Experimental and theoretical investigations of adsorption hysteresis and criticality in MCM-41: Studies with O-2, Ar, and CO2

MCM-41 materials of six different pore diameters were prepared and characterized using X-ray diffraction, transmission electron microscopy, helium pycnometry, small-angle neutron scattering, and gas adsorption (argon at 77.4 and 87.4 K, nitrogen and oxygen at 77.4 K, and carbon dioxide at 194.6 K). A recent molecular continuum model of the authors, previously used for adsorption of nitrogen at 77.4 K, was applied here for adsorption of argon, oxygen, and carbon dioxide. While model predictions of single-pore adsorption isotherms for argon and oxygen are in satisfactory agreement with experimental data, significant deviation was found for carbon dioxide, most likely due to its high quadrupole moment. Predictions of critical pore diameter, below which reversible condensation occurs: were possible by the model and found to be consistent with experimental estimates, for the adsorption of the various gases. On the other hand, existing models such as the Barrett-Joyner-Halenda (BJH), Saito-Foley, and Dubinin-Astakhov models were found to be inadequate, either predicting an incorrect pore diameter or not correlating the isotherms adequately. The wall structure of MCM-41 appears to be close to that of amorphous silica, as inferred from our skeletal density measurements.

Thermal diffusion in molecular dynamics simulations of thin film diamond deposition

Molecular dynamics simulations of carbon atom depositions are used to investigate energy diffusion from the impact zone. A modified Stillinger-Weber potential models the carbon interactions for both sp2 and sp3 bonding. Simulations were performed on 50 eV carbon atom depositions onto the (111) surface of a 3.8 x 3.4 x 1.0 nm diamond slab containing 2816 atoms in 11 layers of 256 atoms each. The bottom layer was thermostated to 300 K. At every 100th simulation time step (27 fs), the average local kinetic energy, and hence local temperature, is calculated. To do this the substrate is divided into a set of 15 concentric hemispherical zones, each of thickness one atomic diameter (0.14 nm) and centered on the impact point. A 50-eV incident atom heats the local impact zone above 10 000 K. After the initial large transient (200 fs) the impact zone has cooled below 3000 K, then near 1000 K by 1 ps. Thereafter the temperature profile decays approximately as described by diffusion theory, perturbed by atomic scale fluctuations. A continuum model of classical energy transfer is provided by the traditional thermal diffusion equation. The results show that continuum diffusion theory describes well energy diffusion in low energy atomic deposition processes, at distance and time scales larger than 1.5 nm and 1-2 ps, beyond which the energy decays essentially exponentially. (C) 1998 Published by Elsevier Science S.A. All rights reserved.

A relative gradient theory for layered materials

It is possible to remedy certain difficulties with the description of short wave length phenomena and interfacial slip in standard models of a laminated material by considering the bending stiffness of the layers. If the couple or moment stresses are assumed to be proportional to the relative deformation gradient, then the bending effect disappears for vanishing interface slip, and the model correctly reduces to an isotropic standard continuum. In earlier Cosserat-type models this was not the case. Laminated materials of the kind considered here occur naturally as layered rock, or at a different scale, in synthetic layered materials and composites. Similarities to the situation in regular dislocation structures with couple stresses, also make these ideas relevant to single slip in crystalline materials. Application of the theory to a one-dimensional model for layered beams demonstrates agreement with exact results at the extremes of zero and infinite interface stiffness. Moreover, comparison with finite element calculations confirm the accuracy of the prediction for intermediate interfacial stiffness.

Red Parkes quasars: Evidence for soft X-ray absorption

The Parkes Half-Jansky Flat-Spectrum Sample contains a large number of sources with unusually red optical-to-near-infrared (NIR) continua. If this is to be interpreted as extinction by dust in the line of sight, then associated material might also give rise to absorption in the soft X-ray regime. This hypothesis is tested using broadband (0.1-2.4 keV) data from the ROSAT All-Sky Survey. Significant (>3 sigma confidence level) correlations between the optical (and NIR)-to-soft X-ray continuum slope and optical extinction are found in the data, consistent with absorption by material with metallicity and a range in the gas-to-dust ratio as observed in the local ISM. Under this simple model, the soft X-rays are absorbed at a level consistent with the range of extinctions (0 < A(V) < 6 mag) implied by the observed optical reddening. Excess X-ray absorption by warm (ionized) gas, (i.e., a warm absorber) is not required by the data.

