Al de Leon

Superhydrophobic Colloidally Textured Polythiophene Film as Superior Anticorrosion Coating

In this paper, we demonstrated for the first time the use of electrodeposited superhydrophobic conducting polythiophene coating to effectively protect the underlying steel substrate from corrosion attack: by first preventing water from being absorbed onto the coating, thus preventing the corrosive chemicals and corrosion products from diffusing through the coating, and second by causing an anodic shift in the corrosion potential as it galvanically couples to the metal substrate. Standard electrochemical measurements revealed the steel coated with antiwetting nanostructured polythiophene film, which was immersed in chloride solution of different pH and temperature for up to 7 days, is very well protected from corrosion evidenced by protection efficiency of greater than 95%. Fabrication of the dual properties superhydrophobic anticorrosion nanostructured conducting polymer coating follows a two-step coating procedure that is very simple and can be used to coat any metallic surface.

Inorganic–Organic Thiol–ene Coated Mesh for Oil/Water Separation

A highly efficient mesh for oil/water separation was fabricated by using a superhydrophobic and superoleophilic coating of thiol-ene hybrid, consisting of pentaerythritol tetra(3-mercaptopropionate) (PETMP), 2,4,6,8-tetramethyl-2,4,6,8-tetravinylcyclotetrasiloxane (TMTVSi), and hydrophobic fumed silica nanoparticles, via a simple two-step fabrication process. Spray deposition and UV curing photopolymerization were sequentially performed, during which solvent evaporation provides microscale roughness while nanoparticle aggregation forms nanoscale roughness. The hierarchical morphologies were stabilized after UV curing photopolymerization. High contact angle (>150°) and low roll-off angle (<5°) were achieved due to the multiscale roughness structure of the hierarchical morphologies. These coatings also have excellent chemical resistance, as well as temperature and pH stability, after curing.

3D Printing Biocompatible Polyurethane/Poly(lactic acid)/Graphene Oxide Nanocomposites: Anisotropic Properties

Blending thermoplastic polyurethane (TPU) with poly(lactic acid) (PLA) is a proven method to achieve a much more mechanically robust material, whereas the addition of graphene oxide (GO) is increasingly applied in polymer nanocomposites to tailor further their properties. On the other hand, additive manufacturing has high flexibility of structure design which can significantly expand the application of materials in many fields. This study demonstrates the fused deposition modeling (FDM) 3D printing of TPU/PLA/GO nanocomposites and its potential application as biocompatible materials. Nanocomposites are prepared by solvent-based mixing process and extruded into filaments for FDM printing. The addition of GO largely enhanced the mechanical property and thermal stability of the nanocomposites. Interestingly, we found that the mechanical response is highly dependent on printing orientation. Furthermore, the 3D printed nanocomposites exhibit good biocompatibility with NIH3T3 cells, indicating promise as biomaterials scaffold for tissue engineering applications.

Coextruded, Aligned, and Gradient-Modified Poly(ε-caprolactone) Fibers as Platforms for Neural Growth

Polymeric fibers are of increasing interest to regenerative medicine, as materials made from these fibers are porous, allowing for cell infiltration, influx of nutrients, and efflux of waste products. Recently, multilayered coextrusion has emerged as a scalable and rapid fabrication method to yield microscale to submicron fibers. In this report, we describe the multilayered coextrusion of aligned poly(ε-caprolactone) (PCL) fibers, followed by a simple photochemical patterning to create surface-immobilized gradients onto the polymer fibers. PCL fibers were photochemically decorated with a linear gradient of propargyl benzophenone using a gradient photomask to control light source intensity. The pendant alkynes were then able to undergo the copper-catalyzed azide-alkyne cycloaddition reaction with an azide-modified IKVAV peptide to further functionalize the surface. Gradient-modified IKVAV fibers were evaluated for neural cell adhesion and neural differentiation, using PC-12 cells cultured onto the fibers. The aligned gradient fibers provided directional cues for neurite outgrowth and alignment of neural cells, as observed by cellular elongation, neurite differentiation, and orientation. The work presented herein describes a scalable fiber system combined with simple chemical patterning to generate aligned fibers with controlled surface gradients as cell-seeding scaffolds.

Reversible superhydrophilicity and superhydrophobicity on a lotus-leaf pattern.

A facile approach of fabricating a temperature-responsive coating capable of switching reversibly from being superhydrophobic to superhydrophilic is presented. The approach combines micromolding, layer-by-layer assembly of the polymer macroinitiators, and surface-initiated polymerization. Changing between superhydrophobicity and superhydrophilicity depends heavily on the surface roughness and the switching of the surface energy levels. In this study, surface roughness was introduced by replicating the surface morphology of a lotus leaf. The switching of surface energy levels was made possible by grafting a temperature-responsive polymer brush. Wetting studies reveal that the reported approach not only replicates nature but also improves its property by making it responsive to stimulus.

