Directional grain growth from anisotropic kinetic roughening of grain boundaries in sheared colloidal crystals

The fabrication of functional materials via grain growth engineering implicitly relies on altering the mobilities of grain boundaries (GBs) by applying external fields. Although computer simulations have alluded to kinetic roughening as a potential mechanism for modifying GB mobilities, its implications for grain growth have remained largely unexplored owing to difficulties in bridging the widely separated length and time scales. Here, by imaging GB particle dynamics as well as grain network evolution under shear, we present direct evidence for kinetic roughening of GBs and unravel its connection to grain growth in driven colloidal polycrystals. The capillary fluctuation method allows us to quantitatively extract shear-dependent effective mobilities. Remarkably, our experiments reveal that for sufficiently large strains, GBs with normals parallel to shear undergo preferential kinetic roughening, resulting in anisotropic enhancement of effective mobilities and hence directional grain growth. Single-particle level analysis shows that the mobility anisotropy emerges from strain-induced directional enhancement of activated particle hops normal to the GB plane. We expect our results to influence materials fabrication strategies for atomic and block copolymeric polycrystals as well.

Phase diagram of a two-species lattice model with a linear instability

We discuss the properties of a one-dimensional lattice model of a driven system with two species of particles in which the mobility of one species depends on the density of the other. This model was introduced by Lahiri and Ramaswamy (Phys. Rev. Lett., 79, 1150 (1997)) in the context of sedimenting colloidal crystals, and its continuum version was shown to exhibit an instability arising from linear gradient couplings. In this paper we review recent progress in understanding the full phase diagram of the model. There are three phases. In the first, the steady state can be determined exactly along a representative locus using the condition of detailed balance. The system shows phase separation of an exceptionally robust sort, termed strong phase separation, which survives at all temperatures. The second phase arises in the threshold case where the first species evolves independently of the second, but the fluctuations of the first influence the evolution of the second, as in the passive scalar problem. The second species then shows phase separation of a delicate sort, in which long-range order coexists with fluctuations which do not damp down in the large-size limit. This fluctuation-dominated phase ordering is associated with power law decays in cluster size distributions and a breakdown of the Porod law. The third phase is one with a uniform overall density, and along a representative locus the steady state is shown to have product measure form. Density fluctuations are transported by two kinematic waves, each involving both species and coupled at the nonlinear level. Their dissipation properties are governed by the symmetries of these couplings, which depend on the overall densities. In the most interesting case,, the dissipation of the two modes is characterized by different critical exponents, despite the nonlinear coupling.

Colloidal dispersions in a liquid crystalline medium

We have prepared stable colloidal suspensions in a lyotropic liquid crystal exhibiting an isotropic-nematic-lamellar phase sequence. Small angle neutron scattering (SANS) and dynamic light scattering (DLS) studies show the existence of attractive interparticle interactions in the nematic phase, which lead to a gas-liquid transition of the particles. The resulting liquid phase is weakly anisotropic. Further, the nematic-lamellar transition of the liquid crystal is found to be accompanied by a liquid-solid transition of the particles.

Study of the Formation of Nano-Networks in Colloidal Particles

The authors studied the formation of a wafer-scale network of connected colloidal beads by reactive ion etching. The dimensions of the connections have been studied as a function of etching time for colloidal beads of different sizes, and could be well controlled. The authors have found that the nano-network forms and disappears for the same time of etching independent of the diameter of the polystyrene beads. With recent interest of connected colloidal networks in various optical sensing applications, such as photonic crystals, as surface-enhanced Raman scattering substrates, the studies have potential uses in the development of wafer-scale nanophotonic sensors.

Glass, Gel, and Liquid Crystals: Arrested States of Graphene Oxide Aqueous Dispersions

Colloidal systems with competing interactions are known to exhibit a range of dynamically arrested states because of the systems' inability to reach its underlying equilibrium state due to intrinsic frustration. Graphene oxide (GO) aqueous dispersions constitute a class of 2D-anisotropic colloids with competing interactions long-range electrostatic repulsion, originating from ionized groups located on the rim of the sheets, and weak dispersive attractive interactions originating from the unoxidized graphitic domains. We show here that aqueous dispersions of GO exhibit a range of arrested states, encompassing fluid, glass, and gels that coexist with liquid-crystalline order with increasing volume fraction. These states can be accessed by varying the relative magnitudes of the repulsive and attractive forces. This can be realized by changing the ionic strength of the medium. We observe at low salt concentrations, where long-range electrostatic repulsion dominates, the formation of a repulsive Wigner glass, while at high salt concentrations, when attractive forces dominate, the formation of gels exhibits a nematic to columnar liquid-crystalline transition. The present work highlights how the chemical structure of GO hydrophilic ionizable groups and hydrophobic graphitic domains coexisting on a single sheet gives rise to a rich and complex array of arrested states.

