Edwin L. Thomas

Difluoroboron β-diketone complexes are versatile light-emitting molecules that exhibit tunable emission in both solution and the solid state. Among this class of dyes, difluoroboron dibenzoylmethane-polylactide (BF₂dbmPLA) polymers have been investigated for their molecular weight dependent fluorescence where the polymer chain plays an important role in BF₂dbm solid-state emission. Here the substituent effects were further examined with a lipid chain replacing polylactide. Surprising process dependent and reversible mechanochromic fluorescence was discovered for the boron dodecane complex (BF₂dbmOC₁₂H₂₅). A thermally annealed spin-cast film of the lipid dye on glass exhibited blue fluorescence under UV light but after shearing or scratching, the mechanically perturbed region turned yellow-green. The blue coloration could be rapidly recovered by thermal treatment of the film. The phenomena were investigated by steady-state fluorescence spectroscopy at room, low, and high temperatures, in situfluorescence microscopy, fluorescence lifetime measurements, and X-ray diffraction. Consistent with previous findings, the ordered-to-amorphous structural change that occurs upon mechanical perturbation may increase molecular rotational freedom, allowing for more efficient excimer emission, which typically occurs at longer wavelengths.

Polystyrene‐block‐poly(2‐vinyl pyridine) (PS‐b‐P2VP) block copolymer photonic gels are fabricated that exhibit controllable optical hysteresis in response to a cyclic pH sweep. The optical hysteresis is tuned by controlling the ion‐pairing affinity between various anions and the protonated pyridinium ions on the P2VP block, which is highly dependent on the hydration energy of the ions, the dielectric constant of the solvent, and the ionic strength of the medium. The pH coercivity defining the magnitude of hysteresis of the photonic gels could be varied from 0.26 to 7.4. Photonic gel films with strong optical hysteresis can serve as wet photonic memory films where information can be cyclically recorded and erased at least 15 times and maintained for at least 96 h. The memory colors can be further tuned by selection of the copolymer molecular weight.

Periodic nanostructures fabricated by interference lithography can be precisely designed to have a specific cell geometry, topology, and porosity in contrast to typical stochastic cellular materials. We use nanoindentation to elucidate the mechanical characteristics of the nanoframe as a function of its relative density and model the deformation behavior via numerical simulations. The nanoframe exhibits a scaling exponent of relative modulus versus relative density of 1.26, which is less sensitive than for conventional foams. Moreover, the nanoframe shows large mechanical energy dissipation/volume (up to 4.5 MJ/m³), comparable to the highest values achieved in the conventional polymer foams but at a far smaller strain. Counterintuitively, a nanoframe of smaller relative density can dissipate more energy per volume because the geometry of the nanoframe evolves during deformation to engage more of the material in plastic deformation. The results demonstrate how geometrical control at the nano- and microstructural scale can tailor modulus and energy dissipation and suggest means for engineering of mechanically superior materials in the future.

We report the observation of a cubic phase consistent with the double gyroid structure in strongly segregated diblock copolymers of PS‐b‐PDMS over a volume fraction (φ_PDMS) range of ∼0.39 to 0.45. The samples have respective molecular weights of 127 kg/mol and 73 kg/mol and degree of segregation Nχ equal to 187 and 106, respectively, at annealing temperature of 130 °C. It is important to highlight that two out of the total four samples investigated, exhibited hexagonally close packed cylindrical domains of PDMS and alternating lamellae at φ_PDMS = 0.39 and 0.45, respectively, indicating the possible narrow range of the DG morphology for the specific diblock copolymers. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2419–2427, 2009

The transformation of periodic microporous structures fabricated by interference lithography followed by their freezing below glass transition is described. Periodic porous microstructures subjected to internal compressive stresses can undergo sudden structural transformation at a critical strain. The pattern transformation of collapsed pores is caused by the stresses originated during the polymerization of acrylic acid (rubbery component) inside of cylindrical pores and the subsequent solvent evaporation in the organized microporous structure. By confining the polymerization of acrylic acid to localized porous areas complex microscopic periodic structures can be obtained. The control over the mechanical instabilities in periodic porous solids at a sub‐micron scale demonstrated here suggests the potential mechanical tunability of photonic, transport, adhesive, and phononic properties of such periodic porous solids.