Controllable Phase Transition Properties in VO2 Films via Metal-Ion Intercalation.

VO2 has shown great promise for sensors, smart windows, and energy storage devices, because of its drastic semiconductor-to-metal transition (SMT) near 340 K coupled with a structural transition. To push its application toward room-temperature, effective transition temperature (Tc) tuning in VO2 is desired. In this study, tailorable SMT characteristics in VO2 films have been achieved by the electrochemical intercalation of foreign ions (e.g., Li ions). By controlling the relative potential with respect to Li/Li+ during the intercalation process, Tc of VO2 can be effectively and systematically tuned in the window from 326.7 to 340.8 K. The effective Tc tuning could be attributed to the observed strain and lattice distortion and the change of the charge carrier density in VO2 introduced by the intercalation process. This demonstration opens up a new approach in tuning the VO2 phase transition toward room-temperature device applications and enables future real-time phase change property tuning.

Multifield and inverse-contrast switching of magnetocaloric high contrast ratio MRI labels.

PURPOSE: Demonstrating multifield and inverse contrast switching of magnetocaloric high contrast ratio MRI labels that either have increasing or decreasing moment versus temperature slopes depending on the material at physiological temperatures and different MRI magnetic field strengths. METHODS: Two iron-rhodium samples of different purity (99% and 99.9%) and a lanthanum-iron-silicon sample were obtained from commercial vendors. Temperature and magnetic field-dependent magnetic moment measurements of the samples were performed on a vibrating sample magnetometer. Temperature-dependent MRI of different iron-rhodium and lanthanum-iron-silicon samples were performed on 3 different MRI scanners at 1 Tesla (T), 4.7T, and 7T. RESULTS: Sharp, first-order magnetic phase transition of each iron-rhodium sample at a physiologically relevant temperature (~37°C) but at different MRI magnetic fields (1T, 4.7T, and 7T, depending on the sample) showed clear image contrast changes in temperature-dependent MRI. Iron-rhodium and lanthanum-iron-silicon samples with sharp, first-order magnetic phase transitions at the same MRI field of 1T and physiological temperature of 37°C, but with positive and negative slope of magnetization versus temperature, respectively, showed clear inverse contrast image changes. Temperature-dependent MRI on individual microparticle samples of lanthanum-iron-silicon also showed sharp image contrast changes. CONCLUSION: Magnetocaloric materials of different purity and composition were demonstrated to act as diverse high contrast ratio switchable MRI contrast agents. Thus, we show that a range of magnetocaloric materials can be optimized for unique image contrast response under MRI-appropriate conditions at physiological temperatures and be controllably switched in situ.

Electronic and Magnetic Properties of a Three-Arm Nonconjugated Open-Shell Macromolecule.

Nonconjugated radical polymers (i.e., macromolecules with aliphatic backbones that have stable open-shell sites along their pendant groups) have arisen as an intriguing complement to π-conjugated polymers in organic electronic devices and may prove to have superior properties in magneto-responsive applications. To date, however, the design of nonconjugated radical polymers has primarily focused on linear homopolymer, copolymer, and block polymer motifs even though conjugated dendritic macromolecules (i.e., polyradicals) have shown significant promise in terms of their response under applied magnetic fields. Here, we address this gap in creating a nonconjugated, three-arm radical macromolecule with nitroxide open-shell sites using a straightforward, single-step reaction, and we evaluated the electronic and magnetic properties of this material using a combined computational and experimental approach. The synthetic approach employed resulted in a high-purity macromolecule with a well-defined molecular weight and narrow molecular weight distribution. Moreover, epoxide-based units were implemented in the three-arm radical macromolecule design, and this resulted in a nonlinear radical macromolecule with a low (i.e., below room temperature) glass transition temperature and one that was an amorphous material in the solid state. These properties allowed thin films of the three-arm radical macromolecule to have electrical conductivity values on par with many linear radical polymers previously reported, and our computational efforts suggest the potential of higher generation open-shell dendrimers to achieve advanced electronic and magnetic properties. Importantly, the three-arm radical macromolecule also demonstrated antiferromagnetic exchange coupling between spins at temperatures < 10 K. In this way, this effort puts forward key structure-property relationships in nonlinear radical macromolecules and presents a clear path for the creation of next-generation macromolecules of this type.