technology 3D prints pure titanium powder according to the component model; (4) adjust the angle of the model during the printing process, change the number of "hanging slag" on the surface of the porous structure, and obtain a super-hydrophobic solution that can achieve underwater super-oleophobic and super-hydrophobic under oil pure titanium porous material. The printed underwater superoleophobic-oil superhydrophobic pure titanium porous material has efficient switchable separation of water-in-oil emulsion and oil-in-water emulsion, as well as excellent mechanical stability and corrosion resistance.

Description

Preparation method and application of super amphiphobic titanium-based three-dimensional porous material

technical field

The invention belongs to the field of super-wetting materials, and in particular relates to a preparation method and application of a super-amphiphobic titanium-based three-dimensional porous material.

Background technique

Due to the increase of oily sewage and frequent oil spill pollution, oil-water separation has attracted worldwide attention. Inspired by nature, superwetting materials have been unprecedentedly studied for oil-water separation. In general, oil/water mixtures include immiscible oil/water mixtures and oil/water emulsions (droplet size typically less than 20um). Emulsified mixtures are more difficult to separate than immiscible oil/water mixtures, especially in the presence of surfactants. Achieving emulsion separation requires smaller pore sizes at the expense of flux. In recent years, superhydrophobic membranes and underwater superoleophobic small-pore membranes have been designed to separate water-in-oil emulsions and oil-in-water emulsions, respectively. Superhydrophobic/superoleophilic (oil removal) materials are only suitable for separating water-in-oil emulsions, and superhydrophilic/underwater superoleophobic (water removal) materials include TiO2 and γ-Al2O3 composite films, silica nanosphere coatings Membrane, and graphene oxide-coated mesh for separation of oil-in-water emulsions. Notably, only one type of emulsion (water-in-oil or oil-in-water) could be separated on all the above membranes. Therefore, it is necessary to design smart membranes that can effectively separate surfactant-stabilized oil-in-water emulsions and efficiently separate water-in-oil emulsions.

At present, many smart superwetting materials can switch wettability between superhydrophobic and superhydrophilic under pH value, electric field, temperature, light and various stimuli, and are used for controllable oil-water separation. However, the fabrication process to achieve controlled wettability is often complex and unstable. Most of the existing methods for preparing switchable superwetting porous materials construct coatings with hybrid micro/nano roughness on the treated mesh/fabric by various processes such as spray coating, solution immersion, surface etching and electrodeposition; The surface structure of , often requires further chemical modification with low surface energy compounds to form a switchable superwetting surface. In addition to the complex multi-step processing, these methods suffer from other inherent drawbacks that limit the performance enhancement of the thus prepared porous materials for oil-water separation. For example, during spray coating or solution immersion, the mesh pores may be blocked by coating parts (e.g., nanoparticle aggregates), or worse, coatings prepared on the mesh structure by conventional methods, due to the coating Limited interfacial adhesion to the network structure or poor cohesion of the coating is prone to delamination and abrasion, thereby losing its superwetting properties. In addition, most porous material substrates with special wettability that can be used for oil-water separation, such as metal substrate porous materials will be corroded by acid and alkali; fabric and fiber substrate porous materials are easy to degrade at high temperature; sponge and foam substrates Porous materials cannot withstand high pressure; moreover, the mesh size of these commercially available porous materials cannot be freely designed, they are usually manufactured according to market standards, and the separation performance (e.g., liquid flux and separation efficiency) of porous materials will be limited . Therefore, there is an urgent need for a solvent-free preparation technology that can control the structure and pore size of porous materials, and develop switchable superwetting porous materials with high wear resistance and high corrosion resistance to improve oil-water separation performance.

Contents of the invention

The purpose of the present invention is to provide a preparation method and application of a super-amphiphobic titanium-based three-dimensional porous material. Selective laser cladding (SLM) technology is used to melt and solidify metal powder with laser to form a molten pool, which is then superimposed layer by layer. Porous materials, and adjust the roughness of the porous material surface by controlling the printing angle, so that the surface of the porous material can achieve underwater super-oleophobic-under-oil super-hydrophobic, and develop a switchable super-wetting porous material with high wear resistance and high corrosion resistance Material improves oil-water separation performance.

