CN111944091B - Preparation method of semi-polymerized ionic liquid-filled super-smooth surface - Google Patents
Preparation method of semi-polymerized ionic liquid-filled super-smooth surface Download PDFInfo
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- CN111944091B CN111944091B CN202010940862.8A CN202010940862A CN111944091B CN 111944091 B CN111944091 B CN 111944091B CN 202010940862 A CN202010940862 A CN 202010940862A CN 111944091 B CN111944091 B CN 111944091B
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
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Abstract
The invention relates to a preparation method of a semi-polymerized ionic liquid perfusion-based super-smooth surface, which is characterized by comprising the following steps of: firstly, modifying the surface of porous anodic aluminum oxide; then uniformly spreading the ionic liquid prepolymer on the modified porous anodic aluminum oxide surface; secondly, horizontally placing for 10 min under the condition of-80 KPa, and rotating at the rotating speed of 1000 rpm for 10 s to obtain porous anodic alumina infused with ionic liquid prepolymer; finally, the porous anodic alumina infused with the ionic liquid prepolymer is subjected to heat preservation for 5 hours at 80 ℃ under the vacuum condition, and a layer of polyion gel film can be formed on the pore wall; and the excessive unpolymerized ionic liquid prepolymer on the surface of the porous anodic aluminum oxide is used as a lubricating layer of the super-smooth surface. The method has the advantages of simple process, easily obtained raw materials, strong stability of the obtained super-smooth surface, good performance and suitability for large-area preparation and application.
Description
Technical Field
The invention relates to the technical field of preparation of ultra-smooth materials, in particular to a preparation method of an ultra-smooth surface based on semi-polymerization ionic liquid perfusion.
Background
Inspired by the action of nepenthes in the slippage area in the insect catching process, many researchers focus their attention on the study of porous super-slippery surfaces into which lubricating fluids are injected. The porous super-lubricious surface into which the lubricating fluid is injected is a solid-liquid composite interfacial system with a porous surface and a low surface energy liquid. In general, to achieve a robust solid-liquid composite interface, the microstructure of the surface, the properties of the lubricant, and the interaction of the solid-liquid interface need to be fully considered. However, most of the porous structures applied to the ultra-smooth surface at present have irregular shapes and sizes, the pores are connected internally, and the sliding performance of the ultra-smooth surface fails under the action of external force because the side wall cannot be sealed and cannot stably lock the lubricant. Meanwhile, the preparation of the ultra-smooth surface material has the problems of complicated steps, poor weather resistance and low practicability.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a semi-polymerized ionic liquid perfusion-based super-smooth surface, which is simple, convenient and easy for industrial production.
In order to solve the problems, the invention provides a preparation method of a semi-polymerized ionic liquid perfusion-based super-smooth surface, which is characterized by comprising the following steps: firstly, modifying the surface of porous Anodic Aluminum Oxide (AAO); then uniformly spreading the ionic liquid prepolymer on the modified porous Anodic Aluminum Oxide (AAO) surface; secondly, horizontally placing for 10 min under the condition of-80 KPa, and rotating at the rotating speed of 1000 rpm for 10 s to obtain porous Anodic Aluminum Oxide (AAO) filled with the ionic liquid prepolymer (IL); finally, the porous Anodic Aluminum Oxide (AAO) infused with the ionic liquid prepolymer is subjected to heat preservation for 5 hours at 80 ℃ under the vacuum condition, and a layer of polyion gel film (PIL) can be formed on the pore wall; and the excessive unpolymerized ionic liquid prepolymer on the surface of the porous anodic aluminum oxide is used as a lubricating layer of the super-smooth surface.
The method for modifying the surface of the porous Anodic Aluminum Oxide (AAO) comprises the steps of cleaning, removing impurities and drying the porous Anodic Aluminum Oxide (AAO), and immersing the porous Anodic Aluminum Oxide (AAO) into a trimethoxy silicon-based propyl methacrylate solution with the volume fraction of 5% for 24 hours; taking out and standing in the shade to obtain the product.
The ionic liquid prepolymer (IL) refers to ionic liquid vinyl hexyl imidazole trifluoromethyl sulfimide ([ VHIM)][NTf2]) Ethylene glycol dimethacrylate and azobisisobutyronitrile 100: 2: 1, and performing ultrasonic treatment for 20 min to mix uniformly to obtain the product.
Compared with the prior art, the invention has the following advantages:
1. the invention takes porous Anodic Aluminum Oxide (AAO) with regular shape and size and high aspect ratio holes as a substrate, and the wall of the AAO hole is coated with a polyion gel film with certain pores.
