Monitoring the Dynamics of Concentrated Suspensions by Enhanced Backward Light Scattering

The shear-induced flocculation of kaolin-polymer flocs in a stirred tank is investigated at medium to high solids concentrations (ϕ=1−10% w/w). The evolution of the average floc size is monitored by the change in intensity of laser light scattered in the 180° direction. The measurements reflect the change in particle number concentration as flocculation proceeds. As flocculation begins, coagulation dominates and the floc size increases (total particle number decreases) and then levels off at a steady state value as fragmentation becomes significant and balances coagulation. At steady state, the measurements indicate the extent of flocculation. Increasing the shear rate increases the coagulation and fragmentation rates, resulting in smaller floc sizes at steady state. Increasing the flocculant concentration increases the steady state floc size by strengthening the bonds between primary particles to resist fragmentation. At constant shear rate and flocculant concentration, increasing the solids fraction decreases the steady state floc size indicating formation of weakly bonded flocs. Flocculant mixing was the most important factor for flocculation efficiency at high solids concentrations.     

Kinetics of colloidal templating using emulsion drop consolidation

The emulsion templating of ordered colloidal microsphere assemblies by Manoharan et al. involves a consolidation process where dispersed phase fluid is transported from droplets into a continuous phase. Consolidation can be approximated as a diffusion process with moving boundaries. The kinetics of consolidation are investigated here by following droplet shrinkage with time as a prelude to understanding rate effects on assembly structure. Consolidation kinetics are influenced by liquid diffusivity, the number of colloidal particles in a droplet, and the surfactant concentration. While surfactant exhibits little effect well below its critical micelle concentration (CMC) value, it significantly slows consolidation above the CMC. For a specific continuous phase (i.e., silicone oil and fluorinated silicone oil), with proper scalings, the droplet size shrinks with time following a power law independent of droplet diameter, surfactant concentrations, and particle number concentration. The power law exponent varies from 1/2 to 2/3 with different continuous oil phases as a result of concentration and interfacial effects. This study leads to an improved understanding of colloidal microstructure development at interfaces that can be applied in novel materials synthesis and drug delivery areas.     

Cobalt half-sandwich, sandwich, and mixed sandwich complexes with soft tripodal ligands

Reaction of sodium hydrotris(methimazolyl)borate (NaTm(Me)) with cobalt halides leads to the formation of paramagnetic pseudotetrahedral [Co(Tm(Me))X] (X = Cl, Br, I), of which the bromide has been crystallographically characterized. Mass spectrometry reveals the presence of higher molecular weight fragments [Co(Tm(Me))(2)](+) and [Co(2)(Tm(Me))(2)X](+) in solution. Aerial oxidation in donor solvents (e.g. MeCN) leads to formation of the [Co(Tm(Me))(2)](+) cation, which has been crystallographically characterized as the BF(4)(-), ClO(4)(-), Br(-), and I(-), salts. Attempts to prepare the mixed sandwich complex, [Co(Cp)(Tm(Me))](+), resulted in ligand decomposition to yield [Co(mtH)(3)I]I (mtH = 1-methylimidazole-2-thione), but with the more electron donating methylcyclopentadienyl (Cp(Me)) ligand, [Co(Cp(Me))(Tm(Me))]I was isolated and characterized. Electrochemical measurements reveal that the cobalt(III) Tm(Me) complexes are consistently more difficult to reduce than their Tp and Cp congeners.     

A monomeric imidazol-2-ylidene-silver(I) chloride complex: synthesis,structure, and solid state 109Ag and 13C CP/MAS NMR characterization

The structure of 1,3-bis(2,4,6-trimethylphenyl)-imidazol-2-ylidene-silver(I) chloride, 1, has been determined to be a monomer with weak head-to-tail H...Cl interactions in the solid state. A multinuclear NMR study using a (13)C(carbene) labeled derivative, 1((13)C), exhibits (13)C-(107,109)Ag coupling in solution. Further, the solid state CP/MAS NMR parameters, including the principal components of the chemical shift tensors for both the (13)C and (109)Ag centers, have been determined. With the aid of DFT calculations, the orientation of the chemical shift tensors have been assigned.     

Reductions of challenging organic substrates by a nickel complex of a noninnocent crown carbene ligand

The first crown-tetracarbene complex of Ni(II) has been prepared, and its crystal structure determined. The complex can be reduced by Na/Hg, with an uptake of two electrons. The reduced complex reductively cleaves arenesulfonamides, including those derived from secondary aliphatic amines, and effects Birch reduction of anthracenes as well as reductive cleavage of stilbene oxides. Computational studies show that the orbital that receives electrons upon reduction of the complex 2 is predominantly based on the crown carbene ligand and also that the HOMO of the parent complex 2 is based on the ligand.     

