Elektrodeponerede overflader med reversibelt skiftende grænsefladeegenskaber

Materialeteknologiske teknologier sigter mod at kontrollere befugtning og væskeafvisning af materialeoverflader til forskellige anvendelser inden for og uden for materialevidenskab. I en nylig rapport vedr Videnskabens fremskridt , Yue Liu og et team af forskere i afdelingerne for Materials Science and Engineering, og kemi og molekylær teknik i Kina udviklede et generelt koncept til at udvikle metalliske porøse overflader med usædvanligt kraftige, befugtnings-switch-funktioner. For at konstruere de nye overflader, de brugte en meget enkel, et-trins elektrokemisk aflejringsproces. Holdet aktiverede fugtbarhedskontakten og manipulerede væskeafvisende egenskaber ved at ændre orienteringen af ​​dodecylsulfationer, der var ionisk bundet til porøse metalliske membraner under elektroaflejring. De resulterende overflader med justerbar befugtning kan efter behov fange forskellige smøremidler i porerne for at skabe væskeinfunderede porøse overflader, tilpasset til en række forskellige væskeafvisende egenskaber. Forskerholdet demonstrerede anvendelserne af væskeinfunderede porøse membraner til kryptering, til at kontrollere dråbeoverførsel og til vandhøst. Derudover materialeforskerne belagde den porøse sølvmembran på et kobbernet for at konstruere en smart, antifouling væskeport for at tillade olie eller vand at passere igennem efter anmodning.

I materialeteknik, forskere sigter mod at udvikle reversibelt omskiftelige grænsefladeegenskaber til forskellige applikationer fra mikrofluidiksystemer, til vandindsamling og transport, samt separatorer, sensorer og medicinafgivelsessystemer. Materialeforskere har i vid udstrækning studeret sådanne omskiftelige befugtningsoverflader styret via eksterne stimuli, herunder lys, pH værdi, termisk og elektrokemisk behandling, modioner og elektriske potentialer. I nærværende arbejde, Liu et al. rapporterede en meget enkel, et-trins elektroaflejringstilgang til at konstruere porøse metaloverflader med robust befugtnings-omskiftningskapacitet koblet til fremragende væskeafvisende egenskaber, der adskilte sig fra tidligere rapporterede mekanismer til at konstruere en ny befugtningsswitch.

Teknisk reversibel befugtning på elektroaflejrede porøse overflader

Liu et al. modulerede orienteringen af ​​dodecylsulfationer, der ionisk bundede til den porøse membran under elektroaflejring for at etablere reversibelt indstillelig overfladebefugtning. For eksempel, når dodecylkæderne pegede udad, membranen bibeholdt superhydrofobicitet (vandhadende natur). Derefter brugte forskerne elektriske potentialer til at overføre befugtningen fra superhydrofob (vandhadende) til den superhydrofile (vandelskende) tilstand. De bekræftede ioniske overfladeorienteringsændringer ved hjælp af overfladeforstærkede Raman-spredningsmålinger (SERS). Baseret på den ioniske orienterings-inducerede udvikling af elektroaflejrede porøse overflader, forskerholdet fangede forskellige smøremidler fast i porerne for at danne forskellige "glatte væskeinfunderede porøse overflader (SLIPS)" til flere anvendelser.

Den nye teknik vil have et betydeligt potentiale i forskellige termokemiske anvendelser på grund af dens tekniske enkelhed, alsidighed og lave omkostninger. For at danne den reversible befugtningskontakt, forskerne elektroafsatte først en sølvporøs membran på en guldbelagt siliciumwafer i en elektrolytopløsning indeholdende sølvnitrat og natriumdodecylsulfat (SDS). Efterhånden som tidslinjen for elektroaflejring steg, the membrane roughness gradually increased, after four minutes, the resulting membrane was superhydrophillic. With the assistance of organic liquids as well as with water containing a minute amount of ethanol (one percent in volume), the scientists could induce the transition of wettability from superhydrophillic (or superoleophillic; water loving) to superhydrophobic (water hating). The instant transition indicated high sensitivity of the membrane toward organic reagents. The water contact angle also increased (hydrophobic character) when they simply exposed the silver porous membrane to an ethanol atmosphere (i.e organic reagent).