2. According to the invention, the interaction between the polyion gel film and the AAO hole wall is realized through olefin polymerization, and the residual unpolymerized ionic liquid is firmly locked through intermolecular force between the ionic liquid and the polyion gel film and certain capillary force remained by the polyion gel film and can be used as a lubricating layer on an ultra-smooth surface, so that the purpose of stably keeping lubricating oil in the holes is realized.
3. The preparation method has the advantages of simple preparation process, simple and easily obtained reaction raw materials and strong stability.
4. The ultra-smooth surface prepared by the polymerization method is suitable for large-area preparation and application.
5. The AAO porous surface coated by the polyion gel film enhances the interaction force between the ionic liquid and the porous surface, so that the ultra-smooth surface is endowed with excellent stability in severe environment.
6. The prepared ionic liquid-filled ultra-smooth surface not only has excellent sliding performance (the sliding angle is 1.35 +/-0.06 degrees) at room temperature, but also can show stable sliding performance (the sliding angle is less than 4 degrees) under severe environments such as high temperature (220 degrees) and high shear rate (7000 rpm), and the like, and also still shows better stability after certain cycle times of washing with ethanol and refilling with the ionic liquid. Meanwhile, the ultra-smooth surface filled with the ionic liquid has excellent corrosion resistance, and can adsorb dye in waste liquid under the condition of not influencing the sliding performance.
The following samples were used for the tests:
the original AAO porous surface was used as sample AAO, the AAO porous surface directly perfused with the ionic liquid prepolymer was used as sample IL/AAO, the AAO porous surface from which excess ionic liquid prepolymer was washed off with absolute ethanol after preparation according to the procedure in example 1 was used as sample PIL/AAO, and the sample prepared according to the procedure in example 1 was used as IL/PIL/AAO. Wherein: IL refers to ionic liquid prepolymer and PIL refers to polyionic gel membranes coated on AAO pore walls. IL/PIL/AAO is a sample of polyionic gel film prepared according to the procedure in example 1 coated with unpolymerized ionic liquid prepolymer coated on the surface.
[ test of sliding Property ] A contact angle and a sliding angle of AAO, IL/AAO, PIL/AAO and IL/PIL/AAO prepared in example 1 were measured, respectively, by dropping 10. mu.L of deionized water on the surface of a sample in an atmosphere at room temperature. As shown in fig. 2, in which the surface without the ionic liquid used as the lubricating liquid showed a large adhesion force, water droplets did not slip off when the AAO and PIL/AAO were placed vertically; and IL/AAO and IL/PIL/AAO have smaller sliding angles, and the sliding performance of the IL/PIL/AAO is more excellent (the sliding angle is 1.35 +/-0.06 degrees). The test results show that the sample in which the ionic liquid was used as the lubricating layer showed good sliding properties.
[ temp. gradient test and high-temp. stability test within a certain time range ] under room-temperature atmospheric environment, 10. mu.L of deionized water was dropped on the surface of IL/PIL/AAO prepared in example 1, and the IL/PIL/AAO was kept at 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃, 180 ℃, 200 ℃, 220 ℃ for 15 min, respectively. The contact angle and the sliding angle of 10. mu.L of a water droplet on the surface of the sample were measured immediately after the sample was taken out. It can be seen from fig. 3(a) that the contact angle and the sliding angle gradually increase as the temperature increases. The sliding angle at 220 ℃ is 3.48 +/-0.06 DEG, and the sliding performance is still excellent.
The IL/PIL/AAO sample prepared in example 1 was maintained at a temperature of 60 ℃, 80 ℃, 100 ℃ and 120 ℃ for 12 hours, and the contact angle and the sliding angle of the sample were measured. The test results are shown in fig. 3(b), and it can be seen that both the contact angle and the sliding angle increase with increasing temperature. However, after 12 hours at 120 ℃, the sliding angle of the sample is still less than 4 ℃, and good sliding performance is still shown.
Thus, the above tests show that: the sample prepared in example 1 has good high temperature stability.
Shear resistance test and ethanol rinse and recharge ionic liquid cycle test IL/AAO samples were subjected to shear resistance tests at different shear rates than IL/PIL/AAO samples prepared using example 1. The ionic liquid content per unit area of the sample at different shear rates was measured. As can be seen from FIG. 4(a), the ionic liquid content per unit area of the IL/PIL/AAO sample was 0.79 mg/cm at a shear rate of 7000 rpm-2Is twice as large as the IL/AAO sample (0.37 mg/cm)-2). Indicating that the presence of the polyion gel membrane improved the oil locking ability of the sample.
FIG. 4(b) is the contact angle and sliding angle for IL/AAO and IL/PIL/AAO under different shear rate conditions. As the ionic liquid content of the sample decreases, the contact angle and the sliding angle also increase. At a shear rate of 7000 rpm, the contact angles of IL/AAO and IL/PIL/AAO were similar, but the sliding angle of IL/PIL/AAO (2.29 ℃ C.) was smaller than that of IL/AAO (6.69 ℃ C.). The result shows that the polyion gel film not only ensures the excellent oil locking capacity of the sample, but also ensures the excellent sliding performance of the sample.