The elastic and inelastic scattering of intermediate energy protons on deuterium at small momentum transfer

The differential cross sections for the elastic and inelastic scattering of protons on deuterium have been measured for scattering angles less than 14° at 198.5, 297.6 and 456.6 MeV. These quantities were determined relative to dσ / dΩ for pp elastic scattering with a precision of typically 2%. The range of excitation energies for the (p, p') reaction was chosen to emphasize the region near the np threshold dominated by the final-state interaction in the ¹S₀ channel. Particular attention was given to the dependence on excitation energy of the spectra at 198.5 MeV to examine the sensitivity to the ¹S₀ scattering length, a_np In this paper all data are compared with a new, detailed formulation of a simple model of the reaction mechanism based on the impulse approximation. The experimental results differ from the predictions by typically 10% and the differential cross sections exhibit a sensitivity to the intermediate-energy nucleon-nucleon amplitudes. If the impulse approximation is used to estimate a_np from the data at 198.5 MeV a value of − 24.7 ± 0.4 fm is obtained.     

Photoenhancement mechanism for oxygen chemisorption on GaAs(110) using visible light

Visible light from an argon ion laser (514.5 nm, 3 W/cm²) is seen to increase oxygen chemisorption on cleaved GaAs(110) surfaces up to a final coverage between one and two monolayers. Using photoemission spectroscopy to measure the oxygen coverage after simultaneous exposure of the surface to oxygen and light, we have determined that oxygen uptake for photoenhanced exposures is independent of sample temperature and doping type. In addition, significantly less enhancement is seen for weakly bound oxidizing molecules (N₂O) relative to the effects with molecular oxygen. These results are explained by a photoenhancement mechanism in which energy is released in a surface recombination event, possibly in the form of nonthermal phonons, causing physisorbed gas molecules to dissociate and thereby overcoming a major rate limiting step of the reaction in the dark. This reaction mechanism is supported by calculations of the surface recombination rates and free carrier densities at the surface which show that only the recombination rate is correlated with enhanced oxygen uptake. Other mechanisms and experimental data are also discussed.     

The determination of microgram and sub-microgram amounts of boron : II. The separation of boron by distillation and the evaporation of distillates

Methyl alcohol distillates containing μg amounts of boron may be evaporated without loss of boron by first adding water, sodium hydroxide and glycerol. The resulting residues can be used directly in the curcumin absorptiometric methods previously described. The distillation techniques developed over the last decade by the United Kingdom Atomic Energy authority are briefly described, as these can be used for the separation of boron from practically all types of sample, including organic matter after it has been ashed with lime. In all cases aqueous solutions of the samples are made slightly acid (pH 1.5–5) and evaporated nearly to dryness Residues are then treated with methyl alcohol in one of three ways according to their properties. It is essential to use all-silica distillation apparatus and platinum dishes for collecting distillates. Notes are given of other precautions necessary to minimize contamination from reagents and other sources. The methods are rapid and suitable for routine analysis on up to 10 g of sample. Under favourable conditions, the limit of detection is of the order of 0.01 p.p.m. of boron. A precision of better than 5% can be obtained with amounts exceeding about 0.2 p.p m.     

Co chemisorption on PtCu surfaces II. (1 × 1)-CO/Pt0.98Cu0.02(110)

The chemisorption of CO on the Pt atoms of an initially (1 × 3) reconstructed Pt_0.98Cu_0.02(110) surface at ~ 373 K can lead to the formation of a (1 × 1) surface. Comparisons are made with (1 × 3)-CO surfaces formed by CO exposures at 293 or 155 K. Thermal desorption shows that the (1 × 1)-CO surface has an enhanced population of high temperature CO peak ( ~ 543 K) from Pt sites. The CO-induced structural conversion also leads to a decrease in the subsequent CO uptake on the low temperature Pt sites and on the Pt-Cu “mixed” sites, with a concomitant increase in adsorption on the Cu-like sites. Such a reduction in the number of the Pt-Cu “ mixed” sites is also reflected in the CO-induced changes of the Cu 3d-derived states and the $\text{Cu 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ core levels. A dynamic interplay between chemisorption and surface structure is thus demonstrated.