Understanding the mechanism of wettability transition

The research team conduced systematical studies to reveal the underlying mechanisms of wettability transition, first by using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) for surface analysis. They proved the existence of SDS ions within the silver porous membrane to form a monolayer structure similar to a previously well-studied surface. Liu et al. hypothesized that hydrophobic dodecyl chain tails hid inside the pores of the freshly prepared silver porous membrane– prompting the silver membrane to initially demonstrate hydrophilicity due to the exposed, hydrophilic sulfate heads.

When the superhydrophillic surface then encountered organic reagents such as ethanol, the hidden dodecyl chain tails changed orientation to face the organic liquids due to their mutually strong affinity. Due to challenges of proving the changing orientation of the dodecyl chains on the rough porous membranes using conventional scanning tunneling microscopy or atomic force microscopy, the team used SERS. The SERS intensity, which mapped the interactions between dodecyl ionic chains and silver sulfate surface, confirmed the transition that facilitated the membrane wettability switch. When they removed the dodecyl ions using oxygen plasma treatment, they eliminated the wettability switch from the silver porous membrane.

Applications of the technique—encryption and liquid transfer

Having developed a new concept to engineer reversible wettability, the research team developed a variety of applications such as information encryption, droplet transfer, liquid-repellence, fog harvesting, and smart liquid gate as well as oil/water separation. For information encryption, Liu et al. dragged a pencil that behaved as a cathode electrode immersed in a droplet, upon the superhydrophobic surface connected to the positive pole of the power supply to write the letters "ZJU." The surface then transformed to maintain hydrophilicity and when the scientists exposed the surface to water or steam, the encrypted invisible words were revealed due to surface attachment of water droplets. They could change the speed of encryption and remove the hydrophilic track using ethanol to recycle the surface multiple times for reuse. By changing surface properties, they could also induce conditions of hydrophobic encryption. The research team then made use of strong surface adhesion to transfer water droplets across from superhydrophillic surfaces using ethanol-treated silver porous membranes, where droplets adhered on top of the silver membrane for easy transfer.

Harnessing the liquid-repellent properties for additional applications

Derefter, the research team designed silver porous membranes to change from superhydrophillic SLIPS1 (slippery liquid-infused porous surfaces) to superhydrophobic SLIPS2 to form a repeatable cycle between SLIP1 and SLIP2 surfaces for a desired timeframe. The work described here were a first in study to engineer such complex wetting and liquid-repellent properties with potential for dynamic adjustment to match diverse lubricants. Derudover bioinspired by the Namib desert beetle that used patterned hydrophilic and hydrophobic elytra (hardened forewing) to retain or remove water droplets, Liu et al. patterned stripes of SLIP2 for excellent water repellence. They engineered surfaces to adhere water molecules for nucleation on hydrophilic surfaces upon exposure to water mist for outstanding fog harvesting efficiency.

Næste, the scientists electrochemically coated the silver porous membrane onto a copper mesh for applications as a smart liquid gate. While the original superhydrophobicity prohibited the passage of water, when they applied a negative electric potential to the copper mesh, the surfaces became superhydrophilic for the immediate passage of water. The surface property could be interchangeably engineered by exposure to ethanol vapor, for reuse. Liu et al. similarly engineered silver-coated copper meshes for selective water/oil separation, which differed from existing prototypes for efficient oil and water isolation and transfer.

På denne måde Yue Liu and colleagues developed a general concept to engineer metallic coatings with switchable wettability liquid repellence using a simple, one-step electrodeposition method. They harnessed the changing orientation of dodecyl sulfate ions ionically bonded to the electrodeposited porous metallic membrane, with organic reagent treatment or an external electric potential to facilitate the wettability switch. They recycled the wettability transition more than 10 times in the study, while forming diverse SLIPS for a variety of applications. The extremely simple and cost-effective materials engineering approach to form switchable wettability and liquid-repellant materials surfaces will have promising applications in liquid/thermal-related fields within and beyond materials science.

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