Engineering of a monodisperse core-shell magnetic Ti-O-Si oxidation nanocatalyst

There has been limited development in catalyst carriers for magnetic separations where superparamagnetic nanoparticles of a high saturation magnetization with no coercivity are required to isolate expensive catalyst reagent that are subjected to repeated magnetic cycles. By using simple stepwise layer-by-layer nanochemistry techniques, we show that an fee FePt nanomagnet can be created inside each silica particle with tailored dimensions to great precision. Subsequent engineering of the external surface with Ti-O-Si species in an optimum structure to create a unique interface gives high activity and excellent selectivity of the composite material for the trans-stilbene oxidation to the corresponding epoxide in the presence of tert-butyl hydroperoxide. Thus, a new magnetic separable epoxidation catalyst is described. This work clearly demonstrates the significance of nanoengineering of a single catalyst particle by a bottom-up construction approach in modern catalyst design, which could lead to new catalytic. properties.

Preparation and magnetic properties of La–Mn and La–Co doped barium hexaferrites prepared via an improved co-precipitation/molten salt method

LaMn and LaCo doped barium hexaferrites of formula Ba(1-x)LaxFe(12-x)MxO19 (M=Mn, Co) (x=0.05 to 0.40) were prepared with an improved co-precipitation/molten salt method. For the synthesis, aqueous solutions of the appropriate metal chlorides were prepared in the ratio required except that the initial mole ratio of Fe and dopants to Ba was chosen to be 11:1, and then mixed with excess Na2CO3. The solutions were then cooled, filtered off, dried, then mixed with KCl flux, and heated at 450 degrees C and for 2 h. The temperature was then raised to 950 degrees C and kept for 4 h, then cooled. This new synthesis method, which employs a lower temperature and shorter reaction time, gives products with improved crystallinity and purity while the saturation magnetization and coercivity values are comparable with those synthesized via the high temperature method.

Variation in dynamic elastic shear modulus of sandstone upon fluid saturation and substitution

Experimental acoustic measurements on sandstone rocks at both sonic and ultrasonic frequencies show that fluid saturation can cause a noticeable change in both the dynamic bulk and shear elastic moduli of sandstones. We observed that the change in dynamic shear modulus upon fluid saturation is highly dependent on the type of saturant, its viscosity, rock microstructure, and applied pressures. Frequency dispersion has some influence on dynamic elastic moduli too, but its effect is limited to the ultrasonic frequency ranges and above. We propose that viscous coupling, reduction in free surface energy, and, to a limited extent, frequency dispersion due to both local and global flow are the main mechanisms responsible for the change in dynamic shear elastic modulus upon fluid saturation and substitution, and we quantify influences.

Feeding rumen-inert fats differing in their degree of saturation decreases intake and increases plasma concentrations of gut peptides in lactating dairy cows

Our objective was to determine the effect of feeding rumen-inert fats differing in their degree of saturation on dry matter intake (DMI), milk production, and plasma concentrations of insulin, glucagon-like peptide 1 (7-36) amide (GLP-1), glucose-dependent insulinotropic polypeptide (GIP), and cholecystokinin (CCK) in lactating dairy cows. Four midlactation, primiparous Holstein cows were used in a 4 x 4 Latin square experiment with 2-wk periods. Cows were fed a control mixed ration ad libitum, and treatments were the dietary addition (3.5% of ration dry matter) of 3 rumen-inert fats as sources of mostly saturated fatty acids (SFA), monounsaturated fatty acids (MUFA), or polyunsaturated fatty acids (PUFA). Daily DMI, milk yield, and composition were measured on the last 4 d of each period. Jugular vein blood was collected every 30 min over a 7-h period on d 12 and 14 of each period for analysis of plasma concentrations of hormones, glucose, and nonesterified fatty acids. Feeding fat decreased DMI, and the decrease tended to be greater for MUFA and PUFA compared with SFA. Plasma concentration of GLP-1 increased when fat was fed and was greater for MUFA and PUFA. Feeding fat increased plasma glucose-dependent insulinotropic polypeptide and CCK concentrations and decreased plasma insulin concentration. Plasma CCK concentration was greater for MUFA and PUFA than for SFA and was greater for MUFA than PUFA. Decreases in DMI in cows fed fat were associated with increased plasma concentrations of GLP-1 and CCK and a decreased insulin concentration. The role of these peptides in regulating DMI in cattle fed fat requires further investigation.

