Stability of underexpanded supersonic jet flames burning H2-CO mixtures

It has been established experimentally that both natural gas and hydrogen discharges, through circular orifices larger than a critical diameter, sustain stable lifted flames irrespective of the reservoir pressure driving the release. At smaller diameters, however, stable burning will only be achieved at operating pressures higher than a particular, diameter-dependent, threshold. This latter is strongly fuel-type dependent but empirical correlations have been developed to describe such behaviour. Given the wide disparity of critical diameters depending upon the fuel type considered, the behaviour of multi-component gaseous mixtures involving hydrogen is much less predictable than the correlations for pure fuels might indicate. A series of experiments has been undertaken in which H₂-CO mixtures are discharged from a high pressure reservoir to ambient through convergent circular nozzles, varying in diameter from 1.3 to 5 mm. A wide range of driving pressures has been investigated, from 3 to 50 bar, embracing fuel mixtures containing up to 20% CO by volume. Stability curves have been derived that identify the region where stable burning is sustained relative to the pressure ratio (reservoir pressure/ambient pressure) and the CO concentration in the fuel mixture. The present experimental data are compared with existing correlations (Kalghatgi 1981), derived from subsonic releases, and Birch et al. (1988a), applied to underexpanded supersonic methane jet flames. Although these correlations reproduce the general trend observed experimentally, they appear to significantly over-estimate the stability region. Furthermore, they do not account for the high sensitivity of the diluent concentration on the blowout stability. A thorough investigation is carried out in order to determine the source of discrepancies observed between the empirical correlations and the present measurements. Differential diffusion between the fuel components is shown to be negligible. The introduction of additional information on the turbulent flowfield from numerical simulation of the isothermal underexpanded jet, immediately upstream of the flame stabilisation region, does not appear to yield discriminating evidence for incipient blow-off instability. The maximum burning velocity alone, a widely employed characterising parameter, does not appear to describe accurately the complex interactions between the turbulent flowfield and the chemical kinetics.     

Enhanced second-harmonic generation in AlGaAs microring resonators

Highly efficient second-harmonic generation can be achieved by harnessing resonance effects in microring resonator structures. We propose an angular quasi-phase-matching scheme based on the position dependence of polarization inside the ring resonator.     

High frequency parallel plate probe for the measurement of the complex viscosity of liquids

In this work an instrument is described which measures the complex shear viscosity of liquids in the kHz frequency range. The instrument is driven electromagnetically and operates in resonant mode. The measurement of the primary data, from which the rheological properties of the fluid sample are inferred, does not include any deflection amplitude measuring step and is purely digital. Models allowing the interpretation of the probe primary data in terms of fluid complex viscosity are presented. The theoretically predicted mechanical behaviour of the probe is compared with the measured one and the rheometric ability of the device is discussed.     

Rheological characterization of well-defined tetrafluoroethylene/hexafluoropropylene copolymers

The rheology of tetrafluoroethylene/hexafluoropropylene (TFE/HFP) copolymers, also known as Teflon FEP polymers, having different molecular weight and composition (HFP content) was studied by means of a parallel-plate rheometer. Two groups of polymers having different molecular weights with nearly constant polydispersity (around 2.5) were considered; namely, one group having a relatively low melting temperature (amorphous with a high content of HFP) and a second group having a higher melting point (semi-crystalline with a lower content of HFP). The relaxation time spectrum, H(λ), calculated by use of the BSW model (developed for monodisperse linear polymers) followed a scaling relationship in the terminal zone with scaling exponent of 0.13. However, at higher frequencies the model fails to predict adequately the experimental data. The longest relaxation time calculated from both the BSW model and discrete relaxation spectra (λ _i ,g _i ), which was determined by use of a parsimonious fitting software, depends on the molecular weight in a similar way as the zero-shear viscosity does with the well-established scaling factor of 3.4. The critical molecular weight for the onset of entanglements, M _c , was found to be about 100000, a value much higher than those previously reported in literature for other polymers. The rheology of resins in the second group (higher melting point) was found to exhibit a strong dependence on thermal history during oscillatory-shear measurements. The data obtained in experiments at different temperatures without a preheating to a certain value (330°C) exhibited a violation of the time-temperature superposition principle and no well-defined values of the zero-shear viscosity. This is attributed to residual crystallinity even at temperatures well above their melting point (260°C). However, the same experiments with preheating and subsequent cooling to desired temperature resulted into a very good time-temperature scaling. Received: 13 January 1998 Accepted: 6 April 1998     

Dynamic theory for smectic A liquid crystals

A dynamic continuum theory is presented for smectic A liquid crystals in which the usual director n and unit layer normal a do not always necessarily coincide. Most previous dynamic continuum theories equate n with a; the theory developed in this article allows n and a to differ in non-equilibrium situations, work that has been motivated by the recent investigations by Auernhammer et al. (Rheol. Acta 39, 215–222, 2000; Phys. Rev. E 66, 061707, 2002) and Soddemann et al. (Eur. Phys. J. E 13, 141–151, 2004). The usual Oseen constraint () for smectics is not imposed upon the unit normal a. Permeation is also included. After a summary of the complete dynamic equations, an application is given via an example which shows that planar aligned layers of smectic A subjected to an arbitrary periodic disturbance are linearly stable.      

