CN113019484A - Underwater oil transportation functional structure and preparation method and application thereof - Google Patents
Underwater oil transportation functional structure and preparation method and application thereof Download PDFInfo
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- CN113019484A CN113019484A CN202110332797.5A CN202110332797A CN113019484A CN 113019484 A CN113019484 A CN 113019484A CN 202110332797 A CN202110332797 A CN 202110332797A CN 113019484 A CN113019484 A CN 113019484A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
- B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
- B01L3/50—Containers for the purpose of retaining a material to be analysed, e.g. test tubes
- B01L3/502—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures
- B01L3/5027—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip
- B01L3/502707—Containers for the purpose of retaining a material to be analysed, e.g. test tubes with fluid transport, e.g. in multi-compartment structures by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip characterised by the manufacture of the container or its components
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Abstract
The invention provides a functional structure for transporting underwater oil, a preparation method and application thereof, and belongs to the technical field of mechanical surface engineering. The underwater oil transportation functional structure comprises an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged on the periphery of the underwater super oleophilic wedge-shaped area; the underwater super-oleophylic wedge-shaped area is formed by wedge-shaped microstructures distributed in an array, each wedge-shaped microstructure comprises a plurality of wedge-shaped grooves connected in series, and in two adjacent wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc along the underwater oil transportation direction; and the bottom of each wedge-shaped groove is provided with an array micro-channel which is arranged in parallel. The functional structure provided by the invention can realize directional and long-distance transportation of underwater oil, particularly has a good directional transportation effect on heavy oil, and has important significance for oil-water separation and underwater oil drop manipulation.
Description
Technical Field
The invention relates to the technical field of mechanical surface engineering, in particular to an underwater oil transportation functional structure and a preparation method and application thereof.
Background
There is a medical need to transport biological samples (oil with high viscosity in nature) such as certain macromolecular proteins to a specific location in an aqueous environment for chemical reaction, and then transport the reacted solution to another specific location to realize Point of care (POC) detection on the biological samples. If the transfer is carried out by using the existing pipettor, the problems of high price and professional operators are also caused, and the biological samples are easy to damage.
Except for pipettors, most of the existing liquid transfer technologies require intervention of external energy, which causes unnecessary energy waste. Xing Li et al (Bioinspired polymeric Surface for direct Oil Lubrication, DOI:10.1021/acsami.9b20345) discloses a functional Surface that can achieve pumpless transport, but has the problem of short transport distances. Thus, there is a need for a functional structure that can achieve self-transport of underwater oil under the action of the substrate itself to improve the efficiency and accuracy of biological detection.
Disclosure of Invention
The invention aims to provide a functional structure for transporting underwater oil, and a preparation method and application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an underwater oil transportation functional structure, which comprises an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged at the periphery of the underwater super oleophilic wedge-shaped area; the underwater super-oleophylic wedge-shaped area is formed by wedge-shaped microstructures distributed in an array, each wedge-shaped microstructure comprises a plurality of wedge-shaped grooves connected in series, and in two adjacent wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc along the underwater oil transportation direction; and the bottom of each wedge-shaped groove is provided with an array micro-channel which is arranged in parallel.
Preferably, the wedge angle of each wedge-shaped groove is 0.5-10 degrees, the depth is-800 micrometers independently, the length is 0.1-50 mm independently, and the width of the groove is 1-10 mm independently;
the depth of each micro channel in the array micro channel is-880-550 mu m independently, and the distance between every two adjacent micro channels is 10-100 mu m.
Preferably, the radius of the transition circular arc is 0.1-15 mm.
Preferably, the array period of the wedge-shaped grooves is 2 μm-6 mm; the period of the wedge-shaped microstructures distributed in the array is 10 micrometers-10 mm.
Preferably, the area ratio of the underwater super oleophobic area to the underwater super oleophilic wedge-shaped area is 0.5-10: 1.
the invention provides a preparation method of an underwater oil transportation functional structure, which comprises the following steps:
respectively preparing an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged on the periphery of the underwater super oleophilic wedge-shaped area on the surface of a substrate, and forming an underwater oil transportation functional structure on the surface of the substrate; the method for preparing the underwater super oleophilic wedge-shaped area comprises a laser liquid phase processing method, and the method for preparing the underwater super oleophobic area comprises a laser direct writing processing method.
