Magnetic dilution of a honeycomb lattice XY magnet CoTiO3

We report our study of cobalt (II) titanate, CoTiO3, in which magnetic Co ions are replaced by non-magnetic ions. The antiferromagnetic ordering transition of CoTiO3 around 37 K is described with ferromagnetic honeycomb layers coupled antiferromagnetically along the crystallographic c direction. The effect of magnetic dilution on the Néel temperature of this material is investigated through the doping of Zn2+ and Mg2+ in place of Co2+ for various dilution levels up to x + y = 0.46 in Co1-x-yZnxMgyTiO3. Single phase polycrystalline samples have been synthesized and their structural and magnetic properties have been examined. A linear relation between dilution and the Néel temperature is observed over a wide doping range. A linear extrapolation would suggest that the required dilution level to suppress magnetic order is around x + y ∽ 0.74, well beyond the classical percolation threshold. The implication of this observation for microscopic models for describing CoTiO3 is discussed.

Solubilization Behavior of Homopolymer in Its Blend with the Block Copolymer Displaying the Feature of Lower Critical Ordering Transition

Blending with homopolymer offers a facile approach for tuning the microdomain morphology of block copolymer, provided that the homopolymer chains are uniformly solubilized in the corresponding microdomain to swell the junction point separation. Here we studied the solubilization behavior of poly(4-vinyl pyridine) homopolymer (h-P4VP) in the lamellar microdomain formed by its blends with a poly(ethylene oxide)-block-poly(4-vinyl pyridine) (PEO-b-P4VP) showing the feature of lower critical ordering transition (LCOT) in terms of weaker segregation strength at lower temperature. We revealed that, while the conventional criterion of homopolymer-to-block molecular weight ratio for attaining uniform solubilization was applicable to LCOT blend, there was an excess swelling of junction point separation upon the addition of homopolymer, leading to a decrease of interdomain distance with increasing homopolymer composition. This anomalous phenomenon was attributed to the reduction of interfacial free energy due to the incorporation of P4VP homopolymer into the microdomain interface.

Evidence for an Ordering Transition near 120 K in an Intrinsically Disordered Protein, Casein

Intrinsically disordered proteins (IDPs) are proteins that possess large unstructured regions. Their importance is increasingly recognized in biology but their characterization remains a challenging task. We employed field swept Electron Spin Echoes in pulsed EPR to investigate low-temperature stochastic molecular librations in a spin-labeled IDP, casein (the main protein of milk). For comparison, a spin-labeled globular protein, hen egg white lysozyme, is also investigated. For casein these motions were found to start at 100 K while for lysozyme only above 130 K, which was ascribed to a denser and more ordered molecular packing in lysozyme. However, above 120 K, the motions in casein were found to depend on temperature much slower than those in lysozyme. This abrupt change in casein was assigned to an ordering transition in which peptide residues rearrange making the molecular packing more rigid and/or more cohesive. The found features of molecular motions in these two proteins turned out to be very similar to those known for gel-phase lipid bilayers composed of conformationally ordered and conformationally disordered lipids. This analogy with a simpler molecular system may appear helpful for elucidation properties of molecular packing in IDPs.

Large Hall and Nernst responses from thermally induced spin chirality in a spin-trimer ferromagnet

The long-range order of noncoplanar magnetic textures with scalar spin chirality (SSC) can couple to conduction electrons to produce an additional (termed geometrical or topological) Hall effect. One such example is the Hall effect in the skyrmion lattice state with quantized SSC. An alternative route to attain a finite SSC is via the spin canting caused by thermal fluctuations in the vicinity of the ferromagnetic ordering transition. Here, we report that for a highly conducting ferromagnet with a two-dimensional array of spin trimers, the thermally generated SSC can give rise to a gigantic geometrical Hall conductivity even larger than the intrinsic anomalous Hall conductivity of the ground state. We also demonstrate that the SSC induced by thermal fluctuations leads to a strong response in the Nernst effect. A comparison of the sign and magnitude of fluctuation–Nernst and Hall responses in fundamental units indicates the need for a momentum–space picture to model these thermally induced signals.

Crystal structure engineering in multimetallic high-index facet nanocatalysts

In the context of metal particle catalysts, composition, shape, exposed facets, crystal structure, and atom distribution dictate activity. While techniques have been developed to control each of these parameters, there is no general method that allows one to optimize all parameters in the context of polyelemental systems. Herein, by combining a solid-state, Bi-influenced, high-index facet shape regulation strategy with thermal annealing, we achieve control over crystal structure and atom distribution on the exposed high-index facets, resulting in an unprecedentedly diverse library of chemically disordered and ordered multimetallic (Pt, Co, Ni, Cu, Fe, and Mn) tetrahexahedral (THH) nanoparticles. Density functional theory calculations show that surface Bi modification stabilizes the {210} high-index facets of the nanoparticles, regardless of their internal atomic ordering. Moreover, we find that the ordering transition temperatures for the nanoparticles are dependent on their composition, and, in the case of Pt3Fe1 THH nanoparticles, increasing Ni substitution leads to an order-to-disorder transition at 900 °C. Finally, we have discovered that ordered intermetallic THH Pt1Co1 nanocatalysts exhibit a catalytic performance superior to disordered THH Pt1Co1 nanoparticles and commercial Pt/C catalysts toward methanol electrooxidation, highlighting the importance of crystal structure and atom distribution control on high-index facets in nanoscale catalysts.

Moulding hydrodynamic 2D-crystals upon parametric Faraday waves in shear-functionalized water surfaces

Faraday waves, or surface waves oscillating at half of the natural frequency when a liquid is vertically vibrated, are archetypes of ordering transitions on liquid surfaces. Although unbounded Faraday waves patterns sustained upon bulk frictional stresses have been reported in highly viscous fluids, the role of surface rigidity has not been investigated so far. Here, we demonstrate that dynamically frozen Faraday waves—that we call 2D-hydrodynamic crystals—do appear as ordered patterns of nonlinear gravity-capillary modes in water surfaces functionalized with soluble (bio)surfactants endowing in-plane shear stiffness. The phase coherence in conjunction with the increased surface rigidity bears the Faraday waves ordering transition, upon which the hydrodynamic crystals were reversibly molded under parametric control of their degree of order, unit cell size and symmetry. The hydrodynamic crystals here discovered could be exploited in touchless strategies of soft matter and biological scaffolding ameliorated under external control of Faraday waves coherence.