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Title: Crystal chemistry and magnetism of ternary actinoid boron carbides UB[sub 1[minus]x]C[sub 1+x] and U[sub 1[minus]x]M[sub x]B[sub 2]C with M = Sc, Lu, and Th

Journal Article · · Journal of Solid State Chemistry; (United States)
 [1];  [2];  [3];  [4]
  1. Universitaet Wien, Vienna (Austria)
  2. Universitaet Wien, Vienna (Austria) Lawrence Livermore National Lab., CA (United States)
  3. Hebrew Univ., Jerusalem (Israel)
  4. Eidgenoessische Technische Hochschule, Zuerich (Switzerland) Paul Scherrer Institut, Villigen (Switzerland)

Within the homogeneous range of uranium monocarbide UB[sub 1[minus]x]C[sub 1+x], the crystal structures of stoichiometric UBC and of the carbon-rich solid solution UB[sub 0.78]C[sub 1.22] have been refined from single-crystal X-ray counter data. From X-ray analysis crystal symmetry in both cases is consistent with the centrosymmetric space group Cmcm and there are no indications of superstructure formation. In contrast to the fully ordered atom arrangement revealed for stoichiometric UBC, random occupation by boron and carbon atoms is observed for the boron site in UB[sub 0.78]C[sub 1.22]. Neutron powder diffraction experiments at 9 and 295 K unambiguously revealed full occupancy by the nonmetal atoms in UB[sub 0.78]C[sub 1.22] and prove the statistical occupation of B and C atoms in the B-sites. The boron-boron chain in Cmcm (B-B = 0.1874 nm) is dissolved into boron pairs (B-B = 0.1706 nm). The formation of C-B-B-C groups corresponds to the structure types of ThBC and Th[sub 3]B[sub 2]C[sub 3]. The magnetic behavior has been investigated in the temperature range from 4.2 K to 1000 K for UB[sub 1[minus]x]C[sub 1+x] (UBC-type) and U[sub 1[minus]x]M[sub x]B[sub 2]C (ThB[sub 2]C-type for the high temperature modification and 1-UB[sub 2]C-type for the low temperature modification) with U partially substituted by Th or Sc, Lu. From magnetic susceptibilities, the alloys UB[sub 1[minus]x]C[sub 1+x] reveal temperature independent paramagnetism with typical intermediate valence fluctuation behavior (T[sub SF] [approximately] 350 K). ThB[sub 2]C and 1-UB[sub 2]C both are temperature independent paramagnets, whereas h-UB[sub 2]C is a ferromagnet with the rather high Curie temperature T[sub M] = 80(2) K. T[sub M] and the saturation magnetization per U atom both successively decrease on substitution of U by Th, Sc, or Lu in UB[sub 2]C, whereas the U-moments remain practically unchanged at [mu][sub eff](U) [approximately] 1.9 [mu][sub B]. 20 refs., 8 figs., 5 tabs.

DOE Contract Number:
W-7405-ENG-48
OSTI ID:
5856220
Journal Information:
Journal of Solid State Chemistry; (United States), Vol. 104:2; ISSN 0022-4596
Country of Publication:
United States
Language:
English

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