Self-efficacy for refusal mediated by outcome expectancies in the prediction of alcohol-dependence amongst young adults

The present study examined the relative importance of outcome expectancies and self-efficacy [1] in the prediction of alcohol dependence [2] and alcohol consumption in a sample of young adult drinkers drawn from a milieu previously reported as supportive of risky drinking. In predicting alcohol dependence, outcome expectancies were found to mediate self-efficacy and the same pattern was found for both males and females. This suggests that male and female drinkers may become more similar as they progress along the drinking continuum from risky drinking to dependent drinking. However, in women, in comparison to men, a greater array of expectancies and self-efficacy scales were found to predict heavy drinking, as measured by quantity and frequency. These results suggest that heavy drinking women are particularly at risk of developing drinking related complications and that preventative education needs to take into account gender differences.

Effect of disorder on quantum phase transitions in anisotropic XY spin chains in a transverse field

We present some exact results for the effect of disorder on the critical properties of an anisotropic XY spin chain in a transverse held. The continuum limit of the corresponding fermion model is taken and in various cases results in a Dirac equation with a random mass. Exact analytic techniques can then be used to evaluate the density of states and the localization length. In the presence of disorder the ferromagnetic-paramagnetic or Ising transition of the model is in the same universality class as the random transverse field Ising model solved by Fisher using a real-space renormalization-group decimation technique (RSRGDT). If there is only randomness in the anisotropy of the magnetic exchange then the anisotropy transition (from a ferromagnet in the x direction to a ferromagnet in the y direction) is also in this universality class. However, if there is randomness in the isotropic part of the exchange or in the transverse held then in a nonzero transverse field the anisotropy transition is destroyed by the disorder. We show that in the Griffiths' phase near the Ising transition that the ground-state energy has an essential singularity. The results obtained for the dynamical critical exponent, typical correlation length, and for the temperature dependence of the specific heat near the Ising transition agree with the results of the RSRODT and numerical work. [S0163-1829(99)07125-8].

The ocular morphology of the southern hemisphere lamprey Geotria australis gray with special reference to optical specialisations and the characterisation and phylogeny of photoreceptor types

This paper describes the ocular morphology of young adults of the southern hemisphere lamprey Geotria australis, the sole representative of the Geotriidae, and makes comparisons with those of holarctic lampreys (Petromyzontidae). As previously reported for the holarctic lamprey Ichthyomyzon unicuspis [Collin and Fritzsch, 1993], the lens of G. australis is non-spherical and possesses a cone-shaped posterior that may be capable of mediating variable focus. The avascular retina of G. australis is well differentiated, containing three retinal ganglion cell populations, three layers of horizontal cells and three photoreceptor types, in contrast to petromyzontids that contain only two photoreceptor types (short and long), G. australis possesses one rod-like (R1) and two cone-like (C1 and C2) photoreceptors. Although the rodlike receptor in G. australis may be homologous with the short receptors of holarctic lampreys, the two cone-like receptors have morphological characteristics that differ markedly from those of the long receptors of their holarctic counterparts. The features which distinguish the two cone-like receptors from those of the long receptor type in holarctic lampreys are the characteristics of the mitochondria and the presence of large amounts of two different types of stored secretory material in the endoplasmic reticulum of the myoid (refractile bodies). The endoplasmic reticulum of each receptor type has a different shape and staining profile and is polymorphic, each showing a continuum of distension. It is proposed that the presence of two cone-like photoreceptors with different characteristics would increase the spectral range of G. australis and thus be of value during the parasitic phase, when this lamprey lives in the surface marine waters. The irideal flap, present in G. australis but not petromyzontids, would assist in reducing intraocular flare during life in surface waters. The results of this study, which are discussed in the context of the proposed evolution of lampreys, emphasise that it is important to take into account the characteristics of the eyes of southern hemisphere lampreys when making generalizations about the eyes of lampreys as a whole.