Preferably, the laser liquid phase processing method is carried out in a fluorinated liquid with the concentration of 0.4-2 wt%, and the distance between the surface to be processed of the substrate and the liquid level of the fluorinated liquid is 0.5-5 mm.
Preferably, the conditions of the laser liquid phase processing method include: picosecond laser pulse energy is 2-1000 mJ, pulse width is 50 fs-24 ps, and repetition frequency is 10-2000 Hz; the scanning mode is single horizontal or single vertical filling scanning, and the scanning interval is 10-50 μm.
Preferably, the operating conditions of the laser direct write machining method include: the laser wavelength is 1060nm, and the laser power is 26W; the scanning mode is horizontal and vertical alternate orthogonal filling scanning, and the scanning interval is 10-50 mu m.
The invention provides an application of the underwater oil transportation functional structure in the technical scheme or the underwater oil transportation functional structure prepared by the preparation method in the technical scheme in underwater oil transportation.
The invention provides an underwater oil transportation functional structure, which comprises an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged at the periphery of the underwater super oleophilic wedge-shaped area; the underwater super-oleophylic wedge-shaped area is formed by wedge-shaped microstructures distributed in an array, each wedge-shaped microstructure comprises a plurality of wedge-shaped grooves connected in series, and in two adjacent wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc along the underwater oil transportation direction; and the bottom of each wedge-shaped groove is provided with an array micro-channel which is arranged in parallel. The functional structure provided by the invention can realize directional and long-distance pump-free conveying of underwater oil, particularly has a good directional conveying effect on heavy oil, and has important significance for oil-water separation and underwater oil drop manipulation. Specifically, in the functional structure provided by the invention, an underwater super-oleophobic area is in an underwater super-oleophilic state, an underwater super-oleophilic wedge-shaped area is in an underwater super-oleophilic state, when the oil drop transport device is used, oil drops at the narrow end of a wedge-shaped groove are spread into a shape with front and rear end radiuses in a gradient form along the wedge-shaped groove, the oil drops can contact with two side walls (namely two wedge-shaped waists) of the wedge-shaped groove to generate a three-phase contact line, so that the oil drops can generate a Laplacian pressure difference gradient along the groove direction at the position of the three-phase contact line along a wedge-shaped contour line, the oil drops can be automatically transported to the wide end from the narrow end of the wedge-shaped groove under the action of capillary force generated by the gradient, two adjacent wedge-shaped grooves connected in series are connected through a transition arc, when the oil drops are transported to the wide end from the narrow end of a single wedge, by the circulation, the directional and long-distance lossless transportation of the underwater oil can be realized. In the underwater oil transportation functional structure provided by the invention, the existence of the transition arc can enable oil drops transported to the wide end of a single wedge-shaped groove to overcome the energy barrier transported from the wide end to the narrow end of the next wedge-shaped groove to the maximum extent, so that the oil drops can be smoothly transported from the previous wedge-shaped groove to the next wedge-shaped groove, and further long-distance transportation is realized. In the underwater oil transportation functional structure provided by the invention, the micro-channel at the bottom of the wedge-shaped groove is hydrophilic, so that water can enter the interior of the micro-channel, and the effect of reducing the contact of oil drops and the surface of the wedge-shaped groove is achieved, thereby reducing the friction resistance during transportation and promoting the self-transportation of oil. In the underwater oil transportation functional structure provided by the invention, the underwater super oleophobic area has the function of limiting oil drops in the underwater super oleophilic wedge area, so that the oil drops present a certain radius gradient under the action of the wedge-shaped groove, and further, a Laplace pressure difference gradient is generated to provide a driving force, and the self transportation of oil is realized; meanwhile, the flow resistance of oil drops at the three-phase contact line is reduced by the underwater super-oleophobic area, so that the self-transportation of oil is promoted.