Charge-Dependent Transport Switching of Single Molecular Ions in a Weak Polyelectrolyte Multilayer

The tunable nature of weak polyelectrolyte multilayers makes them ideal candidates for drug loading and delivery, water filtration, and separations, yet the lateral transport of charged molecules in these systems remains largely unexplored at the single molecule level. We report the direct measurement of the charge-dependent, pH-tunable, multimodal interaction of single charged molecules with a weak polyelectrolyte multilayer thin film, a 10 bilayer film of poly(acrylic acid) and poly(allylamine hydrochloride) PAA/PAH. Using fluorescence microscopy and single-molecule tracking, two modes of interaction were detected: (1) adsorption, characterized by the molecule remaining immobilized in a subresolution region and (2) diffusion trajectories characteristic of hopping (D ∼ 10–9 cm2/s). Radius of gyration evolution analysis and comparison with simulated trajectories confirmed the coexistence of the two transport modes in the same single molecule trajectories. A mechanistic explanation for the probe and condition mediated dynamics is proposed based on a combination of electrostatics and a reversible, pH-induced alteration of the nanoscopic structure of the film. Our results are in good agreement with ensemble studies conducted on similar films, confirm a previously-unobserved hopping mechanism for charged molecules in polyelectrolyte multilayers, and demonstrate that single molecule spectroscopy can offer mechanistic insight into the role of electrostatics and nanoscale tunability of transport in weak polyelectrolyte multilayers.

Electropolymerized and polymer grafted superhydrophobic, superoleophilic, and hemi-wicking coatings

A novel one step approach to fabricate superhydrophobic and superoleophilic electrodeposited coatings is reported. By performing additional surface-initiated atom transfer radical polymerization (SI-ATRP) from the coating, a further change in wettability of the substrates to a variety of liquids was observed.

Grafted Carbazole-Assisted Electrodeposition of Graphene Oxide

The electrodeposition of graphene oxide (GO) by covalently linked electroactive monomer, carbazole (Cbz) is first demonstrated herein. This is based on the electropolymerization and electrodeposition of covalently linked Cbz units when a potential is applied. During the electrochemical process, the Cbz groups electropolymerize and carry the GO nanosheets as it electrodeposits on the substrate. Moreover, the GO-Cbz sheets selectively deposit onto the conducting regions of the substrate, which demonstrates its promise for the fabrication of electropatterned graphene-based devices. In addition, GO-Cbz is a promising material for the fabrication of nanocomposite coatings for anticorrosion application. In as little as 1 wt % GO-Cbz loading, a protection efficiency as high as 95.4% was achieved.

3D Printing of Photocurable Cellulose Nanocrystal Composite for Fabrication of Complex Architectures via Stereolithography

The advantages of 3D printing on cost, speed, accuracy, and flexibility have attracted several new applications in various industries especially in the field of medicine where customized solutions are highly demanded. Although this modern fabrication technique offers several benefits, it also poses critical challenges in materials development suitable for industry use. Proliferation of polymers in biomedical application has been severely limited by their inherently weak mechanical properties despite their other excellent attributes. Earlier works on 3D printing of polymers focus mainly on biocompatibility and cellular viability and lack a close attention to produce robust specimens. Prized for superior mechanical strength and inherent stiffness, cellulose nanocrystal (CNC) from abaca plant is incorporated to provide the necessary toughness for 3D printable biopolymer. Hence, this work demonstrates 3D printing of CNC-filled biomaterial with significant improvement in mechanical and surface properties. These findings may potentially pave the way for an alternative option in providing innovative and cost-effective patient-specific solutions to various fields in medical industry. To the best of our knowledge, this work presents the first successful demonstration of 3D printing of CNC nanocomposite hydrogel via stereolithography (SL) forming a complex architecture with enhanced material properties potentially suited for tissue engineering.

Beyond binary: optical data storage with 0, 1, 2, and 3 in polymer films

The evergrowing amount of data created and collected is met with the increased need to store this data. In compliment to improving data storage capabilities using engineering controls such as decreased pixel size (i.e., Blu-ray) or 3-D pixels (i.e., voxels), chemistry-based approaches are required to move beyond current limitations and meet our future needs. Herein, we present a new methodology to optically store data in a quaternary code of 0, 1, 2, 3 in a commodity polymer containing a low loading of two small molecules, and using heat and UV light to write, and read fluorescence output. The as-prepared film is non-fluorescent (0), and can be written through a wooden or metal mask with thermal treatment (1), light treatment (2), or both (3), giving three different colours of fluorescence under UV irradiation. The flexible polymer film remains colourless and transparent under ambient light after patterning, retains the stored data after exfoliation with sandpaper, and can be removed from the substrate and mechanically deformed without detriment to the pattern. This straightforward and scalable system demonstrates the use of simple and robust chemical reactions to improve data storage capabilities and has the potential to exponentially increase information density.