A superamphiphobic coating with an ammonia-triggered transition to superhydrophilic and superoleophobic for oil-water separation

Superhydrophilic and superoleophobic materials are very attractive for efficient and cost-effective oil-water separation, but also very challenging to prepare. Reported herein is a new superamphiphobic coating that turns superhydrophilic and superoleophobic upon ammonia exposure. The coating is prepared from a mixture of silica nanoparticles and heptadecafluorononanoic acid-modified TiO2 sol by a facile dip-coating method. Commonly used materials, including polyester fabric and polyurethane sponge, modified with this coating show unusual capabilities for controllable filtration of an oil-water mixture and selective removal of water from bulk oil. We anticipate that this novel coating may lead to the development of advanced oil-water separation techniques.

Separation of Ownership from Control and Discretionary Managerial Behaviour in a Transition Economy

This study was the final stage of a four-year study of managerial behaviour and company performance in Bulgaria and examined the influence of changing ownership and control structures of companies on managerial behaviour and initiative. It provides a theoretical summary of the specific types of ownership, control, governance structures and managerial strategies in the Bulgarian transitional economy during 1992-1996. It combines two theoretical approaches, the property-rights approach to show concentrated property-rights structure and private and majority types of control as determinants of efficient enterprise risk bearing and constrained managerial discretion, and the agency theory approach to reveal the efficient role of direct non-market governance mechanisms over managers. Mr. Peev also used empirical information collected from the Central Statistical office in Bulgaria, three different enterprise investigations of corporatised state-owned enterprises between 1992 and 1994, and his own data base of privatised and private de novo industrial companies in 1996-1996. The project gives a detailed description of the main property-rights structures in Bulgaria at the present time and of the various control structures related to these. It found that there is a strong owner type of control in private and privatised firms, although, contrary to expectations, 100% state -owned enterprises tended to be characterised by a separation of ownership from control, leaving scope for managerial discretion. Mr. Peev predicts that after the forthcoming mass privatisation, many companies will acquire a dispersed ownership structure and there will be a greater separation of ownership from control and potential or inefficient managerial behaviour. The next aspect considered in detail was governance structures and the influence of the generally unstable macroeconomic environment in the country during the period in question. In examining managerial strategies, Mr. Peev divided the years since 1990 into 3 periods. Even in the first period (1990-1992) there were some signs of a more efficient role for managers and between 1992 and 1994 the picture of control structures and different managerial behaviour in state-owned companies became more diversified. Managerial strategies identified included managerial initiatives for privatisation, where managers took initiative in resolving problems of property rights and introducing restructuring measures and privatisation proposals, managerial initiatives for restructuring without privatisation, and passive adjustment and passive management, where managers seek outside services for marketing, finance management, etc. in order to adjust to the new environment. During 1995-1996 some similarities and differences between the managerial behaviour of privatised and state-owned firms emerged. Firstly, the former have undergone many changes in investment and technology, while managers of state-owned companies have changed little in this field, indicating that the private property-rights structure is more efficient for the long-term adaptation of enterprises. In the area of strategies relating to product quality, marketing, and pricing policy there was little difference between managers of private, privatised and state-owned firms. The most passive managerial behaviour was found in non-incorporated state-owned firms, although these have only an insignificant stake in the economy.

Fluorine-free superhydrophobic coatings with pH-induced wettability transition for controllable oil-water separation

We present a simple, environmentally friendly approach to fabricating superhydrophobic coatings with pH-induced wettability transition. The coatings are prepared from a mixture of silica nanoparticles and decanoic acid-modified TiO2. When the coating is applied on cotton fabric, the fabric turns superhydrophobic in air but superoleophilic in neutral aqueous environment. It is permeable to oil fluids but impermeable to water. However, when the coated fabric is placed in basic aqueous solution or ammonia vapor, it turns hydrophilic but underwater superoleophobic, thus allowing water to penetrate through but blocking oil. Therefore, such a unique, selective water/oil permeation feature makes the treated fabric have capability to separate either oil or water from a water-oil mixture. It may be useful for development of smart oil-water separators, microfluidic valves, and lab-on-a-chip devices.