Furthermore, the size parameters of the wedge-shaped grooves are adjusted, so that the oil drops can be conveniently transported from the narrow end to the wide end, and the underwater heavy oil (namely high-viscosity oil) can be transported; the long-distance transportation of the high-viscosity oil is facilitated by adjusting the serial number of the wedge-shaped grooves in the wedge-shaped microstructure and the radius size of the transition arc.
Drawings
FIG. 1 is a schematic diagram of 2 serial wedge grooves and a single wedge groove in a functional structure provided by the present invention;
FIG. 2 is a schematic diagram of the depth of a wedge-shaped trench, the depth of a microchannel, and the distance between adjacent microchannels in a functional structure provided by the present invention;
FIG. 3 is a schematic diagram of the principle of the functional structure of the present invention for realizing the directional transportation of underwater oil;
FIG. 4 is a schematic diagram of the principle of long-distance transportation of underwater oil by the functional structure of the present invention;
FIG. 5 is a flow chart of the preparation of a functional structure according to the present invention;
FIG. 6 is a schematic of the microstructure of the functional structure prepared in example 1 of the present invention;
fig. 7 is an SEM image of a functional structure prepared in example 1 of the present invention.
Detailed Description
The invention provides an underwater oil transportation functional structure, which comprises an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged at the periphery of the underwater super oleophilic wedge-shaped area; the underwater super-oleophylic wedge-shaped area is formed by wedge-shaped microstructures distributed in an array, each wedge-shaped microstructure comprises a plurality of wedge-shaped grooves connected in series, and in two adjacent wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc along the underwater oil transportation direction; and the bottom of each wedge-shaped groove is provided with an array micro-channel which is arranged in parallel.
The underwater oil transportation functional structure provided by the invention comprises an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged at the periphery of the underwater super oleophilic wedge-shaped area, wherein the area ratio of the underwater super oleophobic area to the underwater super oleophilic wedge-shaped area is preferably 0.5-10: 1, more preferably 2 to 10: 1, more preferably 3 to 4: 1.
fig. 1 is a schematic diagram of 2 serial wedge-shaped grooves and a single wedge-shaped groove in a functional structure provided by the invention, wherein (a) is a schematic diagram of the 2 serial wedge-shaped grooves and (b) is a schematic diagram of the single wedge-shaped groove in fig. 1; fig. 2 is a schematic diagram of the depth of the wedge-shaped groove, the depth of the micro-channel, and the distance between adjacent micro-channels in the functional structure provided by the present invention, and the underwater super-oleophilic wedge-shaped area in the functional structure provided by the present invention is described below with reference to fig. 1 to 2. In the invention, the wedge angle of each wedge-shaped groove is independently preferably 0.5-10 degrees, more preferably 1-5 degrees, and further preferably 3-4 degrees, and the wedge angle of the wedge-shaped groove specifically refers to an included angle formed by two sides of the wedge; the length of each wedge-shaped groove is preferably 0.1-50 mm independently, more preferably 1-40 mm, and further preferably 5-30 mm; the width of the groove is preferably 1 μm to 10mm, more preferably 5 μm to 8mm, and even more preferably 1mm to 5mm, and specifically, the width of the groove refers to the length of the narrow end side of the wedge-shaped groove. In the invention, the depth of each wedge-shaped groove is preferably-800 μm, more preferably-200-500 μm, and further preferably 120-300 μm independently; the depth of the wedge-shaped groove is specifically the vertical height between the top of the underwater super oleophobic area and the bottom of the wedge-shaped groove (as shown in FIG. 2); when the depth of the wedge-shaped groove is negative, the underwater super oleophilic wedge-shaped area is higher than the surrounding underwater super oleophobic area. The number of the wedge-shaped grooves in series is not particularly limited, and specifically 4-8 wedge-shaped grooves can be connected in series.
