Synthesis of a nitrogen-stabilized hexagonal Re(3)ZnN(x) phase using high pressures and temperatures. 2009

George Serghiou, and Christophe L Guillaume, and Andrew Thomson, and Jean-Paul Morniroli, and Dan J Frost
University of Edinburgh, School of Engineering and Centre for Materials Science, Kings Buildings, Mayfield Road, EH9 3JL UK.

High pressure can induce profound changes in solids. A significant barrier to new alloys and ceramics, however, is that targeted starting materials may not react with each other, even with the help of pressure. We use nitrogen, in a new capacity, to incorporate two otherwise unreactive elements, Re and Zn, in the same structure when pressure alone does not suffice, without nitrogen altering the resulting backbone structure. Synthesis experiments up to 20 GPa and 1800 K show that while no Re-Zn alloy or solid solution is formed, a novel Re(3)ZnN(x) ordered solid solution is formed, at 20 GPa, with nitrogen occupying Re-coordinated cages. We put forth that unlike pure Re(3)Zn, our novel hexagonal Re(3)ZnN(x) structure is stabilized by nitrogen bond formation with rhenium. Pressure lifts the pronounced ambient Zn anisotropy, making it more compatible with Re and likely facilitating incorporation of the structure-stabilizing nitrogen anion. This methodology and result denote further options for removing impasses to material preparation, thus opening new avenues for synthesis. These can also be pursued with other ions including carbon, hydrogen, and oxygen, in addition to nitrogen.

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