Selective catalytic oxidation of alkylaromatic molecules by nanosize water droplets containing Co2+ species in supercritical carbon dioxide fluid

Stabilized nano-sized water droplet carrying water-soluble Co2+ species is employed as a new catalyst system for the oxidation of the alkyl aromatics in the presence of a fluorinated surfactant. This stable system contains no labile C-H structure and can facilitate excellent mixing of catalytic Co(II)/NaBr species, hydrocarbon substrates and oxygen in supercritical carbon dioxide fluid, which is demonstrated to be an excellent alternative solvent system to acetic acid or nitric acid for air oxidation of a number of alkyl aromatic hydrocarbons using Co(II) species at mild conditions. As a result, potential advantages of this 'greener' catalytic method including safer operation, easier separation and purification, higher catalytic activity with selectivity and without using corrosive or oxidation unstable solvent are therefore envisaged.

Modelling metal cutting using modern ductile fracture mechanics: Quantitative explanations for some longstanding problems

The assumption that negligible work is involved in the formation of new surfaces in the machining of ductile metals, is re-examined in the light of both current Finite Element Method (FEM) simulations of cutting and modern ductile fracture mechanics. The work associated with separation criteria in FEM models is shown to be in the kJ/m2 range rather than the few J/m2 of the surface energy (surface tension) employed by Shaw in his pioneering study of 1954 following which consideration of surface work has been omitted from analyses of metal cutting. The much greater values of surface specific work are not surprising in terms of ductile fracture mechanics where kJ/m2 values of fracture toughness are typical of the ductile metals involved in machining studies. This paper shows that when even the simple Ernst–Merchant analysis is generalised to include significant surface work, many of the experimental observations for which traditional ‘plasticity and friction only’ analyses seem to have no quantitative explanation, are now given meaning. In particular, the primary shear plane angle φ becomes material-dependent. The experimental increase of φ up to a saturated level, as the uncut chip thickness is increased, is predicted. The positive intercepts found in plots of cutting force vs. depth of cut, and in plots of force resolved along the primary shear plane vs. area of shear plane, are shown to be measures of the specific surface work. It is demonstrated that neglect of these intercepts in cutting analyses is the reason why anomalously high values of shear yield stress are derived at those very small uncut chip thicknesses at which the so-called size effect becomes evident. The material toughness/strength ratio, combined with the depth of cut to form a non-dimensional parameter, is shown to control ductile cutting mechanics. The toughness/strength ratio of a given material will change with rate, temperature, and thermomechanical treatment and the influence of such changes, together with changes in depth of cut, on the character of machining is discussed. Strength or hardness alone is insufficient to describe machining. The failure of the Ernst–Merchant theory seems less to do with problems of uniqueness and the validity of minimum work, and more to do with the problem not being properly posed. The new analysis compares favourably and consistently with the wide body of experimental results available in the literature. Why considerable progress in the understanding of metal cutting has been achieved without reference to significant surface work is also discussed.

Fracture toughness and cutting

An exploratory model for cutting is presented which incorporates fracture toughness as well as the commonly considered effects of plasticity and friction. The periodic load fluctuations Been in cutting force dynamometer tests are predicted, and considerations of chatter and surface finish follow. A non-dimensional group is put forward to classify different regimes of material response to machining. It leads to tentative explanations for the difficulties of cutting materials such as ceramics and brittlo polymers, and also relates to the formation of discontinuous chips. Experiments on a range of solids with widely varying toughness/strength ratios generally agree with the analysis.

Toughness & cutting: A new way of determining ductile fracture toughness and strength

A review is given of the mechanics of cutting, ranging from the slicing of thin floppy offcuts (where there is negligible elasticity and no permanent deformation of the offcut) to the machining of ductile metals (where there is severe permanent distortion of the offcut/chip). Materials scientists employ the former conditions to determine the fracture toughness of ‘soft’ solids such as biological materials and foodstuffs. In contrast, traditional analyses of metalcutting are based on plasticity and friction only, and do not incorporate toughness. The machining theories are inadequate in a number of ways but a recent paper has shown that when ductile work of fracture is included many, if not all, of the shortcomings are removed. Support for the new analysis is given by examination of FEM simulations of metalcutting which reveal that a ‘separation criterion’ has to be employed at the tool tip. Some consideration shows that the separation criteria are versions of void-initiation-growth-and-coalescence models employed in ductile fracture mechanics. The new analysis shows that cutting forces for ductile materials depend upon the fracture toughness as well as plasticity and friction, and reveals a simple way of determining both toughness and flow stress from cutting experiments. Examples are given for a wide range of materials including metals, polymers and wood, and comparison is made with the same properties independently determined using conventional testpieces. Because cutting can be steady state, a new way is presented for simultaneously measuring toughness and flow stress at controlled speeds and strain rates.