In order to achieve the above object, the technical solution of the present invention is: a preparation method of a super-amphiphobic titanium-based three-dimensional porous material, comprising the following steps:

a) Before printing, the metal powder was cleaned in an ultrasonic machine with alcohol and deionized water for 15 minutes, and then dried in a dryer at 60°C for 10 hours;

b) By using the parametric modeling method, by controlling the seed points generated in the space, the division of the space area is realized, and the outline of each cell of the Voronoi model is extracted as the skeleton of the porous structure, and the irregular porous structure is realized design;

c) Import the model in b) into the SLM-Solution125HL metal 3D printer computer control system, fix the pure titanium substrate on the building platform and level it, then vacuumize the building room and fill it with argon; a) The metal powder is sprinkled on the pure titanium substrate, and the model is printed by laser under the control of the computer control system;

d) Immediately after the construction process is completed, the excess powder is removed from the surface of the part with a blower, and an underwater super-oleophobic-under-oil super-hydrophobic porous material that can switch and separate the water-in-oil emulsion and the oil-in-water emulsion is obtained.

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 range is 10- 100um.

In an embodiment of the present invention, the porous structure is a model of all shapes and sizes generated using a Voronoi model.

In an embodiment of the present invention, the metal powder sprinkled has a thickness of 10-30 um, a laser power of 100-400 W, a laser spot of 70-100 um, and a scanning speed of 200-600 mm/s.

In an embodiment of the present invention, in the step (c), the angle between the upper surface of the model and the substrate during the printing process is 40-70°.

The present invention also provides an application of a super-amphiphobic titanium-based three-dimensional porous material, using the underwater super-oleophobic-under-oil super-hydrophobic porous material that can switch and separate the water-in-oil emulsion and the oil-in-water emulsion prepared by the above-mentioned preparation method The material is used in switchable separation of water-in-oil emulsion and oil-in-water emulsion.

Compared with the prior art, the present invention has the following beneficial effects:

The present invention avoids thermodynamic contradictions by rationally designing printing parameters and adopting metastable state theory in solid-oil-water system, and SLM-3DTi exhibits superhydrophobicity under oil and superoleophobicity under water. Without any persistent external stimulus, the wettability of SLM-3DTi can be reversibly switched between underwater superoleophobicity and underoil superhydrophobicity by simply alternating drying and washing, thereby achieving switchable oil-water separation. , and the separation efficiency is as high as 99.8%, and the flux is above 2000 L/m2h. In addition, pure titanium microspheres are firmly covered on the surface of SLM-3DTi through laser melting and resolidification. This connection method is stronger than any kind of adhesive and has extremely strong mechanical stability. More importantly, no chemical reagents are used in the printing process, and no chemical reaction occurs, and SLM-3DTi still has the excellent corrosion resistance of pure titanium. Therefore, SLM-3DTi has broad practical application prospects in switchable oil-water emulsion separation.

Description of drawings

Fig. 1 is the electron micrograph of commercially pure titanium powder in the embodiment 1 of this scheme.

Fig. 2 is the establishment of the three-dimensional model in embodiment 1 of this scheme.

Figure 3 is the principle of SLM forming in Example 1 of this scheme.

Figure 4 is a structural comparison between the SLM-3DTi design model and the printed object in Example 1 of this scheme. (a) is the enlarged view of the 10*10*10 model, (e)(i)(m) is the 10*10*10 physical electron microscope image; (b) is the enlarged view of the 5*5*5 model, (f)(g )(n) is the 5*5*5 physical electron microscope image; (c) is the 3.5*3.5*3.5 model enlarged image, (g)(k)(o) is the 3.5*3.5*3.5 physical electron microscope image; (d) is The enlarged view of the 2*2*2 model, (h)(i)(p) is the electron microscope image of the 2*2*2 object.

Figure 5 shows the effect of printing angle on surface topography and contact angle; (a) when the printing angle is 30°, the corresponding surface topography and the contact angle of water in air, the contact angle of oil in water, and the contact angle of water in oil Contact angle, (b) the corresponding surface topography and the contact angle of water in air, oil in water, and water in oil when the printing angle is 60°, (c) when the printing angle is 90° Corresponding surface topography and contact angle of water in air, oil in water, water in oil, (d) corresponding surface topography and contact of water in air when the printing angle is 180° angle, contact angle of oil in water, contact angle of water in oil.

Fig. 6 is the wetting universality of SLM-3DTi in Example 1 of this scheme. (a) Wetting behavior of water on SLM-3DTi in air environment, (b) Wetting behavior of oil on SLM-3DTi in air environment, (c) Wetting behavior of SLM-3DTi in oil (n-hexane, petroleum ether, cetyl Wetting behavior of water on SLM-3DTi under water environment, (d) oil (n-hexane, petroleum ether, hexadecane and dichloroethane) on SLM-3DTi under water environment wetting behavior.