Vortex dynamics at rf frequencies in Bi2Sr2CaCu2O8 single crystals

We have studied the low magnetic field high temperature region of the H-T phase diagram of Bi2Sr2CaCu2O8 single crystals using the technique of non-resonant rf response at a frequency of 20 MHz. With H(rf)parallel to a, H parallel to c, the isothermal magnetic field scans below T-c show that the frequency f(H) of the tank circuit decreases continuously with increase in H before saturating at H similar to H-D(T). Such a decrease in f(H) reflects increasing rf penetration into the weakly screened region between CuO bilayers. The saturation of f(H) at its lowest value for H similar to H-D(T) indicates complete rf penetration land hence the disappearance of field dependence) due to the vanishing of the screening rf currents I-rf(c) in those regions or equivalently when the phase coherence between adjacent superconducting layers vanishes. Therefore H,(T) represents the decoupling of the adjacent superconducting bilayers, and hence also a 3D to 2D decoupling transition of the vortex structure. Simultaneous monitoring of the field dependent rf power dissipation P(H) shows a maximum in dP/dH at H-D(T). The observed H-D(T) line in many crystals is in excellent agreement with the (l/t-1) behavior proposed for decoupling.

Phase transitions and rare-earth magnetism in hexagonal and orthorhombic $DyMnO_{3}$ single crystals

The floating-zone method with different growth ambiences has been used to selectively obtain hexagonal or orthorhombic DyMnO3 single crystals. The crystals were characterized by x-ray powder diffraction of ground specimens and a structure refinement as well as electron diffraction. We report magnetic susceptibility, magnetization and specific heat studies of this multiferroic compound in both the hexagonal and the orthorhombic structure. The hexagonal DyMnO3 shows magnetic ordering of Mn3+ (S = 2) spins on a triangular Mn lattice at T-N(Mn) = 57 K characterized by a cusp in the specific heat. This transition is not apparent in the magnetic susceptibility due to the frustration on the Mn triangular lattice and the dominating paramagnetic susceptibility of the Dy3+ (S = 9/2) spins. At T-N(Dy) = 3 K, a partial antiferromagnetic order of Dy moments has been observed. In comparison, the magnetic data for orthorhombic DyMnO3 display three transitions. The data broadly agree with results from earlier neutron diffraction experiments, which allows for the following assignment: a transition from an incommensurate antiferromagnetic ordering of Mn3+ spins at T-N(Mn) = 39 K, a lock-in transition at Tlock-in = 16 K and a second antiferromagnetic transition at T-N(Dy) = 5 K due to the ordering of Dy moments. Both the hexagonal and the orthorhombic crystals show magnetic anisotropy and complex magnetic properties due to 4f-4f and 4f-3d couplings.

Growth and characterization of pure and doped single crystals of $CuGeO_{3}$

Good quality single crystals of copper metagermanite, CuGeO3, are grown by flux technique. Growth is carried out at relatively low temperatures by using Bi2O3 along with CuO in an optimal flux ratio. Besides rendering the procedure simple, lower growth temperature reduces growth defect concentration. Single crystals of Cu1 - xCoxGeO3 and CuGe1 - yGayO3 are grown by the same method for different values of x and y to investigate the influence of in-chain and off-chain doping on spin-Peierls (SP) transition. Change in color, morphology and surface features as a result of doping are briefly discussed. Spin-Peierls transition of these crystals is studied by susceptibility measurements on a commercial SQUID magnetometer. Cationic substitution resulted in reduction of spin-Peierls transition temperature (T-SP) of CuGeO3. Substitution of magnetic impurity cobalt in-chain site caused more pronounced effects such as suppression of SP phase.

Influence of cobalt doping on superconducting transition in as-grown YBCO single crystals

The role of a charge buffer layer in the superconductivity of high-T-c materials is best studied by cationic substitutions. In this work, the chain copper in YBCO single crystals is substituted by Co3+ ion and consequent effect on superconducting transition temperature (T-c) studied. The T-c is measured using non-resonant Microwave Absorption technique, which is a highly sensitive and contactless method. It is seen that T-c of as-grown crystals is considerably enhanced by cobalt doping in low concentration regime. In contrast, higher T-c is achieved in undoped crystals only after extended oxygen anneal. When dopant concentration increases beyond an optimal value, T-c decreases and the system does not show superconductivity when cobalt content is high (x > 0.5 in YBa2Cu3-xCOxO7+/-delta). This behaviour consequent to cobalt substitution is discussed with reference to the apical oxygen model. Optimal cobalt doping can be thought of as an alternative to extended oxygen anneal in as-grown crystals of YBCO.