Cutting, by 'pressing and slicing,' of thin floppy slices of materials illustrated by experiments on cheddar cheese and salami

Why it is easier to cut with even the sharpest knife when 'pressing down and sliding' than when merely 'pressing down alone' is explained. A variety of cases of cutting where the blade and workpiece have different relative motions is analysed and it is shown that the greater the 'slice/push ratio' xi given by ( blade speed parallel to the cutting edge/blade speed perpendicular to the cutting edge), the lower the cutting forces. However, friction limits the reductions attainable at the highest.. The analysis is applied to the geometry of a wheel cutting device (delicatessan slicer) and experiments with a cheddar cheese and a salami using such an instrumented device confirm the general predictions. (C) 2004 Kluwer Academic Publishers.

An investigation into the mechanics of cutting using data from orthogonally cutting Nylon 66

Cutting force data for Nylon 66 has been examined in terms of various different models of cutting. Theory that includes significant work of separation at the tool tip was found to give the best correlation with experimental data over a wide range of rake angles for derived primary shear plane angle. A fracture toughness parameter was used as the measure of the specific work of separation. Variation in toughness with rake angle determined from cutting is postulated to be caused by mixed mode separation at the tool tip. A rule of mixtures using independently determined values of toughness in tension (mode 1) and shear (mode 11) is found to describe well the variation with rake angle. The ratio of modes varies with rake angle and, in turn, with the primary shear plane angle. Previous suggestions that cutting is a means of experimentally determining fracture toughness are now seen to be extended to identify the mode of fracture toughness as well.

Flavonoid supplement improves leg health and reduces fluid retention in pre-menopausal women in a double-blind, placebo-controlled study

Flavonoid extracts derived from plant foods have been shown to benefit certain types of fluid retention. However, no studies have investigated these compounds for use in premenstrual fluid retention, a complaint common among women with otherwise normal menstrual cycles. Therefore, we conducted a double-blind, placebo-controlled, pilot study into the effect of a daily flavonoid extract (Colladeen(R), 320 mg oligomeric procyanidins) on premenstrual fluid retention. Fluid retention was assessed at baseline and throughout 4 menstrual cycles of the intervention using validated questionnaires. Leg girth was also measured at baseline and at the end of the study. Thirty subjects completed the study (n = 18 active treatment; n = 12 placebo). Although no significant changes in leg girth measurements were noted, there was a significant improvement in subjective "leg health" scores after flavonoid treatment compared to placebo (p = 0.013). Furthermore, this was accompanied by an improvement in reported premenstrual fluid retention nearing significance (p = 0.066). We conclude that flavonoids supplements may provide a new therapeutic direction to counter premenstrual fluid retention and improve leg health. A larger study is now warranted.

Age and flexible thinking: an experimental demonstration of the beneficial effects of increased cognitively stimulating activity on fluid intelligence in healthy older adults

The disuse hypothesis of cognitive aging attributes decrements in fluid intelligence in older adults to reduced cognitively stimulating activity. This study experimentally tested the hypothesis that a period of increased mentally stimulating activities thus would enhance older adults' fluid intelligence performance. Participants (N = 44, mean age 67.82) were administered pre- and post-test measures, including the fluid intelligence measure, Cattell's Culture Fair (CCF) test. Experimental participants engaged in diverse, novel, mentally stimulating activities for 10-12 weeks and were compared to a control condition. Results supported the hypothesis; the experimental group showed greater pre- to post-CCF gain than did controls (effect size d = 0.56), with a similar gain on a spatial-perceptual task (WAIS-R Blocks). Even brief periods of increased cognitive stimulation can improve older adults' problem solving and flexible thinking.

Droplets of structured fluid on a flat substrate

We study the equilibrium morphology of droplets of symmetric AB diblock copolymer on a flat substrate. Using self-consistent field theory (SCFT), we provide the first predictions for the equilibrium droplet shape and its internal structure. When the sustrate affinity for the A component, $\eta_A$, is small, the droplet adopts a nearly spherical shape much like that of simple fluids. Inside the spherical droplet, however, concentric circular lamellar layers stack on top of each other; hence the thickness of the droplet is effectively quantized by a half-integer or integer number of layers. At larger $\eta_A$ and smaller contact angle, the area of the upper-most layer becomes relatively large, resulting in a nearly flat, faceted top surface, followed by a semi-spherical slope. This geometry is remarkably reminiscent of the droplet shapes observed with smetic liquid crystals.

A simple fluid cell for the study of aqueous solutions using THz time-domain spectroscopy

We describe a fluid cell for the measurement of aqueous solutions of biomolecules adapted particularly for the requirements of THz time-domain spectroscopy. The design is simple, requires small-volume samples, avoids cross-contamination and is inexpensive.