Thermo-responsive Fluorinated Organogels Showing Anti-fouling and Long-Lasting/Repeatable Icephobic Properties.

Accumulations of ice on modern infrastructures often cause severe consequences. As such, there is significant interest in developing functional coatings/surfaces that can prevent this. One such approach has been demonstrated with slippery liquid-infused porous surfaces (SLIPS) and organogels where the ice adhesion strength is reduced to the critical point (less than 10 kPa) where it can be removed by natural forces such as gravity, wind, vibrations, and so forth. However, both designs are limited by lubricant depletion. If lubricant release and reabsorption (syneresis) of organogels can be arbitrarily controlled by the surrounding temperature, the loss due to unfavorable evaporation and drainage of infused lubricants can be minimized and its durability can be extended. This study demonstrates the tunable thermo-responsive syneresis of transparent fluorinated organogels (F-ORGs) prepared from a commercial silicone elastomer and a lubricant mixture of fluorinated silicone oil and either poly(dimethylsiloxane) or poly(methylphenylsiloxane). By carefully tuning the ratio of the two lubricants in the mixture, the corresponding F-ORGs demonstrated arbitrarily tunable critical syneresis temperatures from -15 to 40 °C, below which the lubricant is released on the surface and above which the lubricant is re-absorbed. The resulting surfaces showed not only exceptionally long-lasting/repeatable low ice adhesion strengths (≤10 kPa over 50 icing/de-icing cycles) but also significant improvements in their repellency toward a variety of organic liquids. Compared to non-fluorinated organogels, F-ORGs could offer improved protection against outdoor pollutants to further enhance their practicality.

Ice-Shedding Polymer Coatings with High Hardness but Low Ice Adhesion.

Ice readily sheds from weak oil-swollen polymer gels but tends to adhere to mechanically robust coatings. This paper reports bilayer coatings that simultaneously possess high bulk hardness but low ice adhesion. These coatings are prepared by cocuring a triisocyanate, P#'-g-PDMS [a methacrylate polyol bearing poly(dimethylsiloxane) (PDMS) side chains with # being 1, 2, or 3 and g denoting graft], and optionally a methacrylate polyol P#. The self-assembly of the system during coating formation yields a PDMS brush layer on the surface of the cross-linked polyurethane matrix. After the surface PDMS layer is lubricated with a silicone oil, this coating exhibits an ice adhesion τ that is 10 000-fold lower than that of a triisocyanate/P# coating. Ice slides under its own weight on such a coating at a tilt angle of 3°. Yet, the coating matrix is harder than poly(ethylene terephthalate), a widely used plastic. Additionally, such a coating maintains its low τ values for more than 10 consecutive icing/deicing cycles. Subsequent increases in τ are reversed by allowing time for the replenishment of the depleted surface lubricant with that released from the coating matrix. This design opens the door for effective yet hard ice-shedding polymer coatings.

Effect of Counterions on the Self-Assembly of Polystyrene-Polyphosphonium Block Copolymers.

The ability to manipulate block copolymers on the nanoscale has led to many scientific and technological advances. These include nanoscale ordered bulk and thin films and also solution phase components; these are promising materials for making smaller ordered electronics, selective membranes, and also biomedical applications. The ability to manipulate block copolymer material architectures on such small scales has risen from thorough investigations into the properties that affect the architectures. Polyelectrolytes are an important class of polymers that are used to make amphiphilic block copolymers. In this context the authors synthesized polystyrene-b-polyphosphonium block copolymers with different anions coordinated to the polyphosphonium block in order to study the effect of the anion on the aqueous self-assembly of the polymers. The anions play an important role in the solubility of the monomeric materials which results in differences in the self-assembly observed through dynamic light scattering and transmission electron microscopy.

Boron Difluoride Adducts of a Flexidentate Pyridine-Substituted Formazanate Ligand: Property Modulation via Protonation and Coordination Chemistry.

The synthesis and characterization of a flexidentate pyridine-substituted formazanate ligand and its boron difluoride adducts, formed via two different coordination modes of the title ligand, are described. The first adduct adopted a structure that was typical of other boron difluoride adducts of triarylformazanate ligands and contained a free pyridine subsituent, while the second was formed via the chelation of nitrogen atoms from the formazanate backbone and the pyridine substituent. Stepwise protonation of the pydridine-functionalized adduct, which is essentially nonemissive, resulted in a significant increase in the fluorescence quantum yield up to a maximum of 18%, prompting the study of this adduct as a pH sensor. The coordination chemistry of each adduct was explored through reactions with nickel(II) bromide [NiBr2(CH3CN)2], triflate [Ni(OTf)2], and 1,1,1,4,4,4-hexafluoroacetylacetonate [Ni(hfac)2(H2O)2] salts. Coordination to nickel(II) ions altered the physical properties of the boron difluoride formazanate adducts, including red-shifted absorption maxima and less negative reduction potentials. Together, these studies have demonstrated that the physical and electronic properties of boron difluoride adducts of formazanate ligands can be readily modulated through protonation and coordination chemistry.