Fig. 7 is the emulsion separation performance test in Example 1 of this scheme. (a) Particle size distribution and optical microscope images of oil-in-water emulsion before and after separation (SS-H-in-W, SS-P-in-W, SS-B-in-W, SS-D-in-W ), (b) particle size distribution and optical microscope images of water-in-oil emulsion before and after separation (SS-W-in-H, SS-W-in-P, SS-W-in-B, SS-W-in -D).

Fig. 8 Emulsion separation efficiency and flux. (a) efficiency and flux of oil-in-water emulsion separation, (b) efficiency and flux of water-in-oil emulsion separation, (c) continuous separation of oil-in-water emulsion 250ml flux and efficiency change, (d) water-in-water emulsion Changes in flux and efficiency of continuous separation of 100ml oil emulsion, (e) flux change in alternating separation of water-in-oil emulsion and oil-in-water emulsion, (f) change in efficiency of alternating separation of water-in-oil emulsion and oil-in-water emulsion.

Fig. 9 is the corrosion resistance test in Example 1 of this scheme, (a) the Tafel curve of SLM-3DTi in acid-base salt solution, (b) the immersion time of SLM-3DTi in acid-base salt and aqua regia versus water The influence of oil contact angle and water contact angle under oil, (c) Surface morphology, oil contact angle and water contact angle under oil of SLM-3DTi after soaking for 15 days.

Figure 10 shows the durability test in Example 1 of this program (a) Wear mode, (b) Underwater super-oleophobicity-the change of superhydrophobicity under oil with the wear distance.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.

Example 1

(1) Purchase the industrial pure titanium powder from SLM-Solution, and observe the powder with a scanning electron microscope (SEM). As shown in Figure 1, the industrial pure titanium powder is highly spherical, with a diameter of about 20-50 um . Before the experiment, the powder was cleaned in an ultrasonic machine with alcohol and deionized water for 15 minutes, and then dried in a desiccator at 60 °C for 10 hours.

(2) Using the parametric modeling method, by controlling the seed points generated in the space, the division of the space area is realized. The area conforms to the normal distribution, and the contour line of each cell of the Voronoi model is extracted as the skeleton of the porous structure. To realize the design of irregular porous structure, the modeling process is shown in Figure 2.

(3) Import the model into the computer control system of the SLM-Solution125HL metal 3D printer produced in Germany, fix the 15mm thick pure titanium substrate on the building platform and level it, then vacuumize the building room and fill it with argon gas; then use The automatic powder spreading system sprinkles industrial pure titanium powder on the pure titanium substrate, the thickness of each layer is 25 um, the laser power is 200W, the scanning speed is 400 mm/s, and the three-dimensional porous structure of pure titanium (SLM-3DTi) is printed. . Figure 3 shows a schematic diagram of SLM processing using an alternating X-Y direction laser scanning strategy. Immediately after the build process is complete, excess powder is removed from the surface of the part with a blower. Furthermore, the sample surface was kept in rough as-built condition without any post-processing. We ensured that the structure of the model remained unchanged, and printed samples of four sizes: 10*10*10, 5*5*5, 3.5*3.5*3.5, and 2*2*2 mm. Their structural dimensions are shown in Figure 4.

(4) wettability test. In order to verify that SLM-3DTi has underwater superoleophobicity and oil superhydrophobicity, four common oils (n-hexane, petroleum ether, hexadecane and dichloroethane) were selected for wettability test. Underwater superoleophobic test method: soak SLM-3DTi in water and use a contact angle meter to measure the contact angle (UWOCA) of n-hexane, petroleum ether, hexadecane and dichloroethane on the surface of SLM-3DTi; The following superhydrophobicity test method: soak SLM-3DTi in different oils (n-hexane, petroleum ether, hexadecane and dichloroethane) and then use a contact angle meter to measure the contact angle of water droplets on the surface of SLM-3DTi (UOWCA ), the result is shown in Figure 5. Figure 5 (a) The corresponding surface morphology and the contact angle of water in air, oil in water, and water in oil when the printing angle is 30°, and Figure 5 (b) when the printing angle is 60° The corresponding surface topography and the contact angle of water in air, oil in water, and water in oil, Fig. 5 (c) The corresponding surface topography and water in air when the printing angle is 90° The contact angle in , the contact angle of oil in water, the contact angle of water in oil, Fig. 5 (d) The corresponding surface morphology when the printing angle is 180°, the contact angle of water in air, the contact angle of oil in water angle, contact angle of water in oil.