In the invention, the bottom of each wedge-shaped groove is provided with array micro-channels which are arranged in parallel, and the depth of each micro-channel in the array micro-channels is preferably-880-550 μm, more preferably-300-200 μm, and further preferably 50-80 μm independently; the distance between adjacent microchannels is preferably 10-100 μm, and more preferably 50-80 μm, wherein the distance between adjacent microchannels is specifically the distance between tops of adjacent microchannels (as shown in FIG. 2).
In the invention, when the underwater super oleophilic wedge-shaped area is higher than the surrounding underwater super oleophobic area, the depth of the micro-channel is equal to the depth of the wedge-shaped groove; when the underwater super oleophilic wedge area is lower than the surrounding underwater super oleophobic area, the depth of the micro-channel is less than or equal to the depth of the wedge-shaped groove.
In the invention, the radius of the transition arc is preferably 0.1-15 mm, and more preferably 1-3 mm.
In the invention, the array period of the wedge-shaped groove is preferably 2 mu m-6 mm, and more preferably 1-5 mm; the array period of the wedge-shaped grooves specifically refers to the distance between the middle point of the wide end of the previous wedge-shaped groove and the middle point of the narrow end of the next wedge-shaped groove of two adjacent wedge-shaped grooves.
In the invention, the period of the wedge-shaped microstructures distributed in the array is preferably 10 micrometers to 10mm, more preferably 0.5mm to 5mm, and further preferably 2mm to 3 mm; the period of the wedge-shaped microstructures distributed in the array specifically refers to the distance between two adjacent wedge-shaped microstructures.
In the invention, the underwater super oleophobic area is preferably formed by a microstructure array, the shape of the microstructure in the microstructure array preferably comprises one or more of micro-protrusions, groove-shaped and pit-shaped, and more preferably the micro-protrusions. The invention has no special limitation on the size, the array interval and the array group number of the microstructure, and can adopt the technical scheme which is well known by the technicians in the field; in an embodiment of the present invention, the microstructure array can be designed specifically with reference to patent CN107283062 (a method for laser preparation of lyophobic surfaces in liquid phase). In the embodiment of the invention, the shapes of the microstructures in the microstructure array are specifically micro-protrusions, and the distance between every two adjacent micro-protrusions is preferably 2-5 μm.
The invention provides a preparation method of an underwater oil transportation functional structure, which comprises the following steps:
respectively preparing an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged on the periphery of the underwater super oleophilic wedge-shaped area on the surface of a substrate, and forming an underwater oil transportation functional structure on the surface of the substrate; the method for preparing the underwater super oleophilic wedge-shaped area comprises a laser liquid phase processing method, and the method for preparing the underwater super oleophobic area comprises a laser direct writing processing method.
According to the invention, an underwater super oleophilic wedge-shaped area is preferably prepared in a partial area of the surface of the substrate, and then an underwater super oleophobic area is prepared in other areas of the surface of the substrate, wherein the underwater super oleophobic area is arranged at the periphery of the underwater super oleophilic wedge-shaped area. In the present invention, the material of the substrate is preferably an alloy, and the alloy is preferably an aluminum alloy or a copper alloy; the specific grade of the alloy is not particularly limited, and in the embodiment of the invention, the alloy is specifically treated by taking an aluminum alloy 2524 or copper H62 as a matrix.
In the invention, the laser liquid phase processing method is preferably carried out in a fluorinated liquid with the concentration of 0.4-2 wt%, and the surface to be processed of the substrate is preferably 0.5-5 mm, more preferably 1-3 mm away from the liquid surface of the fluorinated liquid. In the present invention, the solute of the fluorinated liquid preferably includes fluorosilane F1060 (CFH)2CH2-Si(OC2H5)3) Trimethylsilane or a fluorine-containing acrylate copolymer, more preferably fluorosilane F1060; the solvent of the fluorinated liquid preferably comprises an alcohol solvent or toluene, and the alcohol solvent preferably comprises absolute ethyl alcohol or ethylene glycol; the concentration of the fluorizating liquid is preferably 0.8-1.5 wt%.