Monodisperse binary nanocomposite in silica with enhanced magnetization for magnetic separation

The majority of research on magnetic nanoparticles has focused on optical, electrical, and magnetic storage areas. Recently, the application of magnetic nanoparticles as magnetically separable nanovehicles for chemical or biological species has become an area of intensive research but with rather different challenging criteria that are yet to be addressed. For example, the enhancement of intrinsically weak magnetic properties, avoidance of magnetic interactions among particles, and improvement of the stability of the nanoparticles remain key issues. Here, it is demonstrated using sequential nanochemistry preparation techniques that exchange-coupled nanomagnets, such as FePt-Fe3Pt or FePt-Fe3O4 with dramatically enhanced magnetization, can be placed inside a silica nanosphere. The advantages of enhanced magnetization and the provision of protective coating and anchored sites on the silica shell surface render these new coated particles suitable for use in magnetic separation.

On nonlinear symmetric stability and the nonlinear saturation of symmetric instability

A nonlinear symmetric stability theorem is derived in the context of the f-plane Boussinesq equations, recovering an earlier result of Xu within a more general framework. The theorem applies to symmetric disturbances to a baroclinic basic flow, the disturbances having arbitrary structure and magnitude. The criteria for nonlinear stability are virtually identical to those for linear stability. As in Xu, the nonlinear stability theorem can be used to obtain rigorous upper bounds on the saturation amplitude of symmetric instabilities. In a simple example, the bounds are found to compare favorably with heuristic parcel-based estimates in both the hydrostatic and non-hydrostatic limits.

Nonlinear saturation of baroclinic instability: part III: bounds on the energy

Rigorous upper bounds are derived on the saturation amplitude of baroclinic instability in the two-layer model. The bounds apply to the eddy energy and are obtained by appealing to a finite amplitude conservation law for the disturbance pseudoenergy. These bounds are to be distinguished from those derived in Part I of this study, which employed a pseudomomentum conservation law and provided bounds on the eddy potential enstrophy. The bounds apply to conservative (inviscid, unforced) flow, as well as to forced-dissipative flow when the dissipation is proportional to the potential vorticity. Bounds on the eddy energy are worked out for a general class of unstable westerly jets. In the special case of the Phillips model of baroclinic instability, and in the limit of infinitesimal initial eddy amplitude, the bound states that the eddy energy cannot exceed ϵβ2/6F where ϵ = (U − Ucrit)/Ucrit is the relative supercriticality. This bound captures the essential dynamical scalings (i.e., the dependence on ϵ, β, and F) of the saturation amplitudes predicted by weakly nonlinear theory, as well as exhibiting remarkable quantitative agreement with those predictions, and is also consistent with heuristic baroclinic adjustment estimates.

Nonlinear saturation of baroclinic instability: part II: continuously stratified fluid

Rigorous upper bounds are derived that limit the finite-amplitude growth of arbitrary nonzonal disturbances to an unstable baroclinic zonal flow in a continuously stratified, quasi-geostrophic, semi-infinite fluid. Bounds are obtained bath on the depth-integrated eddy potential enstrophy and on the eddy available potential energy (APE) at the ground. The method used to derive the bounds is essentially analogous to that used in Part I of this study for the two-layer model: it relies on the existence of a nonlinear Liapunov (normed) stability theorem, which is a finite-amplitude generalization of the Charney-Stern theorem. As in Part I, the bounds are valid both for conservative (unforced, inviscid) flow, as well as for forced-dissipative flow when the dissipation is proportional to the potential vorticity in the interior, and to the potential temperature at the ground. The character of the results depends on the dimensionless external parameter γ = f02ξ/β0N2H, where ξ is the maximum vertical shear of the zonal wind, H is the density scale height, and the other symbols have their usual meaning. When γ ≫ 1, corresponding to “deep” unstable modes (vertical scale ≈H), the bound on the eddy potential enstrophy is just the total potential enstrophy in the system; but when γ≪1, corresponding to ‘shallow’ unstable modes (vertical scale ≈γH), the eddy potential enstrophy can be bounded well below the total amount available in the system. In neither case can the bound on the eddy APE prevent a complete neutralization of the surface temperature gradient which is in accord with numerical experience. For the special case of the Charney model of baroclinic instability, and in the limit of infinitesimal initial eddy disturbance amplitude, the bound states that the dimensionless eddy potential enstrophy cannot exceed (γ + 1)2/24&gamma2h when γ ≥ 1, or 1/6;&gammah when γ ≤ 1; here h = HN/f0L is the dimensionless scale height and L is the width of the channel. These bounds are very similar to (though of course generally larger than) ad hoc estimates based on baroclinic-adjustment arguments. The possibility of using these kinds of bounds for eddy-amplitude closure in a transient-eddy parameterization scheme is also discussed.

