Condensation pressures in small pores: An analytical model based on density functional theory

Adsorption and condensation are critical to many applications of porous materials including filtration, separation, and the storage of gases. Integral methods are used to derive an analytical expression describing fluid condensation pressures in slit pores bounded by parallel plane walls. To obtain this result, the governing equations of Density Functional Theory (DFT) are integrated across the pore width assuming that fluid densities within adsorbed layers are spatially uniform. The thickness, density, and energy of these layers are expressed as composite functions constructed from asymptotic limits applicable to small and large pores. By equating the total energy of the adsorbed layers to that of a liquid-full pore, the authors arrive at a closed-form expression for the condensation pressure in terms of the pore size, surface tension, and Lennard-Jones parameters of the adsorbent and adsorbate molecules. The resulting equation reduces to the Kelvin equation in the large-pore limit. It further reproduces the condensation pressures computed by means of the full DFT equations for all pore sizes in which phase transitions are abrupt. Finally, in the limit of extremely small pores, for which phase transitions may be smooth and continuous, this simple analytical expression provides a good approximation to the apparent condensation pressure indicated by the steepest portion of the adsorption isotherm computed via DFT

Fundamental limitations of LIGA x-ray lithography : sidewall offset, slope and minimum feature size.

Analytical and numerical methods are used to examine photoelectron doses and their effect on the dimensions of features produced by deep x-ray lithography. New analytical models describing electron doses are presented and used to compute dose distributions for several feature geometries. The history of development and final feature dimensions are also computed, taking into account the dose field, dissolution kinetics based on measured development rates, and the transport of PMMA fragments away from the dissolution front. We find that sidewall offsets, sidewall slope and producible feature sizes all exhibit at least practical minima and that these minima represent fundamental limitations of the LIGA process. The minimum values under optimum conditions are insensitive to the synchrotron spectrum, but depend strongly on resist thickness. This dependence on thickness is well approximated by simple analytical expressions describing the minimum offset, minimum sidewall slope, minimum producible size of positive and negative features, maximum aspect ratio and minimum radius of inside and outside corners

Experimental device for measuring the momentum of disperse granular materials

An experimental device for measuring the time averaged momentum associated with a steady stream of a disperse granular material has been developed. The mathematical basis for the device is presented including a discussion of using the momentum measurement to compute the local mass or energy fluxes. The analysis considers both nonuniform particle mass and nonuniform velocities for the various constituents of an aggregate material. The results of calibration experiments conducted with a prototype transducer are shown with theoretical predictions of these results

Dimensional errors in LIGA-produced metal structures due to thermal expansion and swelling of PMMA.

Numerical methods are used to examine dimensional errors in metal structures microfabricated by the LIGA process. These errors result from elastic displacements of the PMMA mold during electrodeposition and arise from thermal expansion of the PMMA when electroforming is performed at elevated temperatures and from PMMA swelling due to absorption of water from aqueous electrolytes. Both numerical solutions and simple analytical approximations describing PMMA displacements for idealized linear and axisymmetric geometries are presented and discussed. We find that such displacements result in tapered metal structures having sidewall slopes up to 14 {micro}m per millimeter of height for linear structures bounded by large areas of PMMA. Tapers for curved structures are of similar magnitude, but these structures are additionally skewed from the vertical. Potential remedies for reducing dimensional errors are also discussed. Here we find that auxiliary moat-like features patterned into the PMMA surrounding mold cavities can reduce taper by an order of magnitude or more. Such moats dramatically reduce tapers for all structures, but increase skew for curved structures when the radius of curvature is comparable to the structure height

Analytical models for high-temperature corrosion of silica refractories in glass-melting furnaces

Corrosion of refractory silica brick used to line the crown of many glass-melting furnaces is a serious problem in furnaces using oxygen-fuel rather than air-fuel mixtures. To better understand and to quantify this process analytical models are utilized to evaluate the importance of four potential rate-limiting processes: a) gas-phase transport of NaOH to the crown surface; b) diffusion of sodium-containing reactants through a liquid product layer that forms on the brick face; c) gas-phase diffusion of NaOH into refractory pores; and d) chemical-kinetic limitations at the silica grain surface. Predictions are compared with reported corrosion rates and product compositions previously determined by post-mortem analysis of refractory samples. It is concluded that corrosion occurs largely by reaction and removal of material from the exposed brick face, rather than by transport of reactants into the porous bricks. The observed presence of corrosion products deep within the brick pores is shown to be consistent with capillary suction of high-viscosity liquid products from the hot face into the interior. The results further suggest that mechanisms (b) and (c) do not substantially limit the rate of corrosion, but that mechanisms (a) and (d) may both be important. Comparison of measurements with equilibrium predictions of corrosion-product composition indicate that the corrosion reactions are likely to be close to equilibrium at the conditions and lifetimes typical of full-scale furnaces, but that significant departures from equilibrium may occur in short-duration tests. Although computed corrosion rates based on mass transport through a gas boundary layer are somewhat greater than those observed, the results are very sensitive to the gas-phase concentration of NaOH and to the refractory temperature, both of which contain significant uncertainties