In the present invention, the conditions of the laser liquid phase processing method preferably include: picosecond laser pulse energy is 2-1000 mJ, pulse width is 50 fs-24 ps, and repetition frequency is 10-2000 Hz; more preferably, it comprises: the picosecond laser pulse energy is 20-300 mJ, the pulse width is 75 fs-15 ps, and the repetition frequency is 100-1000 Hz. In the invention, the scanning mode of the laser liquid phase processing method is preferably single horizontal or single vertical filling scanning, and the scanning interval is preferably 10-50 μm, and more preferably 30-40 μm.
In the invention, after an underwater super oleophilic wedge-shaped area is prepared on a partial area of the surface of a substrate by adopting a laser liquid phase processing method, the obtained substrate is preferably taken out of a fluorinated liquid, heated after being dried by nitrogen to fully remove a solvent on the surface of the substrate, and cooled to obtain the substrate with the underwater super oleophilic wedge-shaped area on the surface. In the invention, the nitrogen used for drying the nitrogen is preferably high-purity nitrogen; the temperature of the heating treatment is preferably 145-155 ℃, more preferably 150 ℃, and the time of the heating treatment is preferably 40-50 min, more preferably 45 min; the cooling is preferably natural cooling to room temperature, and in the embodiment of the present invention, room temperature specifically means 25 ℃.
In the present invention, the operating conditions of the laser direct write processing method preferably include: the laser wavelength was 1060nm and the laser power was 26W. In the invention, the scanning mode of the laser direct writing processing method is preferably horizontal and vertical sequentially alternate orthogonal filling scanning, more preferably, after the horizontal filling scanning is carried out for 5 times, the vertical filling scanning is carried out for 5 times, and the horizontal and vertical filling scanning is sequentially repeated; the scanning pitch is preferably 10 to 50 μm, and more preferably 10 to 30 μm. According to the invention, horizontal and vertical filling scanning is preferably adopted, and the scanning distance is controlled within the range, so that the adhesion of the solid surface is favorably reduced, and the transportation efficiency is improved.
In the invention, after an underwater super oleophobic area is prepared on other areas of the surface of a substrate by adopting a laser direct writing processing method, the obtained substrate is preferably subjected to ultrasonic cleaning, the cleaning solution adopted by the ultrasonic cleaning is preferably acetone, the ultrasonic cleaning time is preferably 10-20 min, and the equipment adopted by the ultrasonic cleaning is preferably a KQ2200B type ultrasonic cleaner.
The invention provides an application of the underwater oil transportation functional structure in the technical scheme or the underwater oil transportation functional structure prepared by the preparation method in the technical scheme in underwater oil transportation. In the present invention, the oil transportation functional structure is preferably used for underwater heavy oil transportation, and the heavy oil is not particularly limited in the present invention, and may be heavy oil well known to those skilled in the art. In the embodiment of the present invention, it may be specifically simethicone, peanut oil or n-dodecane; the surface tension of the dimethyl silicone oil is 20.1mN/m, and the dynamic viscosity is 100-500 mPa & s; the peanut oil has the surface tension of 33.956mN/m and the dynamic viscosity of 57.4mPa & s; n-dodecane had a surface tension of 25.35mN/m and a dynamic viscosity of 1.3588 mPas. The underwater oil transportation functional structure provided by the invention can be particularly used for underwater oil transportation in the field of biological detection, for example, in medical treatment, a biological sample (oil with high viscosity essentially) such as certain macromolecular proteins and the like needs to be transported to a specific position in a water environment to perform chemical reaction, and then a solution after the reaction is transported to another specific position to realize fixed-point detection on the biological sample. The underwater oil transportation functional structure provided by the invention can realize the self transportation of the underwater oil, and avoids the problems that a liquid transfer device is expensive, needs professional operation and is easy to damage a biological sample.
Fig. 3 is a schematic diagram of a principle that the functional structure provided by the present invention realizes underwater oil transportation, and as can be seen from fig. 3, oil drops at the narrow end of the wedge-shaped groove are spread along the wedge-shaped groove into a shape with front and rear end radii being in a gradient, so that the oil drops generate a laplacian pressure difference gradient along the direction of the groove at a three-phase contact line along a wedge-shaped contour line, and the oil drops can be automatically transported from the narrow end to the wide end of the wedge-shaped groove under the action of capillary force generated by the gradient, thereby realizing directional transportation of the underwater oil.