The IL/PIL/AAO samples prepared in example 1 were rinsed with ethanol and then re-perfused with ionic liquid and spun at a shear rate of 7000 rpm for 10 seconds. The ionic liquid content per unit area and the contact angle and sliding angle were measured by cycling 50 times.
As can be seen from FIGS. 4(c) and 4(d), the oil-locking ability and sliding performance of the IL/PIL/AAO sample were substantially unchanged at the first 30 cycles, but the oil-locking ability and sliding performance after 30 cycles were degraded and were close to those of the IL/AAO sample at 7000 rpm. It shows that the polyion gel film of the IL/PIL/AAO sample is completely dissolved away by ethanol after 50 times of ethanol washing.
Thus, the above tests show that: the sample prepared using example 1 has good shear properties.
[ Corrosion resistance test ] AAO, PIL/AAO and IL/PIL/AAO samples prepared using example 1 were subjected to corrosion resistance testing in a 3.5wt% sodium chloride solution. Tafel plots of the AAO, PIL/AAO and IL/PIL/AAO samples before bending (FIG. 5(a)) and after bending (FIG. 5(b)) were measured, as well as a plot of the corrosion current density for the different samples before and after bending (FIG. 5 (c)). It can be seen from the figure that the ionic liquid infused surface still has excellent corrosion resistance after bending. The test results show that the sample prepared in example 1 has good corrosion resistance characteristics.
[ dye adsorption test ] A methylene blue solution with a concentration of 1.5 mg/L, a rhodamine B solution with a concentration of 1 mg/L and a Congo red solution with a concentration of 5 mg/L are prepared. 50 μ L of the dye solution was dropped onto the surface of the IL/PIL/AAO sample prepared in example 1 for 30 seconds each time and collected, and the UV-visible absorption spectrum test was performed every 1mL collected. FIG. 6(a), FIG. 6(B) and FIG. 6(c) are UV-Vis spectra of different adsorption degrees of methylene blue, rhodamine B and Congo red, respectively, and FIG. 6(d) is the change of contact angle and sliding angle of different adsorption degrees of methylene blue of 1.5 mg/L. The result shows that the IL/PIL/AAO sample has certain adsorption capacity on the dye on the premise of not influencing the sliding performance.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
Fig. 1 is a three-dimensional contour diagram of the original AAO porous surface (a, b), the AAO porous surface coated with polyion gel film (d, e) and its cross section (g-i) at different magnifications in example 1 of the present invention, and the original AAO porous surface (c) and the AAO porous surface impregnated with ionic liquid (f).
Fig. 2 is a contact angle and a rolling angle of a water drop in air on the surface of a sample prepared in example 1 of the present invention.
FIG. 3 shows the contact angle versus sliding angle (a) for IL/PIL/AAO prepared according to example 1 of the present invention at different temperature gradients and the contact angle versus sliding angle (b) over 12h at different temperature conditions.
FIG. 4 is a graph of ionic liquid content per unit area (a), contact angle and sliding angle (b) for IL/AAO and IL/PIL/AAO prepared according to example 1 of the present invention under different shear rate conditions and ionic liquid content per unit area (c), contact angle and sliding angle (d) for a reperfusion of the ionic liquid by 50 ethanol rinses and at a shear rate of 7000 rpm.
FIG. 5 is a Tafel plot of AAO, IL/AAO and IL/PIL/AAO prepared in example 1 of the present invention before (a) and after (b) bending and a graph of corrosion current density for different samples before and after bending (c).
FIG. 6 is a graph showing the difference in degree of adsorption of IL/PIL/AAO prepared in example 1 of the present invention to methylene blue (a) at 1.5 mg/L, rhodamine B (b) at 1 mg/L, Congo red (c) at 5 mg/L, and the change in contact angle and sliding angle to methylene blue at 1.5 mg/L.
Detailed Description
A preparation method of a semi-polymerized ionic liquid infused super-smooth surface comprises the following steps:
firstly, modifying the surface of porous Anodic Aluminum Oxide (AAO): ultrasonically cleaning porous Anodic Aluminum Oxide (AAO) by absolute ethyl alcohol to remove impurities on the surface of the porous Anodic Aluminum Oxide (AAO), drying the porous Anodic Aluminum Oxide (AAO) for 30 min at 30 ℃, and then immersing the porous Anodic Aluminum Oxide (AAO) into trimethoxysilyl propyl methacrylate solution with the volume fraction of 5% for 24 h; taking out and standing in the shade to obtain the product. At this time, the methoxy-terminal ends of trimethoxysilylpropyl methacrylate were grafted onto the hydroxyl-rich AAO surface.
