Size effect in spin-crossover systems investigated by FORC measurements, for surfacted [Fe(NH2-trz)3](Br)2·3H2O nanoparticles: reversible contributions and critical size
We investigated the thermal transition of coated nano-particles of the title compound, on a set of samples of average diameter ⟨d⟩ ~ 30, 50, 70, 110 nm, with rather broad size distributions. As expected, the width of the major hysteresis loop was an increasing function of ⟨d⟩. We recorded first-order reversal curves (FORC), the initial parts of which displayed a finite slope, revealing the presence of reversible contributions expected from particles smaller than the critical size d C associated with the collapse of the hysteresis loop. Kinetic effects were also evidenced thanks to isothermal stages. Reversibility of the FORC curves at the vicinity of the reversal temperature was controlled. Thanks to the reversibility property we could determine the reversible contributions to the total response of all samples and derive the corresponding d C values. Consistent results were obtained by accounting for an anhysteretic contribution from the large particles, leading to an accurate determination d C ~ 45−50 nm, much better than the width of the size distributions.
KeywordsHysteresis Loop Critical Size FORC Curve Reversal Temperature Hysteresis Width
Unable to display preview. Download preview PDF.
- 1.Topics in Current Chemistry, Spin Crossover in Transition Metal Compounds I-III, edited by P. Gütlich, H.A. Goodwin (Springer, Heidelberg, Berlin, 2004), 233–235 Google Scholar
- 3.J.-F. Létard, N. Daro, O. Nguyen, Nanoparticules d’un composé à transition de spin (CNRS, France Brevet FR 2005/0512476 (2005-08-12)), International Patent WO 2007/065996 (2007-06-14), United State Patent US 2008/0311401 (2008-12-18), Japon Patent JP 2009/0519876 (2008-12-29), European Patent EP 2010/ 06841859.9 (2010-01-20)Google Scholar
- 5.T. Kawamoto, S. Abe, Chem. Commun. 3933 (2005) Google Scholar
- 10.O. Fouché, J. Degert, N. Daro, T. Forestier, C. Desplanches, J.-F. Létard, E. Freysz, presented at European Conf. on Molecular Magnetism (Tomar, Portugal, 2006)Google Scholar
- 22.A. Rotaru, Ph.D. thesis, University of Versailles, 2009Google Scholar
- 34.C. Etrillard, Ph.D. thesis, University of Bordeaux, 2011, in preparationGoogle Scholar