Despina Fragouli

Magnetically Driven Floating Foams for the Removal of Oil Contaminants from Water

In this study, we present a novel composite material based on commercially available polyurethane foams functionalized with colloidal superparamagnetic iron oxide nanoparticles and submicrometer polytetrafluoroethylene particles, which can efficiently separate oil from water. Untreated foam surfaces are inherently hydrophobic and oleophobic, but they can be rendered water-repellent and oil-absorbing by a solvent-free, electrostatic polytetrafluoroethylene particle deposition technique. It was found that combined functionalization of the polytetrafluoroethylene-treated foam surfaces with colloidal iron oxide nanoparticles significantly increases the speed of oil absorption. Detailed microscopic and wettability studies reveal that the combined effects of the surface morphology and of the chemistry of the functionalized foams greatly affect the oil-absorption dynamics. In particular, nanoparticle capping molecules are found to play a major role in this mechanism. In addition to the water-repellent and oil-absorbing capabilities, the functionalized foams exhibit also magnetic responsivity. Finally, due to their light weight, they float easily on water. Hence, by simply moving them around oil-polluted waters using a magnet, they can absorb the floating oil from the polluted regions, thereby purifying the water underneath. This low-cost process can easily be scaled up to clean large-area oil spills in water.

Water-Repellent Cellulose Fiber Networks with Multifunctional Properties

We demonstrate a simple but highly efficient technique to introduce multifunctional properties to cellulose fiber networks by wetting them with ethyl-cyanoacrylate monomer solutions containing various suspended organic submicrometer particles or inorganic nanoparticles. Solutions can be applied on cellulosic surfaces by simple solution casting techniques or by dip coating, both being suitable for large area applications. Immediately after solvent evaporation, ethyl-cyanoacrylate starts cross-linking around cellulose fibers under ambient conditions because of naturally occurring surface hydroxyl groups and adsorbed moisture, encapsulating them with a hydrophobic polymer shell. Furthermore, by dispersing various functional particles in the monomer solutions, hydrophobic ethyl-cyanoacrylate nanocomposites with desired functionalities can be formed around the cellulose fibers. To exhibit the versatility of the method, cellulose sheets were functionalized with different ethyl-cyanoacrylate nanocomposite shells comprising submicrometer wax or polytetrafluoroethylene particles for superhydophobicity, MnFe(2)O(4) nanoparticles for magnetic activity, CdSe/ZnS quantum dots for light emission, and silver nanoparticles for antimicrobial activity. Morphological and functional properties of each system have been studied by scanning and transmission electron microscopy, detailed contact angle measurements, light emission spectra and E. coli bacterial growth measurements. A plethora of potential applications can be envisioned for this technique, such as food and industrial packaging, document protection, catalytic cellulosic membranes, textronic (electrofunctional textiles), electromagnetic devices, authentication of valuable documents, and antimicrobial wound healing products to name a few.

Dynamical Formation of Spatially Localized Arrays of Aligned Nanowires in Plastic Films with Magnetic Anisotropy

We present a simple technique for magnetic-field-induced formation, assembling, and positioning of magnetic nanowires in a polymer film. Starting from a polymer/iron oxide nanoparticle casted solution that is allowed to dry along with the application of a weak magnetic field, nanocomposite films incorporating aligned nanocrystal-built nanowire arrays are obtained. The control of the dimensions of the nanowires and of their localization across the polymer matrix is achieved by varying the duration of the applied magnetic field, in combination with the evaporation dynamics. These multifunctional anisotropic free-standing nanocomposite films, which demonstrate high magnetic anisotropy, can be used in a wide field of technological applications, ranging from sensors to microfluidics and magnetic devices.

Spatially controlled surface energy traps on superhydrophobic surfaces.

Water wetting and adhesion control on polymeric patterns are achieved by tuning the configuration of their surfaces structural characteristics from single to dual and triple length-scale. In particular, surfaces with combined micro-, submicrometer-,and nanoroughness are developed, using photolithographically structured SU-8 micro-pillars as substrates for the consecutive spray deposition of polytetrafluoroethylene (PTFE) submicrometer particles and hydrophobically capped iron oxide colloidal nanoparticles. The PTFE particles alone or in combination with the nanoparticles render the SU-8 micropillars superhydrophobic. The water adhesion behaviour of the sprayed pillars is more complex since they can be tuned gradually from totally adhesive to completely non adhesive. The influence of the hierarchical geometrical features of the functionalized surfaces on this behaviour is discussed within the frame of the theory. Specially designed surfaces using the described technique are presented for selective drop deposition and evaporation. This simple method for liquid adhesion control on superhydrophobic surfaces can find various applications in the field of microfluidics, sensors, biotechnology, antifouling materials, etc.

Elastomeric Nanocomposite Foams for the Removal of Heavy Metal Ions from Water

We report the fabrication and utilization of elastomeric polymer nanocomposite foams for the efficient removal of Pb2+ and Hg2+ heavy metal ions from polluted water. The polydimethylsiloxane (PDMS) foams are properly modified in order to become hydrophilic and allow the polluted water to penetrate in their volume. The ZnSe colloidal nanocrystals (NCs) that decorate the surface of the foams, act as active components able to entrap the metal ions. In this way, after the dipping of the nanocomposite foams in water polluted with Pb2+ or Hg2+, a cation exchange reaction takes place, and the heavy metal ions are successfully removed. The removal capacity for the Pb2+ ions exceeds 98% and the removal of Hg2+ ions approaches almost 100% in the studied concentrations region of 20-40 ppm. The reaction is concluded after 24 h, but it should be noticed that after the first hour, more than 95% of both the metal ions is removed. The color of the foams changes upon heavy metal ions entrapment, providing thus the opportunity of an easy detection of the presence of the ions in water. Taking into account that the fabricated foams provide good elastic properties and resistance to heat, they can be used in different conditions of water remediation.