Then the ionic liquid prepolymer (IL) was evenly laid on the modified AAO surface. Wherein the ionic liquid prepolymer (IL) refers to ionic liquid vinyl hexyl imidazole trifluoromethyl sulfimide ([ VHIM)][NTf2]) Ethylene glycol dimethacrylate and azobisisobutyronitrile 100: 2: 1 (g/g) and then evenly mixing by ultrasonic treatment for 20 min.
And horizontally placing for 10 min under the condition of-80 KPa to fill the ionic liquid prepolymer (pores on the surface of the AAO, and rotating at the rotating speed of 1000 rpm for 10 s to remove the redundant ionic liquid prepolymer, thereby obtaining the porous Anodic Aluminum Oxide (AAO) infused with the ionic liquid prepolymer.
Finally, in order to realize the semi-polymerization state of the ionic liquid prepolymer, the porous Anodic Aluminum Oxide (AAO) filled with the ionic liquid prepolymer is subjected to heat preservation at 80 ℃ for 5 hours, namely a layer of polyion gel membrane (PIL) is formed on the pore wall of the AAO, and certain pores exist, namely the polyion gel membrane only covers the pore wall of the AAO, and certain capillary force remains, as shown in figure 1. As can be seen from fig. 1, the polyion gel membrane is uniformly attached to the pore wall of the AAO, and certain pores are left to provide space for capillary adsorption of the ionic liquid. The excess unpolymerized ionic liquid prepolymer on the surface of the porous anodized aluminum is used as a lubricating layer of the ultra-smooth surface.
Claims (1)
1. A preparation method of a semi-polymerized ionic liquid infused ultra-smooth surface is characterized by comprising the following steps: firstly, modifying the surface of porous anodic aluminum oxide; then uniformly spreading the ionic liquid prepolymer on the modified porous anodic aluminum oxide surface; secondly, horizontally placing for 10 min under the condition of-80 KPa, and rotating at the rotating speed of 1000 rpm for 10 s to obtain porous anodic alumina infused with ionic liquid prepolymer; finally, the porous anodic alumina infused with the ionic liquid prepolymer is subjected to heat preservation for 5 hours at 80 ℃ under the vacuum condition, and a layer of polyion gel film can be formed on the pore wall; the excessive unpolymerized ionic liquid prepolymer on the surface of the porous anodic aluminum oxide is used as a lubricating layer of the super-smooth surface; the surface modification method of the porous anodic aluminum oxide comprises the steps of cleaning, impurity removing and drying the porous anodic aluminum oxide, and immersing the porous anodic aluminum oxide into a 5% trimethoxysilyl propyl methacrylate solution by volume fraction for 24 hours; taking out and standing in a shade place to obtain the product; the ionic liquid prepolymer is prepared by mixing ionic liquid vinyl hexyl imidazole trifluoromethyl sulfimide, ethylene glycol dimethacrylate and azobisisobutyronitrile 100: 2: 1, and performing ultrasonic treatment for 20 min to mix uniformly to obtain the product.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014209441A2 (en) * | 2013-03-13 | 2014-12-31 | President And Fellows Of Harvard College | Solidifiable composition for preparation of liquid-infused slippery surfaces and methods of applying |
| CN104704067A (en) * | 2012-07-12 | 2015-06-10 | 哈佛学院院长及董事 | Slippery self-lubricating polymer surfaces |
| CN109438606A (en) * | 2018-11-09 | 2019-03-08 | 北京化工大学 | A kind of construction method of fluid injection porous material smooth surface |
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| US10557042B2 (en) * | 2016-03-28 | 2020-02-11 | Wisconsin Alumni Research Foundation | Slippery liquid-infused porous surfaces that prevent microbial surface fouling |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104704067A (en) * | 2012-07-12 | 2015-06-10 | 哈佛学院院长及董事 | Slippery self-lubricating polymer surfaces |
| WO2014209441A2 (en) * | 2013-03-13 | 2014-12-31 | President And Fellows Of Harvard College | Solidifiable composition for preparation of liquid-infused slippery surfaces and methods of applying |
| CN109438606A (en) * | 2018-11-09 | 2019-03-08 | 北京化工大学 | A kind of construction method of fluid injection porous material smooth surface |
Non-Patent Citations (2)
| Title |
|---|
| "Multi-functional fluorinated ionic liquid infused slippery surfaces with dual-responsive wettability switching and self-repairing";Qingqing Rao等;《Journal of Materials Chemistry A》;20181224;第7卷(第5期);第2172-2183页 * |
| "灌注液体型光滑多孔表面制备及应用";韦存茜等;《化学进展》;20160125;第28卷(第1期);第9-17页 * |
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