Fig. 6 is the wetting universality of SLM-3DTi in Example 1 of this scheme. Figure 6 (a) In the air environment, the wetting behavior of water on SLM-3DTi, Figure 6 (b) In the air environment, the wetting behavior of oil on SLM-3DTi, Figure 6 (c) in the oil (n-hexane , petroleum ether, hexadecane and dichloroethane) environment, the wetting behavior of water on SLM-3DTi, Figure 6 (d) in the water environment, oil (n-hexane, petroleum ether, hexadecane and dichloroethane ethane) on the wetting behavior of SLM-3DTi.

(5) Emulsion separation test. First, add 80mg Tween 80 and 1ml oil (n-hexane, petroleum ether, xylene (1,4-dimethyl-benzene) and dichloroethane) into 99 ml deionized water, and stir vigorously on a magnetic stirrer 3 h, followed by 3 h of ultrasonication at 40 kHz 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, 80 mg of Span 80 and 1 ml of water were added to 99 ml of oil (n-hexane, petroleum ether, dichloromethane, and dichloroethane), and stirred vigorously on a magnetic stirrer for 3 hours, followed by ultrasonication at 40 kHz for 3 hours. Hours, a surfactant-stabilized water-in-oil emulsion (SSE(w/o)) was prepared. These emulsions were named 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 was placed and sealed in the middle of the self-made filter system, and the poured oil-water emulsion was separated under a pressure of 0.04 mPa. The flux is 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. Use a chemical oxygen demand (COD) detector to test the COD in the filtrate of the oil-in-water emulsion and convert it to the separation efficiency of the oil-in-water emulsion; use a KF coulometer to test the water content of the filtrate of the water-in-oil emulsion to calculate the water-in-oil emulsion separation efficiency.

To further understand the separation process, we recorded the size and distribution of droplets in the emulsion before and after separation using dynamic light scattering (DLS) techniques and optical microscopy. The first column of Figure 7(a) is the particle size distribution diagram of SSE (o/w) before separation (no signal was received after separation, so it is not shown), the second column is the optical microscope photos before and after separation and the comparison of the real object (1. SS-H-in-W, 2. SS-P-in-W, 3. SS-B-in-W, 4. SS-D-in-W). Before filtration, the droplet size distribution range of SSE (o/w) was observed from the particle size distribution diagram in the first column to be 0.1-10 μm, most of which were in the range of 1-10 μm, and it can be seen in the optical microscope photos A large number of liquid droplets were evenly distributed, but after filtration, the filtrate became very clear from the comparison picture of the actual object, and the DLS instrument did not receive the collected filtrate signal, and no water droplets were found in the optical microscope photos. It was confirmed that SLM-3DTi has excellent separation performance of oil-in-water emulsion. The SLM-3DTi was then dried and then wetted with oil for the separation test of the water-in-oil emulsion. The experimental process is the same as above, and the separation video is shown in V3. And the same method was used to record the particle size and distribution of droplets in the water-in-oil emulsion before and after separation, as shown in Figure 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 is similar to that of oil-in-water emulsion. This confirms that SLM-3DTi still has excellent separation performance of water-in-oil emulsion.

After calculation, the separation flux and separation efficiency of the oil-in-water emulsion are shown in Fig. 8(a). The separation efficiencies of SS-H-in-W, SS-P-in-W, SS-B-in-W, and SS-D-in-W are 2298, 2540, 2019, and 2111, respectively; the efficiencies are all greater than 99%. The separation flux and separation efficiency of the water-in-oil emulsion are shown in Fig. 8(b). The separation efficiencies of SS-W-in-H, SS-W-in-P, SS-W-in-B and SS-W-in-D are 5093, 6634, 5590 and 4585 respectively; the calculated separation purities are also about 99%. The results show that FGPA has fast and efficient separation ability for water in oil emulsion, and the separation flux of water-in-oil emulsion is faster because SLM-3DTi itself has super lipophilicity, and the penetration resistance of oil in the separation process is higher than that of water. much lower.