Micro-Raman imaging of Te precipitates in CdZnTe (Zn similar to 4%) crystals

Micro-Raman imaging of the distribution of Te precipitates in CdZnTe crystals in different phases is reported. For the normal phase of Te precipitates, the Raman modes appear centered around 121(A1), 141(E)/TO(CdTe) cm−1 and a weak mode around 92(E) cm−1 in CdZnTe indicating the presence of trigonal lattice of Te. Under high pressure phase, the volume of Te precipitates collapses, giving more bond energy resulting in the blueshift of the corresponding Raman bands. Also, the spatial distribution of the area ratio of 121 to 141 cm−1 Raman modes is used to quantify Te precipitates. Further, near-infrared microscopy images support these results.

Families of asymptotic tensile crack tip stress fields in elastic-perfectly plastic single crystals

In this work, two families of asymptotic near-tip stress fields are constructed in an elastic-ideally plastic FCC single crystal under mode I plane strain conditions. A crack is taken to lie on the (010) plane and its front is aligned along the [(1) over bar 01] direction. Finite element analysis is first used to systematically examine the stress distributions corresponding to different constraint levels. The general framework developed by Rice (Mech Mater 6:317-335, 1987) and Drugan (J Mech Phys Solids 49:2155-2176, 2001) is then adopted to generate low triaxiality solutions by introducing an elastic sector near the crack tip. The two families of stress fields are parameterized by the normalized opening stress (tau(A)(22)/tau(o)) prevailing in the plastic sector in front of the tip and by the coordinates of a point where elastic unloading commences in stress space. It is found that the angular stress variations obtained from the analytical solutions show good agreement with finite element analysis.

Directed Synthesis of Rocksalt AuCl Crystals

We report the first-time experimental realization of rocksalt AuCl crystals. Our approach involves Au(III) complexing and reduction to Au(I) using an amine-terminated surfactant in a low dielectric permittivity solvent. The low charge screening in nonpolar solvents promotes crystallization of rocksalt AuCl, in which the bonding is predominantly ionic, in preference over tetragonal AuCl. The rocksalt AuCl crystals obtained here will facilitate studies to unveil the nexus between electronic structure and crystal structure in AuCl polymorphs, and provide insights on these relationships in other polymorphic crystal systems. Our approach provides a new means for crystallizing selective polymorphs of inorganic compounds by subtly influencing the cation electronic structure by varying the dielectric permittivity of the synthesis medium. In addition, the AuCl crystals can serve as inexpensive Au(I) precursors for forming a variety of Au nanostructures.

Dipolar reorientation and phase-transition in mixed alkali-halide crystals

We show that the results of Lüty and Ortiz-Lopez relating the cyanide reorientation rates to the high-temperature phase diagrams of alkali-halide-alkali-cyanide mixed crystals can be understood within simple mean-field theory.

Conformational transitions in a Pro-Pro peptide on dissolution of single crystals

The peptide t-butyloxycarbonyl-α-aminoisobutyryl-L-prolyl-L-prolyl-N-methylamide has been shown to adopt an extended structure in the solid state. The Pro-Pro segment occurs in the poly-proline II conformation. On dissolution of single crystals at not, vert, similar 233°K, a single species corresponding to the all Image peptide backbone is observed by 270 MHz 1H NMR. On warming, Image to Image isomerization about the Pro-Pro bond is facilitated. Both Image (ψ not, vert, similar−50°) and Image (ψ not, vert, similar 130°) rotamers about the Pro3 Cα---CO bond are detectable in the Pro-Pro Image conformer, at low temperature. These observations demonstrate unambiguously the large differences in the solid state and solution conformations of a Pro-Pro sequence.

Using lead sulphate instead of lead oxide in flux growth of yttrium iron garnet(YIG) crystals

Crystal growth of YIG from fluxes containing lead sulphate in place of lead oxide in the usual lead oxide-lead fluoride-boron oxide flux system has been tried. Lead sulphate decomposes during crystal growth giving lead oxide and sulphur trioxide. Due to the influence of sulphur trioxide in the system the yield of crystals almost doubles. There is no change either in the morphology of the crystals or their lattice parameter. It is possible that solubility of YIG is different in the new flux and the changed solubility causes the increase in yield of crystals.