Electrically conductive and high temperature resistant superhydrophobic composite films from colloidal graphite

Electrically conductive and self-cleaning superhydrophobic films (water contact angles >160°, droplet roll off angles <5°) were fabricated by simply solution casting sub-micron polytetrafluoroethylene (Teflon) particle dispersed alcohol-based colloidal graphite solutions. The process is very suitable for forming conductive superhydrophobic coatings on glasses, metals, ceramics and high performance polymers such as polyimide (Kapton®). The solutions were deposited on microscope glass slides and Kapton® films by drop casting. After solvent evaporation under ambient conditions, the coatings were annealed to melt Teflon. Upon melting, Teflon particles fused into one another forming a hydrophobic polymer matrix. The degree of superhydrophobicity and the surface morphology of the coatings together with their electrical conductivity were studied in detail by varying Teflon-to-graphite weight fractions. A number of applications can be envisioned for these coatings such as electrode materials for energy conversion devices, high performance electromagnetic shielding materials, flexible electronic components and heat exchanger surfaces, to name a few.

Control of the water adhesion on hydrophobic micropillars by spray coating technique

We present an alternative approach for controlling the water adhesion on solid superhydrophobic surfaces by varying their coverage with a spray coating technique. In particular, micro-, submicro-, and nanorough surfaces were developed starting from photolithographically tailored SU-8 micropillars that were used as substrates for spraying first poly(tetrafluoroethylene) submicrometer particles and subsequently iron oxide nanoparticles. The sprayed particles serve to induce surface submicrometer and nanoscale roughness, rendering the SU-8 patterns superhydrophobic (apparent contact angle values of more than 150°), and also to tune the water adhesion between extreme states, turning the surfaces from “non-sticky” to “sticky” while preserving their superhydrophobicity. The influence of the chemical properties and of the geometrical characteristics of the functionalized surfaces on the wetting properties is discussed within the frame of the theory. This simple method can find various applications in the fabrication of microfluidic devices, smart surfaces, and biotechnological and antifouling materials.

Superparamagnetic cellulose fiber networks via nanocomposite functionalization

We present a simple and cost-effective method for rendering networks of cellulose fibers, such as paper, fabrics or membranes, superparamagnetic by impregnating the individual fibers with a reactive acrylic monomer. The cellulose fibers are wetted by a cyanoacrylate monomer solution containing superparamagnetic manganese ferrite colloidal nanoparticles. Upon moisture initiated polymerization of the monomer on the fiber surfaces, a thin nanocomposite shell forms around each fiber. The nanocomposite coating renders the cellulose fibers water repellent and magnetically responsive. Magnetic and microscopy studies prove that the amount of the entrapped nanoparticles in the nanocomposite shell is fully controllable, and that the magnetic response is directly proportional to this amount. A broad range of applications can be envisioned for waterproof magnetic cellulose materials (such as magnetic paper/tissues) obtained by such a simple yet highly efficient method.

Solvent resistant superhydrophobic films from self-emulsifying carnauba wax–alcohol emulsions

By dispersing molten carnauba wax in warm isopropyl alcohol or ethanol with subsequent mild ultrasonic mixing, highly stable surfactant-free natural wax-in-alcohol emulsions were prepared for the first time. These emulsions can easily suspend hydrophobic colloidal organics or solids. We demonstrate fabrication of superhydrophobic films from sub-micron polytetrafluoroethylene (PTFE) particle-dispersed emulsions by a simple drop and/or spray casting procedure and subsequent thermal annealing above the melting point of carnauba wax. We investigate effect of wax and Teflon concentration and thermal annealing on the degree of superhydrophobicity. Moreover, the films display superior resistance to solvent etching against aggressive solvents such as chloroform, toluene, acetone and alcohols upon immersion into such solvent baths for one hour. Composite films remain superhydrophobic after solvents evaporate from their surfaces following their removal from the solvent baths. Moreover, detailed contact angle hysteresis measurements revealed that solvent bath immersion does not downgrade “self-cleaning” superhydrophobicity to “sticky” superhydrophobicity.

Patterned structures of in situ size controlled CdS nanocrystals in a polymer matrix under UV irradiation

A method of in situ formation of patterns of size controlled CdS nanocrystals in a polymer matrix by pulsed UV irradiation is presented. The films consist of Cd thiolate precursors with different carbon chain lengths embedded in TOPAS polymer matrices. Under UV irradiation the precursors are photolyzed, driving to the formation of CdS nanocrystals in the quantum size regime, with size and concentration defined by the number of incident UV pulses, while the host polymer remains macroscopically/microscopically unaffected. The emission of the formed nanocomposite materials strongly depends on the dimensions of the CdS nanocrystals, thus, their growth at the different phases of the irradiation is monitored using spatially resolved photoluminescence by means of a confocal microscope. X-ray diffraction measurements verified the existence of the CdS nanocrystals, and defined their crystal structure for all the studied cases. The results are reinforced by transmission electron microscopy. It is proved that the selection of the precursor determines the efficiency of the procedure, and the quality of the formed nanocrystals. Moreover it is demonstrated that there is the possibility of laser induced formation of well-defined patterns of CdS nanocrystals, opening up new perspectives in the development of nanodevices.