Bryan E. Barton

Metal-free atom transfer radical polymerization

Overcoming the challenge of metal contamination in traditional ATRP systems, a metal-free ATRP process, mediated by light and catalyzed by an organic-based photoredox catalyst, is reported. Polymerization of vinyl monomers are efficiently activated and deactivated with light leading to excellent control over the molecular weight, polydispersity, and chain ends of the resulting polymers. Significantly, block copolymer formation was facile and could be combined with other controlled radical processes leading to structural and synthetic versatility. We believe that these new organic-based photoredox catalysts will enable new applications for controlled radical polymerizations and also be of further value in both small molecule and polymer chemistry.

High-Modulus Low-Cost Carbon Fibers from Polyethylene Enabled by Boron Catalyzed Graphitization

Currently, carbon fibers (CFs) from the solution spinning, air oxidation, and carbonization of polyacrylonitrile impose a lower price limit of ≈

High-temperature tensile cell for in situ real-time investigation of carbon fibre carbonization and graphitization processes

10 per lb, limiting the growth in industrial and automotive markets. Polyethylene is a promising precursor to enable a high-volume industrial grade CF as it is low cost, melt spinnable and has high carbon content. However, sulfonated polyethylene (SPE)-derived CFs have thus far fallen short of the 200 GPa tensile modulus threshold for industrial applicability. Here, a graphitization process is presented catalyzed by the addition of boron that produces carbon fiber with >400 GPa tensile modulus at 2400 °C. Wide angle X-ray diffraction collected during carbonization reveals that the presence of boron reduces the onset of graphitization by nearly 400 °C, beginning around 1200 °C. The B-doped SPE-CFs herein attain 200 GPa tensile modulus and 2.4 GPa tensile strength at the practical carbonization temperature of 1800 °C.

Highly Photoluminescent Nonconjugated Polymers for Single-Layer Light Emitting Diodes

A new high-temperature fibre tensile cell is described, developed for use at the Advanced Photon Source at Argonne National Laboratory to enable the investigation of the carbonization and graphitization processes during carbon fibre production. This cell is used to heat precursor fibre bundles to temperatures up to ∼2300°C in a controlled inert atmosphere, while applying tensile stress to facilitate formation of highly oriented graphitic microstructure; evolution of the microstructure as a function of temperature and time during the carbonization and higher-temperature graphitization processes can then be monitored by collecting real-time wide-angle X-ray diffraction (WAXD) patterns. As an example, the carbonization and graphitization behaviour of an oxidized polyacrylonitrile fibre was studied up to a temperature of ∼1750°C. Real-time WAXD revealed the gradual increase in microstructure alignment with the fibre axis with increasing temperature over the temperature range 600-1100°C. Above 1100°C, no further changes in orientation were observed. The overall magnitude of change increased with increasing applied tensile stress during carbonization. As a second example, the high-temperature graphitizability of PAN- and pitch-derived commercial carbon fibres was studied. Here, the magnitude of graphitic microstructure evolution of the pitch-derived fibre far exceeded that of the PAN-derived fibres at temperatures up to ∼2300°C, indicating its facile graphitizability.