Fig. 4 is a schematic diagram of a principle that the functional structure provided by the invention realizes underwater oil long distance transportation, and when oil drops are transported from a narrow end to a wide end of a single wedge-shaped groove, the oil drops enter a narrow end of a next wedge-shaped groove from a transition arc, so that the oil drops are transported in the next wedge-shaped groove, and the underwater oil long distance transportation is realized through circulation.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The functional structure is prepared according to the flow chart shown in fig. 5, comprising the following steps:
with fluorosilane F1060 (CFH)2CH2-Si(OC2H5)3) Preparing 1.5 mass percent of fluorinated solution by using solute and toluene as solvent;
taking a hard alloy YG8 plate as a substrate, immersing the substrate in the fluorination liquid, enabling the fluorination liquid to submerge the upper surface of the substrate by 1mm, scanning and processing part of the surface of the substrate by adopting a laser liquid phase processing method to obtain an underwater super oleophilic wedge-shaped area, taking the substrate out of the fluorination liquid, drying the substrate by utilizing high-purity nitrogen, then carrying out heat preservation and heating in a heat preservation furnace at 150 ℃ for 45min to fully remove toluene on the surface of the substrate, and naturally cooling to room temperature (25 ℃) to obtain the substrate with the underwater super oleophilic wedge-shaped area; wherein the operating conditions of the laser liquid phase processing method comprise: the picosecond laser pulse energy is 20mJ, the pulse width is 75fs, and the repetition frequency is 1000 Hz; the scanning mode is single horizontal filling scanning, and the scanning interval is 30 mu m; the underwater super-oleophylic wedge-shaped area is formed by wedge-shaped microstructures distributed in an array, each wedge-shaped microstructure comprises a plurality of wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc in two adjacent wedge-shaped grooves connected in series along the underwater oil transportation direction, and the bottom of each wedge-shaped groove is provided with array micro-channels arranged in parallel; specifically, the wedge angle of each wedge-shaped groove is 4 degrees, the depth of each wedge-shaped groove is 300 microns, the width of each groove is 1mm, the radius of each transition arc is 3mm, each wedge-shaped microstructure is formed by 4 wedge-shaped grooves connected in series, the length of the first wedge-shaped groove is 9mm, the length increment of every two adjacent wedge-shaped grooves is 4mm, and the array period of the wedge-shaped grooves is 5 mm; the depth of the micro-channel is 60 μm, and the distance between adjacent micro-channels is 50 μm; the array period of the wedge-shaped microstructures is 2 mm;
in an air atmosphere, filling and scanning the periphery of the underwater wedge-shaped oleophylic region by using a laser direct writing processing method to obtain an underwater oleophobic region, wherein the underwater oleophobic region consists of a microprotrusion array, and the distance between adjacent microprotrusions is 2-5 microns; then placing the obtained substrate in a KQ2200B type ultrasonic cleaner for cleaning for 15min (the cleaning solution is acetone) to obtain a functional structure; wherein, the operating conditions of the laser direct writing processing method comprise: the laser wavelength is 1060nm, the laser power is 26W, the scanning mode is horizontal and vertical sequential alternate orthogonal filling scanning, specifically, after the horizontal filling scanning is performed for 5 times, the vertical filling scanning is performed for 5 times, the horizontal and vertical filling scanning is performed sequentially, and the scanning interval is 10 μm;
in the functional structure prepared by the embodiment, the area ratio of the underwater super oleophobic area to the underwater super oleophilic wedge-shaped area is 4: 1.
fig. 6 is a schematic view of the micro-morphology of the functional structure prepared in example 1, and fig. 7 is an SEM image of the functional structure prepared in example 1, it can be seen from the figure that the underwater superoleophobic area is composed of a microprotrusion array, and in the underwater superoleophilic wedge area, the bottom of the wedge-shaped groove is provided with array microchannels arranged in parallel. Because the underwater super oleophilic wedge-shaped area adopts a single scanning direction, an array micro-channel is formed; and the underwater super oleophobic area adopts two scanning modes vertical to the direction, so that a micro-bump array is formed, and the distance between adjacent micro-bumps is 2-5 mu m.
