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Reduction of the bulk modulus at high pressure in CrN

Nature Materials volume 8, pages 947–951 (2009)Cite this article

Abstract

Nitride coatings are increasingly demanded in the cutting- and machining-tool industry owing to their hardness, thermal stability and resistance to corrosion. These properties derive from strongly covalent bonds; understanding the bonding is a requirement for the design of superhard materials with improved capabilities. Here, we report a pressure-induced cubic-to-orthorhombic transition at ≈1 GPa in CrN. High-pressure X-ray diffraction and ab initio calculations show an unexpected reduction of the bulk modulus, K0, of about 25% in the high-pressure (lower volume) phase. Our combined theoretical and experimental approach shows that this effect is the result of a large exchange striction due to the approach of the localized Cr:t3 electrons to becoming molecular-orbital electrons in Cr–Cr bonds. The softening of CrN under pressure is a manifestation of a strong competition between different types of chemical bond that are found at a crossover from a localized to a molecular-orbital electronic transition.

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Figure 1: Summary of the X-ray results at different pressures and temperatures.
Figure 2: Volume–pressure data of CrN fitted to the Birch–Murnaghan equation of state, truncated at second order (K′=4).
Figure 3: Ab initio calculation of the charge-density difference between the high-pressure Pnma and low-pressure Fm3m phases of CrN.
Figure 4: Pressure dependence of the magnetic transition temperature, TN, of the Pnma phase.

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Acknowledgements

B. Dacuña from the X-ray service of USC (Spain) is acknowledged for his help during the thermal X-ray experiments, as are A. Lennie, S. Blanco-Canosa and M. Otero-Leal for their collaboration in the high-pressure X-ray experiments at Daresbury SRS. C. Serra from the University of Vigo, Spain, is acknowledged for the X-ray photoemission spectroscopy analysis. We acknowledge financial support from Xunta de Galicia (PXIB20919PR and O8PXIB236053PR) MEC of Spain (MAT2009-08165) and the Robert A. Welch Foundation of Houston, TX (Grant F-1066).

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Authors and Affiliations

  1. Physical-Chemistry Department, University of Santiago de Compostela, 15782-Santiago de Compostela, Spain

    Francisco Rivadulla, Manuel Bañobre-López & Manuel Arturo López-Quintela

  2. Applied Physics Department, University of Santiago de Compostela, 15782-Santiago de Compostela, Spain

    Camilo X. Quintela, Alberto Piñeiro, Victor Pardo, Daniel Baldomir & José Rivas

  3. Instituto de Investigaciones Tecnológicas, Universidad de Santiago de Compostela, E-15782, Santiago de Compostela, Spain

    Alberto Piñeiro, Victor Pardo & Daniel Baldomir

  4. Centro Atómico de Bariloche, 8400 San Carlos de Bariloche, Rio Negro, Argentina

    Carlos A. Ramos & Horacio Salva

  5. Texas Materials Institute, ETC 9.102, The University of Texas at Austin, Austin, Texas 78712, USA

    Jian-Shi Zhou & John B. Goodenough

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  1. Francisco Rivadulla
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Contributions

F.R. conceived the project, synthesized the samples, carried out the synchrotron and magnetic experiments, analysed the results and wrote the paper. M.B.-L. carried out and analysed the synchrotron X-ray data and participated in the discussion. C.X.Q. made electrical and thermal conductivity measurements, and collaborated in the synthesis. A.P., V.P. and D.B. carried out the ab inito calculations and participated in the discussions. M.A.L.-Q. and J.R. participated in the discussion. C.A.R. and H.S. measured the thermal expansion and Young modulus. J.-S.Z. carried out high-pressure X-ray experiments. J.B.G. participated in the discussion and wrote the paper.

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Correspondence to Francisco Rivadulla.

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Rivadulla, F., Bañobre-López, M., Quintela, C. et al. Reduction of the bulk modulus at high pressure in CrN. Nature Mater 8, 947–951 (2009). https://doi.org/10.1038/nmat2549

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