HIGH EXPRESSION OF OSMOTICALLY RESPONSIVE GENES1 Is Required for Circadian Periodicity through the Promotion of Nucleo-Cytoplasmic mRNA Export in Arabidopsis.

notes: PMCID: PMC3875725This is an open access article that is freely available in ORE or from the publisher's web site. Please cite the published version. © 2013 American Society of Plant Biologists. All rights reserved.Cold acclimation has been shown to be attenuated by the degradation of the INDUCER OF CBF EXPRESSION1 protein by the E3 ubiquitin ligase HIGH EXPRESSION OF OSMOTICALLY RESPONSIVE GENES1 (HOS1). However, recent work has suggested that HOS1 may have a wider range of roles in plants than previously appreciated. Here, we show that hos1 mutants are affected in circadian clock function, exhibiting a long-period phenotype in a wide range of temperature and light environments. We demonstrate that hos1 mutants accumulate polyadenylated mRNA in the nucleus and that the circadian defect in hos1 is shared by multiple mutants with aberrant mRNA export, but not in a mutant attenuated in nucleo-cytoplasmic transport of microRNAs. As revealed by RNA sequencing, hos1 exhibits gross changes to the transcriptome with genes in multiple functional categories being affected. In addition, we show that hos1 and other previously described mutants with altered mRNA export affect cold signaling in a similar manner. Our data support a model in which altered mRNA export is important for the manifestation of hos1 circadian clock defects and suggest that HOS1 may indirectly affect cold signaling through disruption of the circadian clock.Biotechnology and Biological Science Research Counci

Measuring health-related quality of life in chronic headache: A comparative evaluation of the Chronic Headache Quality of Life Questionnaire and Headache Impact Test (HIT-6).

OBJECTIVE: To compare the quality and acceptability of a new headache-specific patient-reported measure, the Chronic Headache Quality of Life Questionnaire (CHQLQ) with the six-item Headache Impact Test (HIT-6), in people meeting an epidemiological definition of chronic headaches. METHODS: Participants in the feasibility stage of the Chronic Headache Education and Self-management Study (CHESS) (n = 130) completed measures three times during a 12-week prospective cohort study. Data quality, measurement acceptability, reliability, validity, responsiveness to change, and score interpretation were determined. Semi-structured cognitive interviews explored measurement relevance, acceptability, clarity, and comprehensiveness. RESULTS: Both measures were well completed with few missing items. The CHQLQ's inclusion of emotional wellbeing items increased its relevance to participant's experience of chronic headache. End effects were present at item level only for both measures. Structural assessment supported the three and one-factor solutions of the CHQLQ and HIT-6, respectively. Both the CHQLQ (range 0.87 to 0.94) and HIT-6 (0.90) were internally consistent, with acceptable temporal stability over 2 weeks (CHQLQ range 0.74 to 0.80; HIT-6 0.86). Both measures responded to change in headache-specific health at 12 weeks (CHQLQ smallest detectable change (improvement) range 3 to 5; HIT-6 2.1). CONCLUSIONS: While both measures are structurally valid, internally consistent, temporally stable, and responsive to change, the CHQLQ has greater relevance to the patient experience of chronic headache.Trial registration number: ISRCTN79708100. Registered 16th December 2015, http://www.isrctn.com/ISRCTN79708100

Measuring health-related quality of life in chronic headache:a comparative evaluation of the Chronic Headache Quality of Life Questionnaire and Headache Impact Test (HIT-6)

Objective: To compare the quality and acceptability of a new headache-specific patient-reported measure the Chronic Headache Quality of Life Questionnaire (CHQLQ), with the Headache Impact Test–6 item (HIT-6), in people meeting an epidemiological definition of chronic headaches.Methods: Participants in the feasibility stage of the Chronic Headache Education and Self-management Study (CHESS) (N=130) completed measures three times during a 12-week prospective cohort study. Data quality, measurement acceptability, reliability, validity, responsiveness to change, and score interpretation were determined. Semi-structured cognitive interviews explored measurement relevance, acceptability, clarity, and comprehensiveness.Results: Both measures were well completed with few missing items. The CHQLQ’s inclusion of emotional wellbeing items increased its relevance to participant’s experience of chronic headache. End effects were present at item level only for both measures. Structural assessment supported the three and one-factor solutions of the CHQLQ and HIT-6, respectively. Both the CHQLQ (range 0.87 to 0.94) and HIT-6 (0.90) were internally consistent, with acceptable temporal stability over 2-weeks (CHQLQ range 0.74 to 0.80; HIT-6 0.86). Both measures responded to change in headache-specific health at 12-weeks (CHQLQ smallest detectable change (improvement) range 3 to 5; HIT-6 2.1). Conclusions: While both measures are structurally valid, internally consistent, temporally stable and responsive to change, the CHQLQ has greater relevance to the patient experience of chronic headache. <br/