On the origin of the inflectional instability of a laminar separation bubble

This is an experimental and theoretical Study of a laminar separation bubble and the associated linear stability mechanisms. Experiments were performed over a flat plate kept in a wind tunnel, with an imposed pressure gradient typical of an aerofoil that would involve a laminar separation bubble. The separation bubble was characterized by measurement of surface-pressure distribution and streamwise velocity using hot-wire anemometry. Single component hot-wire anemometry was also used for a detailed study of the transition dynamics. It was foundthat the so-called dead-air region in the front portion of the bubble corresponded to a region of small disturbance amplitudes, with the amplitude reaching a maximum value close to the reattachment point. An exponential growth rate of the disturbance was seen in the region upstream of the mean maximum height of the bubble, and this was indicative of a linear instability mechanism at work. An infinitesimal disturbance was impulsively introduced into the boundary layer upstream of separation location, and the wave packet was tracked (in an ensemble-averaged sense) while it was getting advected downstream. The disturbance was found to be convective in nature. Linear stability analyses (both the Orr-Sommerfeld and Rayleigh calculations) were performed for mean velocity profiles, starting from an attached adverse-pressure-gradient boundary layer all the way up to the front portion of the separation-bubble region (i.e. up to the end of the dead-air region in which linear evolution of the disturbance could be expected). The conclusion from the present work is that the primary instability mechanism in a separation bubble is inflectional in nature, and its origin can be traced back to upstream of the separation location. In other words, the inviscid inflectional instability of the separated shear layer should be logically seen as an extension of the instability of the upstream attached adverse-pressure-gradient boundary layer. This modifies the traditional view that pegs the origin of the instability in a separation bubble to the detached shear layer Outside the bubble, with its associated Kelvin-Helmholtz mechanism. We contendthat only when the separated shear layer has moved considerably away from the wall (and this happens near the maximum-height location of the mean bubble), a description by the Kelvin-Helmholtz instability paradigm, with its associated scaling principles, Could become relevant. We also propose a new scaling for the most amplified frequency for a wall-bounded shear layer in terms of the inflection-point height and the vorticity thickness and show it to be universal.

In Situ Phase Separation Following Dehydration in Bimetallic Sulfates: A Variable-Temperature X-Ray Diffraction Study

Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O and K4Cd3-(SO4)(5)center dot 3H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O is trigonal, space group R (3) over bar. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na2Mn(SO4)(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K4Cd3(SO4)(5)center dot 3H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K4Cd3(SO4)(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

Boundary layer transition observations on a body of revolution with surface heating and cooling in water

Boundary layer flow visualization in water with surface heat transfer was carried out on a body of revolution which had the predicted possibility of laminar separation under isothermal conditions. Flow visualization was by in-line holographic technique. Boundary layer stabilization, including elimination of laminar separation, was observed to take place on surface heating. Conversely, boundary layer destabilization was observed on surface cooling. These findings are consistent with the theoretical predictions of Wazzan et al. in The stability and transition of heated and cooled incompressible laminar boundary layers, in Proceedings of the Fourth International Heat Transfer Conference, Vol. 2, FCI 4. Elsevier, Amsterdam (1970).

Localised instability in unsteady separation bubbles

We propose in experimental method to study the instability of thin unsteady separation bubbles, i.e. of unsteady boundary layers with reverse flow. The unsteady boundary layer is created by controlled temporal and spatial variations of the velocity external to the boundary layer. We present results of the evolution of instability in different temporally varying flows in a shallow angle diffuser. Depending on the extent of reverse flow in the boundary we observe that instability can be spatially localised.

On the bursting criterion for laminar separation bubbles

Traditionally, laminar separation bubbles have been characterised as being 'long' or 'short' on the basis of a two parameter 'bursting' criterion involving a pressure gradient parameter and Reynolds Number at separation. In the present work we suggest a refined bursting criterion, which takes into account not just the length of the bubble but also the maximum height of the bubble, thereby shedding some light on the less understood phenomenon of 'bursting' in laminar separation bubbles.

Electronic phase separation in correlated oxides: The phenomenon, its present status and future prospects

Many transition metal oxide materials of high chemical purity are not necessarily monophasic. Thus, single crystals of chemically pure rare earth manganites and cobaltates of the general formula Ln1-xAxMO3 (Ln=rare earth metal, A=alkaline earth metal, M=Mn, Co) exhibit the phenomenon of electronic phase separation wherein phases of different electronic and magnetic properties coexist. Such phase separation, the length scale of which can vary anywhere between a few nanometers to microns, gives distinct signatures in X-ray and neutron diffraction patterns, electrical and magnetic properties, as well as in NMR and other spectroscopies. While the probe one employs to investigate electronic phase separation depends on the length scale, it is noteworthy that direct imaging of the inhomogeneities has been accomplished. Some understanding of this phenomenon has been possible on the basis of some of the theoretical models, but we are far from unraveling the varied aspects of this new phenomenon. Herein, we present the highlights of experimental techniques and theoretical approaches, and comment on the future outlook for this fascinating phenomenon

Disorder-driven electronic localization and phase separation in superconducting Fe1+yTe0.5Se0.5 single crystals

We have investigated the influence of Fe excess on the electrical transport and magnetism of Fe1+yTe0.5Se0.5 (y=0.04 and 0.09) single crystals. Both compositions exhibit resistively determined superconducting transitions (T-c) with an onset temperature of about 15 K. From the width of the superconducting transition and the magnitude of the lower critical field H-c1, it is inferred that excess of Fe suppresses superconductivity. The linear and nonlinear responses of the ac susceptibility show that the superconducting state for these compositions is inhomogeneous. A possible origin of this phase separation is a magnetic coupling between Fe excess occupying interstitial sites in the chalcogen planes and those in the Fe-square lattice. The temperature derivative of the resistivity d(rho)/d(T) in the temperature range T-c < T < T-a with T-a being the temperature of a magnetic anomaly, changes from positive to negative with increasing Fe. A log 1/T divergence of the resistivity above T-c in the sample with higher amount of Fe suggests a disorder-driven electronic localization.