Nonlinear saturation of baroclinic instability: part I: the two-layer model

A rigorous bound is derived which limits the finite-amplitude growth of arbitrary nonzonal disturbances to an unstable baroclinic zonal flow within the context of the two-layer model. The bound is valid for conservative (unforced) flow, as well as for forced-dissipative flow that when the dissipation is proportional to the potential vorticity. The method used to derive the bound relies on the existence of a nonlinear Liapunov (normed) stability theorem for subcritical flows, which is a finite-amplitude generalization of the Charney-Stern theorem. For the special case of the Philips model of baroclinic instability, and in the limit of infinitesimal initial nonzonal disturbance amplitude, an improved form of the bound is possible which states that the potential enstrophy of the nonzonal flow cannot exceed ϵβ2, where ϵ = (U − Ucrit)/Ucrit is the (relative) supereriticality. This upper bound turns out to be extremely similar to the maximum predicted by the weakly nonlinear theory. For unforced flow with ϵ < 1, the bound demonstrates that the nonzonal flow cannot contain all of the potential enstrophy in the system; hence in this range of initial supercriticality the total flow must remain, in a certain sense, “close” to a zonal state.

Rigorous bounds on the nonlinear saturation of instabilities to parallel shear flows

A novel method is presented for obtaining rigorous upper bounds on the finite-amplitude growth of instabilities to parallel shear flows on the beta-plane. The method relies on the existence of finite-amplitude Liapunov (normed) stability theorems, due to Arnol'd, which are nonlinear generalizations of the classical stability theorems of Rayleigh and Fjørtoft. Briefly, the idea is to use the finite-amplitude stability theorems to constrain the evolution of unstable flows in terms of their proximity to a stable flow. Two classes of general bounds are derived, and various examples are considered. It is also shown that, for a certain kind of forced-dissipative problem with dissipation proportional to vorticity, the finite-amplitude stability theorems (which were originally derived for inviscid, unforced flow) remain valid (though they are no longer strictly Liapunov); the saturation bounds therefore continue to hold under these conditions.

Nonlinear stability and the saturation of instabilities to axisymmetric vortices

Nonlinear stability theorems are presented for axisymmetric vortices under the restriction that the disturbance is independent of either the azimuthal or the axial coordinate. These stability theorems are then used, in both cases, to derive rigorous upper bounds on the saturation amplitudes of instabilities. Explicit examples of such bounds are worked out for some canonical profiles. The results establish a minimum order for the dependence of saturation amplitude on supercriticality, and are thereby suggestive as to the nature of the bifurcation at the stability threshold.

Molecular dynamics study on the equilibrium magnetization properties and structure of ferrofluids

We investigate in detail the initial susceptibility, magnetization curves, and microstructure of ferrofluids in various concentration and particle dipole moment ranges by means of molecular dynamics simulations. We use the Ewald summation for the long-range dipolar interactions, take explicitly into account the translational and rotational degrees of freedom, coupled to a Langevin thermostat. When the dipolar interaction energy is comparable with the thermal energy, the simulation results on the magnetization properties agree with the theoretical predictions very well. For stronger dipolar couplings, however, we find systematic deviations from the theoretical curves. We analyze in detail the observed microstructure of the fluids under different conditions. The formation of clusters is found to enhance the magnetization at weak fields and thus leads to a larger initial susceptibility. The influence of the particle aggregation is isolated by studying ferro-solids, which consist of magnetic dipoles frozen in at random locations but which are free to rotate. Due to the artificial suppression of clusters in ferrosolids the observed susceptibility is considerably lowered when compared to ferrofluids.

The only way is up: retail format saturation and the demise of the American five and dime store, 1914-1941

We examine a classic ‘wheel of retailing’ episode – the abandonment of the five and dime pricing formula by American variety chains. These switched from a conventional product lifecycle, focusing on cost reduction through standardisation, to a reverse path up the ‘service cost - unit value’ continuum. We show that, rather than reflecting deteriorating managerial acumen, this was a response to the continued imperative for growth following retail format saturation. Firm-specific (rather than format-specific) competitive advantages were too weak for any chain to be confident it could win a within-format price war, making inter-format competition through raising price points more attractive.