Example 2
The functional structure is prepared according to the flow chart shown in fig. 5, comprising the following steps:
with fluorosilane F1060 (CFH)2CH2-Si(OC2H5)3) Preparing 0.8 mass percent of fluorinated solution by using solute and toluene as solvent;
immersing a copper H62 substrate into the fluorination liquid, enabling the fluorination liquid to submerge 1mm above the upper surface of the substrate, scanning and processing the surface of part of the substrate by adopting a laser liquid phase processing method to obtain an underwater super oleophilic wedge-shaped area, taking the substrate out of the fluorination liquid, drying the substrate by utilizing high-purity nitrogen, then carrying out heat preservation and heating in a heat preservation furnace at 150 ℃ for 60min to fully remove toluene on the surface of the substrate, and naturally cooling to room temperature (25 ℃) to obtain the substrate with the underwater super oleophilic wedge-shaped area; wherein the operating conditions of the laser liquid phase processing method comprise: the picosecond laser pulse energy is 20mJ, the pulse width is 75fs, and the repetition frequency is 1000 Hz; the scanning mode is single horizontal filling scanning, and the scanning interval is 0.02 mm; the underwater super-oleophylic wedge-shaped area is formed by wedge-shaped microstructures distributed in an array, each wedge-shaped microstructure comprises a plurality of wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc in every two adjacent wedge-shaped grooves connected in series, and the bottom of each wedge-shaped groove is provided with array micro-channels distributed in parallel; specifically, the wedge angle of each wedge-shaped groove is 5 degrees, the depth of each wedge-shaped groove is 120 microns, the width of each groove is 0.5mm, the radius of each transition arc is 0.2mm, each wedge-shaped microstructure is formed by 8 wedge-shaped grooves connected in series, the length of the first wedge-shaped groove is 3mm, the length increment of every two adjacent wedge-shaped grooves is 1mm, and the array period of the wedge-shaped grooves is 2 mm; the depth of the micro-channel is 70 μm, and the distance between adjacent micro-channels is 60 μm; the array period of the wedge-shaped microstructures is 3 mm;
in an air atmosphere, filling and scanning the periphery of the underwater wedge-shaped oleophylic region by using a laser direct writing processing method to obtain an underwater oleophobic region, wherein the underwater oleophobic region consists of a microprotrusion array, and the distance between adjacent microprotrusions is 2-5 microns; then placing the obtained substrate in a KQ2200B type ultrasonic cleaner for cleaning for 15min (the cleaning solution is acetone) to obtain a functional structure; wherein, the operating conditions of the laser direct writing processing method comprise: the laser wavelength is 1060nm, the laser power is 20W, the scanning mode is horizontal and vertical sequential alternate orthogonal filling scanning, specifically, after the horizontal filling scanning is performed for 5 times, the vertical filling scanning is performed for 5 times, the horizontal and vertical filling scanning is performed sequentially, and the scanning interval is 10 μm;
in the functional structure prepared by the embodiment, the area ratio of the underwater super oleophobic area to the underwater super oleophilic wedge-shaped area is 4: 1.
performance testing
Preparing a wedge-shaped microstructure on the surface of a substrate according to the method in the embodiment 1, wherein the wedge-shaped microstructure comprises 4 wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc, specifically, the wedge angle of the wedge-shaped groove is 3 degrees, the depth of the wedge-shaped groove is 180 μm, the groove width is 2mm, the radius of the transition arc is 5mm, the length of the first wedge-shaped groove is 20mm, the length increment of two adjacent wedge-shaped grooves is 3mm, and the array period of the wedge-shaped grooves is 2 mm; the depth of the microchannels is 60 μm and the distance between adjacent microchannels is 30 μm.