Subsequently, the sample is continuously separated by emulsion, each separation is 25ml, without cleaning, 10 times in a row, the oil-in-water emulsion is n-hexane in water, and the water-in-oil emulsion is water-in-methylene chloride, and the separation time is recorded, and the separation efficiency and separation efficiency are calculated. purity. Figure 8(c) shows the separation efficiency and separation purity of the continuous separation of n-hexane emulsion in water, in which the flux will gradually decrease and then stabilize at around 1200, this is because the pores of SLM-3DTi will increase The intercepted oil droplets are clogged, and the flux will gradually decrease. When the clogging reaches the peak, because the SLM-3DTi is in an underwater super-oleophobic state, water has a lower breakthrough pressure than oil, and it will be separated under the action of surface tension. The oil droplets squeezed through the clogged pores permeate down, so when the clogging occurs and reaches the maximum, the flux will stabilize near the constant value; the efficiency has been stable at about 99.9%. Figure 8(d) shows the separation efficiency and separation purity of the continuous separation of water-in-dichloromethane emulsion. The flux phenomenon is the same as that of n-hexane-in-water emulsion separation, and the efficiency increases slowly, because the clogging occurs equivalent to the pore size of SLM-3DTi Oil droplets with smaller particle sizes will also be intercepted. Next, the alternating cycle separation experiment of oil-in-water emulsion and water-in-oil emulsion was carried out. Before the alternating experiment, the samples were cleaned and dried, and 25ml was separated each time, and the cycle was repeated 10 times. The separation flux of the alternating separation experiment is shown in Fig. 8(e), and the separation efficiency is shown in Fig. 8(f). It can be seen that the flux and efficiency remain basically unchanged after each alternation. Through a series of experimental tests, it is shown that SLM-3DTi has switchable, continuous, fast and efficient emulsion separation capabilities, and shows superior multiple applicability in processing various complex oil-water emulsions.

(6) Carry out corrosion resistance test. The electrochemical workstation used a three-electrode system at room temperature: a platinum plate as the counter electrode, a CHI150 saturated calomel electrode (SCE) as the reference electrode, and SLM-3DTi with an exposed surface area of 4 ^cm2 as the working electrode. The relationship between the polarization curve and the open circuit potential (Eocp) was measured in the range of 300 mV to 300 mV at a scan rate of 5 mV/s in HCl (pH=2), 3.5 wt% NaCl and KOH (pH=13) solutions . The parameters of corrosion potential (Ecorr) and corrosion current density (Icorr) were calculated by Tafel extrapolation method to evaluate the corrosion resistance of the surface of the tested sample. The surface wettability and surface morphology of SLM-3DTi after corrosion in HCl (pH=2), 3.5 wt% NaCl, KOH (pH=13) solutions and the most corrosive aqua regia were measured. The four groups of samples were soaked in 50 mL equal volume of HCl (pH=2), 3.5 wt% NaCl, KOH (pH=13) solution and the most corrosive aqua regia, and the contact angle was recorded every other day. Finally, it was sealed at 20 °C for 15 days, and the corresponding contact angle and surface morphology were measured.

Its dynamic potential polarization curve, as shown in Figure 9(a), shows that the corrosion potential is as small as 10 ^-6 , it is difficult to be corroded, and it has extremely strong corrosion resistance in acid, alkali and salt solutions. The change curves of UOWCA and UWOCA (n-hexane) of SLM-3DTi with immersion time are shown in Fig. 9(b). The values of underwater oil contact angle and oil-water contact angle are very stable with time without large fluctuations. are greater than 150°. To make the experiment more convincing, the immersion time was extended to 15 days, and the corresponding WCA and surface topography were measured, as shown in Fig. 9(c). The sample still maintains the underwater superoleophobicity and oily superhydrophobicity, and shows no change in morphology, indicating that SLM-3DTi has high corrosion resistance.

(7) Abrasion resistance test. The mechanical durability of SLM-3DTi was evaluated by performing wear tests under load on sandpaper. The SLM-3DTi is loaded with a heavy object and moved in one direction over the SiC sandpaper, maintaining the same speed as possible. Here, we chose 400-mesh SiC sandpaper and 200g different loads for experiments. As shown in Fig. 10(a), the prepared SLM-3DTi was placed on the sandpaper under the weight of the load, and then moved forcefully in one direction at as constant a speed as possible. At the same time, during the wear test, the oil contact angle under water and the water contact angle under oil were measured and recorded every 40 cm of movement. However, the relationship between the underwater oil contact angle and the oil-water contact angle and the wear distance is fluctuating. The illustration shows the original surface morphology of SLM-3DTi and the surface morphology after 240cm of wear (Fig. 10(b)). The overall trend of the test is that with the increase of the wear distance, the oil contact angle under water slowly increases, while the water contact angle under oil slowly decreases. The surface wettability of -3DTi is close to the intrinsic contact angle of pure titanium. However, within a wear distance of 240 cm, the SLM-3DTi surface can maintain underwater superoleophobicity-underoil superhydrophobicity (9(b)), which is one of the longest distances reported so far. In conclusion, the underwater superoleophobic-underoil superhydrophobic SLM-3DTi surface exhibits excellent mechanical durability.

The above are the preferred embodiments of the present invention, and all changes made according to the technical solution of the present invention, when the functional effect produced does not exceed the scope of the technical solution of the present invention, all 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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