Enantioselective Palladium(0)‐Catalyzed Nazarov‐Type Cyclization

A Pd⁰‐catalyzed asymmetric Nazarov‐type cyclization is described. The optimized ligand for the reaction incorporates a weakly coordinating pyridine ring into a TADDOL‐derived phosphoramidite (TADDOL=α,α,α,α‐tetraaryl‐1,3‐dioxolane‐4,5‐dimethanol). The reaction leads to the formation of cyclopentenones as single diastereoisomers that incorporate two contiguous asymmetric centers, one tertiary and one an all‐carbon‐atom quaternary stereocenter, in high yield and optical purity. It is noteworthy that the reaction does not require that substrates should be activated by aryl substituents.     

Survey of UV Emissions from Sunbeds in the UK

Increased use of indoor tanning for cosmetic purposes has led to concerns for its impact on the risk of cutaneous cancers. The effects on UVR on skin depend on radiant dose, i.e. combination of irradiance and exposure duration. While a number of studies surveyed accessible emission from sunbeds, majority did not include the information on doses received during tanning sessions. Spectral irradiance of 195 sunbeds in five areas of the United Kingdom was measured in order to assess the radiant doses for comparison with the SED. Erythema weighted irradiance of more than 85% of all tested solaria exceeded 0.3 W m^?2, consistent with the findings of other studies. However, evaluation of radiant doses showed no evidence of increasing exposure per session in the United Kingdom in the last decade despite the increasing sunbed emission levels. Use of sunbeds for cosmetic purposes should be discouraged, with effective enforcement of the ban on under‐18 use, strict control on tanning duration and promotion of information on health risks of sunbed use. Such an integrated approach on safe equipment, safe use, and information should reduce the risk of detrimental impact of sunbed use on public health.     

Natural underwater adhesives

The general topic of this review is protein‐based underwater adhesives produced by aquatic organisms. The focus is on mechanisms of interfacial adhesion to native surfaces and controlled underwater solidification of natural water‐borne adhesives. Four genera that exemplify the broad range of function, general mechanistic features, and unique adaptations are discussed in detail: blue mussels, acorn barnacles, sandcastle worms, and freshwater caddisfly larva. Aquatic surfaces in nature are charged and in equilibrium with their environment, populated by an electrical double layer of ions as well as adsorbed natural polyelectrolytes and microbial biofilms. Surface adsorption of underwater bioadhesives likely occurs by exchange of surface bound ligands by amino acid sidechains, driven primarily by relative affinities and effective concentrations of polymeric functional groups. Most aquatic organisms exploit modified amino acid sidechains, in particular phosphorylated serines and hydroxylated tyrosines (dopa), with high‐surface affinity that form coordinative surface complexes. After delivery to the surfaces as a fluid, permanent natural adhesives solidify to bear sustained loads. Mussel plaques are assembled in a manner superficially reminiscent of in vitro layer‐by‐layer strategies, with sequentially delivered layers associated through Fe(dopa)₃ coordination bonds. The adhesives of sandcastle worms, caddisfly larva, and barnacles may be delivered in a form somewhat similar to in vitro complex coacervation. Marine adhesives are secreted, or excreted, into seawater that has a significantly higher pH and ionic strength than the internal environment. Empirical evidence suggests these environment triggers could provide minimalistic, fail‐safe timing mechanisms to prevent premature solidification (insolubilization) of the glue within the secretory system, yet allow rapid solidification after secretion. Underwater bioadhesives are further strengthened by secondary covalent curing. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Selective pressurized liquid extraction of estrogenic compounds in soil and analysis by gas chromatography-mass spectrometry

A selective pressurized liquid extraction (SPLE) method, followed by gas chromatography–mass spectrometry (GC–MS), for the simultaneous extraction and clean-up of estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), estriol (E3) and bisphenol A (BPA) from soil samples is described. The on-line clean-up of soil by SPLE was achieved using different organic matter retainers, including silica, alumina and Florisil, the most effective being silica. Thus, different amounts of silica, in conjunction with different extraction solvents (acetone, ethyl acetate, isohexane and dichloromethane), either alone or in combination, were used to extract the target chemicals from spiked soil samples. It was shown that 3 g silica resulted in satisfactory rates of recovery of target compounds and acetone:dichloromethane (1:3, v/v) was efficient in extracting and eluting estrogenic compounds for SPLE. Variables affecting the SPLE efficiency, including temperature and pressure were studied; the optimum parameters were 60 °C and 1500 psi, respectively. The limits of detection (LODs) of the proposed method were 0.02–0.37 ng g⁻¹ for the different estrogenic chemicals studied. The outputs using the proposed method were linear over the range from 0.1 to 120 ng g⁻¹ for E1, E2, EE2, 0.2–120 ng g⁻¹ for E3, and 0.5–120 ng g⁻¹ for BPA. The optimized method was further verified by performing spiking experiments in natural soil matrices; good rates of recovery and reproducibility were achieved for all selected compounds and the method was successfully applied to soil samples from Northeast Scotland, for the determination of the target compounds.