Dependence of the strength of interaction of carbon monoxide with transition metal clusters on the cluster size

The interaction of CO with Cu, Pd, and Ni at different coverages of the metals on solid substrates has been investigated by He II and core-level spectroscopies, after the nature of variation of the metal core-level binding energies with the coverage or the cluster size is established. The separation between the (1 pi + 5 sigma) and 4 sigma levels of CO increases with a decrease in the size of the metal clusters, accompanied by an increase in the desorption temperature. In the case of Cu, the intramolecular shakeup satellite of CO disappears on small clusters. More importantly, CO dissociates on small Ni clusters, clearly confirming that metal-CO interaction strength increases with a decrease in the cluster size.

Vesicle formation from dimeric surfactants through ion-pairing. Adjustment of polar headgroup separation leads to control over vesicular thermotropic properties

Eight new vesicle-forming dimeric surfactants are synthesized: the polar headgroup separation in such dimeric amphiphiles strongly influences their vesicular thermotropic phase-transition behaviour.

Sol-Gel Transition in Dispersions of Layered Double-Hydroxide Nanosheets

Surfactant-intercalated layered double-hydroxide solid Mg-Al LDH-dodecyl sulfate (DDS) undergoes rapid and facile delamination to its ultimate constituent, single sheets of nanometer thickness and micrometer size, in a nonpolar solvent such as toluene to form stable dispersions. The delaminated nanosheets are electrically neutral because the surfactant chains remain tethered to the inorganic layer even on exfoliation. With increasing volume fraction of the solid, the dispersion transforms from a free-flowing sol to a solidlike gel. Here we have investigated the sol-gel transition in dispersions of the hydrophobically modified Mg-Al LDH-DDS in toluene by rheology, SAXS, and (1)H NMR measurements. The rheo-SAXS measurements show that the sharp rise in the viscosity of the dispersion during gel formation is a consequence of a tactoidal microstructure formed by the stacking of the nanosheets with an intersheet separation of 3.92 nm. The origin and nature of the attractive forces that lead to the formation of the tactoidal structure were obtained from 1D and 2D (1)H NMR measurements that provided direct evidence of the association of the toluene solvent molecules with the terminal methyl of the tethered DDS surfactant chains. Gel formation is a consequence of the attractive dispersive interactions of toluene molecules with the tails of DDS chains anchored to opposing Mg-Al LDH sheets. The toluene solvent molecules function as molecular ``glue'' holding the nanosheets within the tactoidal microstructure together. Our study shows how rheology, SAXS, and NMR measurements complement each other to provide a molecular-level description of the sol-gel transition in dispersions of a hydrophobically modified layered double hydroxide.

Electronic structure of early transition metal oxides, Ca1−xSrxVO3 and La1−xCaxVO3: What can we learn from photoelectron spectroscopy

Photoemission spectroscopy offers the unique possibility of mapping out the electronic structure of the occupied electron states. However, the extreme surface sensitivity of this technique ensures that only the surface and the near-surface regions of any sample are probed. An important question arises in this context—Is the electronic structure of the surface region the same as that of the bulk? We address this issue using two different series of vanadium oxides, Ca1−xSrxVO3 and La1−xCaxVO3. Our results clearly establish that the electronic structure of the surface region is drastically different from that of the bulk in both these cases. We provide a method to separate the two contributions: one arising from the near-surface region and the other representative of the bulk. This separation allows us to deduce some very unusual behaviors of the electronic structures in these systems.

Relevance of local parallel theory to the linear stability of laminar separation bubbles

Laminar separation bubbles are thought to be highly non-parallel, and hence global stability studies start from this premise. However, experimentalists have always realized that the flow is more parallel than is commonly believed, for pressure-gradient-induced bubbles, and this is why linear parallel stability theory has been successful in describing their early stages of transition. The present experimental/numerical study re-examines this important issue and finds that the base flow in such a separation bubble becomes nearly parallel due to a strong-interaction process between the separated boundary layer and the outer potential flow. The so-called dead-air region or the region of constant pressure is a simple consequence of this strong interaction. We use triple-deck theory to qualitatively explain these features. Next, the implications of global analysis for the linear stability of separation bubbles are considered. In particular we show that in the initial portion of the bubble, where the flow is nearly parallel, local stability analysis is sufficient to capture the essential physics. It appears that the real utility of the global analysis is perhaps in the rear portion of the bubble, where the flow is highly non-parallel, and where the secondary/nonlinear instability stages are likely to dominate the dynamics.