Nanoscale magnetic phase competition throughout the Ni50-xCoxMn40Sn10 phase diagram: Insights from small-angle neutron scattering

The Ni2MnSn-derived Ni(50-x)Co(x)Nn(25+y)Sn(25-y) alloys are premier examples of a class of off-stoichiometric Heusler alloys recently discovered to exhibit attractive magnetic properties in tandem with extraordinarily reversible martensitic phase transformations. Multiferroicity, magnetic phase competition and separation, field-induced martensitic transformations, magnetic shape memory behavior, and sizable magneto-, elasto-, and barocaloric effects result, generating substantial interest and application potential. In this work we expand on a prior small-angle neutron scattering (SANS) study at a single composition (Ni44Co6Mn40Sn10) by exploring all three main regions of the recently established Ni50-xCoxMn40Sn10 phase diagram, i.e., at the representative y = 15 composition. Wide temperature and scattering wave-vector range (20-500 K, 0.004-0.2 angstrom(-1)) SANS data on x = 2, 6, and 14 polycrystals provide a detailed picture of the evolution in magnetic order and inhomogeneity. Consistent with recent studies with a variety of techniques, phase separation into short-range coexisting ferromagnetic and antiferromagnetic regions is deduced below the martensitic transformation at x = 2 and 6, with average ferromagnetic cluster spacing of similar to 13 nm. Remarkably, at x = 14, where the martensitic transformation is suppressed and ferromagnetic austenite is stabilized to low temperatures, nanoscopic magnetic inhomogeneity nevertheless persists. Distinct ferromagnetic clusters (similar to 36-nm average spacing) in a ferromagnetic matrix are observed at intermediate temperatures, homogenizing into a uniform long-range ordered ferromagnet only at low temperatures. This unusual ferromagnet cluster/ferromagnet matrix inhomogeneity, as well as x-dependent subtleties of the superparamagnetic freezing of ferromagnetic clusters, are discussed in light of Mn-55 nuclear magnetic resonance data, and the recent observation of annealing-induced core/shell nanoprecipitates. The origins of nanoscale magnetic inhomogeneity are discussed in terms of statistical variations in local composition and structure, tendency to chemical phase separation, and other forms of disorder.