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Title: Selective Metal Exsolution in BaFe 2-yMy(PO 4) 2 (M = Co 2+, Ni 2+) Solid Solutions

The 2D-Ising ferromagnetic phase BaFe 2+ 2(PO 4) 2 shows exsolution of up to one-third of its iron content (giving BaFe 3+ 1.33(PO 4) 2) under mild oxidation conditions, leading to nanosized Fe 2O 3 exsolved clusters. Here we have prepared BaFe 2–yMy(PO 4) 2 (M = Co 2+, Ni 2+; y = 0, 0.5, 1, 1.5) solid solutions to investigate the feasibility and selectivity of metal exsolution in these mixed metallic systems. For all the compounds, after 600 °C thermal treatment in air, a complete oxidation of Fe 2+ to Fe 3+ leaves stable M 2+ ions, as verified by 57Fe Mössbauer spectroscopy, TGA, TEM, microprobe, and XANES. Furthermore, the size of the nanometric α-Fe 2O 3clusters coating the main phase strongly depends on the y M metal concentration. For M-rich phases the iron diffusion is hampered so that a significant fraction of superparamagnetic α-Fe2O3 particles (100% for BaFe 0.5–xCo 1.5(PO 4) 2) was detected even at 78 K. Although Ni 2+and Co 2+ ions tend to block Fe diffusion, the crystal structure of BaFe 0.67Co 1(PO 4) 2demonstrates a fully ordered rearrangement of Fe 3+ and Co 2+ ions after Fe exsolution. We found that the magnetic behaviorsmore » of the Fe-depleted materials are mostly dominated by antiferromagnetic exchange, while Co 2+-rich compounds show metamagnetic transitions reminiscent of the BaCo 2(PO 4) 2 soft helicoidal magnet.« less
Authors:
 [1] ;  [1] ;  [2] ;  [3] ;  [1] ;  [4] ;  [1] ;  [1]
  1. Universite Lille Nord de France (France)
  2. Universite Picardie Jules Verne (France)
  3. Moscow State Univ., Moscow (Russian Federation)
  4. Univ. of Edinburgh (United Kingdom)
Publication Date:
OSTI Identifier:
1225094
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Inorganic Chemistry; Journal Volume: 54; Journal Issue: 17
Publisher:
American Chemical Society (ACS)
Research Org:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
ENGLISH