Christopher N. Young

Room-temperature carbonization of poly(diiododiacetylene) by reaction with Lewis bases.

Poly(diiododiacetylene) (PIDA) is a conjugated polymer containing an all-carbon backbone and only iodine atom substituents. Adding a Lewis base to the blue PIDA suspension at room temperature leads first to rapid disappearance of the absorption peaks attributed to PIDA, followed more slowly by release of free iodine. The resulting solid material gives a Raman scattering spectrum consistent with graphitic carbon, and it has a much higher conductivity than PIDA itself. Further investigation has led to the discovery of a previously unreported transformation, the reaction of a Lewis base such as pyrrolidine with a trans-diiodoalkene to form the corresponding alkyne. The generality of this iodine elimination further suggests that reaction of PIDA with Lewis bases dehalogenates the polymer, presenting a new method to prepare carbon nanomaterials at room temperature under very mild conditions.

Synthesis of the Stable Ordered Conjugated Polymer Poly(dibromodiacetylene) from an Explosive Monomer

Dibromobutadiyne is an extremely unstable compound that explodes at room temperature, even under inert atmosphere. This instability has limited the studies of dibromobutadiyne almost entirely to spectroscopic characterization. Here we report an approach to control the reactivity of dibromobutadiyne, via topochemical reaction in cocrystals, leading to the ordered polymer poly(dibromodiacetylene), PBDA. At low temperatures (-15 to -18u2009°C), dibromobutadiyne can form cocrystals with oxalamide host molecules containing either pyridyl or nitrile side groups, in which halogen bonds align the dibromobutadiyne monomers for topochemical polymerization. The cocrystals with the bis(nitrile) oxalamide host undergo complete ordered polymerization to PBDA, demonstrated by solid-state MAS-NMR, Raman, and optical absorption spectroscopy. Once formed, the polymer can be separated from the host; unlike the monomer, PBDA is stable at room temperature.

Depth Profiling of Polymer Composites by Ultrafast Laser Ablation

Past work has shown femtosecond laser ablation to be a non-thermal process at low fluences in polymer systems. The ablation rate in this low fluence regime is very low, allowing for micro-scale removal of material. We have taken advantage of this fact to perform shallow depth profiling ablation on carbon fiber reinforced polymer (CFRP) composites. Neat resin and composite samples were studied to establish reference ablation profiles. These profiles and the effects of the heterogeneous distribution of carbon fibers were observed through optical and scanning electron microscopy. Weathered materials that have been subjected to accelerated tests in artificial sunlight or high temperature conditions were ablated to evaluate any correlation between exposure and change in ablation characteristics. Preliminary Raman and micro-ATR analysis performed before and after ablation shows no chemical changes indicative of thermal effects. The low-volume-ablation property was utilized in an attempt to expose the sizing-matrix interphase for analysis.Copyright