Dripping 50 mu L of dimethyl silicone oil with surface tension of 20.1mN/m and dynamic viscosity of 300mPa & s at the narrow end of the first wedge-shaped groove on the surface of the substrate, and rapidly advancing the liquid drop to the wide end of the first wedge-shaped groove when t is 30 ms; when t is 1000ms, the liquid drops are gradually converged to the narrow end of the second wedge-shaped groove from the arc transition region; when t is 1032ms, the liquid drop is transported from the narrow end of the second wedge-shaped groove to the wide end of the second wedge-shaped groove; when t is 2042ms, the liquid drop is transported from the wide end of the second wedge-shaped groove to the narrow end of the third wedge-shaped groove; 2087ms, the liquid drop is transported from the narrow end of the third wedge-shaped groove to the wide end of the third wedge-shaped groove, and the process continues until the liquid drop is transported to the wide end of the fourth wedge-shaped groove.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. An underwater oil transportation functional structure comprises an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged at the periphery of the underwater super oleophilic wedge-shaped area; the underwater super-oleophylic wedge-shaped area is formed by wedge-shaped microstructures distributed in an array, each wedge-shaped microstructure comprises a plurality of wedge-shaped grooves connected in series, and in two adjacent wedge-shaped grooves connected in series, the wide end of one wedge-shaped groove is connected with the narrow end of the other wedge-shaped groove through a transition arc along the underwater oil transportation direction; and the bottom of each wedge-shaped groove is provided with an array micro-channel which is arranged in parallel.
2. The underwater oil transportation functional structure according to claim 1, wherein a wedge angle of each of the wedge-shaped grooves is independently 0.5 to 10 °, a depth is independently-800 to 800 μm, a length is independently 0.1 to 50mm, and a groove width is independently 1 to 10 mm;
the depth of each micro channel in the array micro channel is-880-550 mu m independently, and the distance between every two adjacent micro channels is 10-100 mu m.
3. The underwater oil transportation functional structure according to claim 2, wherein the radius of the transition arc is 0.1 to 15 mm.
4. The underwater oil transportation functional structure according to claim 2, wherein an array period of the wedge-shaped grooves is 2 μm to 6 mm; the period of the wedge-shaped microstructures distributed in the array is 10 micrometers-10 mm.
5. The underwater oil transportation functional structure according to any one of claims 1 to 4, wherein an area ratio of the underwater superoleophobic area to the underwater superoleophilic wedge area is 0.5 to 10: 1.
6. a method of making an underwater oil transport functional structure as claimed in any one of claims 1 to 5, comprising the steps of:
respectively preparing an underwater super oleophilic wedge-shaped area and an underwater super oleophobic area arranged on the periphery of the underwater super oleophilic wedge-shaped area on the surface of a substrate, and forming an underwater oil transportation functional structure on the surface of the substrate; the method for preparing the underwater super oleophilic wedge-shaped area comprises a laser liquid phase processing method, and the method for preparing the underwater super oleophobic area comprises a laser direct writing processing method.
7. The method according to claim 6, wherein the laser liquid phase processing is performed in a fluorinated liquid having a concentration of 0.4 to 2 wt%, and the surface to be processed of the substrate is 0.5 to 5mm from the surface of the fluorinated liquid.
8. The production method according to claim 6 or 7, wherein the conditions of the laser liquid phase processing method include: picosecond laser pulse energy is 2-1000 mJ, pulse width is 50 fs-24 ps, and repetition frequency is 10-2000 Hz; the scanning mode is single horizontal or single vertical filling scanning, and the scanning interval is 10-50 μm.
9. The production method according to claim 6, wherein the operating conditions of the laser direct write processing method include: the laser wavelength is 1060nm, and the laser power is 26W; the scanning mode is horizontal and vertical alternate orthogonal filling scanning, and the scanning interval is 10-50 mu m.
10. Use of the underwater oil transportation functional structure according to any one of claims 1 to 5 or the underwater oil transportation functional structure prepared by the preparation method according to any one of claims 6 to 9 in underwater oil transportation.
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