Endorsement of CIDI psychosis screening items in the Australian Survey of Mental Health and Well being

This paper presents preliminary analysis of the endorsement of the CIDI Psychosis Screening items in a large Australian community sample. CIDI interviews were completed on a representative sample of 10,641 individuals living in private dwellings in Australia. The items examined constructs related to thought control/interference (G1), ideas of reference (G2), and special powers (G3). If endorsed, each item had a follow-up probe (G1A telepathy; G2A things arranged with special meaning; G3A -- group acceptability). The final item (G4) asked if the respondent had been told that they had schizophrenia. This paper presents the frequency of endorsement, and examines the impact of age and sex on these items. Endorsement of the items was G1 =5.86°/,,, G1A=0.70%, G2=4.84%, G2A=l.31%, G3=3.41%, G3A=2.65%, and G4=0.65%. If screen-positives are defined as two or more 'hits', then 0.41% of the sample met this criterion. Younger participants were significantly more likely to be screen-positive. Items G1, G1A, G2 and G2A were endorsed more frequently by younger participants while there were no significant age effects identified in items G3 or G4. There was a nonsignificant trend for females to endorse item G1 more frequently than males (p = 0.07), but there were no signficant gender differences on the other items. Many individuals who were 'screen-negative' for psychosis endorsed CIDI items related to thought controls, ideas of reference and special powers, suggesting that there may be a 'continuum' of experiences in the population. The impact of age on the distribution of these measures suggests either differential biological vulnerability to these experiences and/or differential cultural factors influencing endorsement of the items. The implications of these findings on our understanding of the symptoms of psychosis will be discussed. The survey was funded by the Commonwealth Dept. of Health and Family Services. The Stanley Foundation supported this project.

A model for adsorption of condensable vapors on nonporous materials

A new isotherm is proposed here for adsorption of condensable vapors and gases on nonporous materials having type II isotherms according to the Brunauer-Deming-Deming-Teller (BDDH) classification. The isotherm combines the recent molecular-continuum model in the multilayer region, with other widely used models for sub-monolayer coverage, some of which satisfy the requirement of a Henry's law asymptote. The model is successfully tested using isotherm data for nitrogen adsorption on nonporous silica, carbon and alumina, as well as benzene and hexane adsorption on nonporous carbon. Based on the data fits, out of several different alternative choices of model for the monolayer region, the Freundlich and the Unilan models are found to be the most successful when combined with the multilayer model to predict the whole isotherm. The hybrid model is consequently applicable over a wide pressure range. (C) 2000 Elsevier Science B.V. All rights reserved.

Characterization of pore size distributions of mesoporous materials from adsorption isotherms

In this article, a new hybrid model for estimating the pore size distribution of micro- and mesoporous materials is developed, and tested with the adsorption data of nitrogen, oxygen, and argon on ordered mesoporous materials reported in the literature. For the micropore region, the model uses the Dubinin-Rudushkevich (DR) isotherm with the Chen-Yang modification. A recent isotherm model of the authors for nonporous materials, which uses a continuum-mechanical model for the multilayer region and the Unilan model for the submonolayer region, has been extended for adsorption in mesopores. The experimental data is inverted using regularization to obtain the pore size distribution. The present model was found to be successful in predicting the pore size distribution of pure as well as binary physical mixtures of MCM-41 synthesized with different templates, with results in agreement with those from the XRD method and nonlocal density functional theory. It was found that various other recent methods, as well as the classical Broekhoff and de Beer method, underpredict the pore diameter of MCM-41. The present model has been successfully applied to MCM-48, SBA's, CMK, KIT, HMS, FSM, MTS, mesoporous fly ash, and a large number of other regular mesoporous materials.

Initial results of ultrasound screening for aneurysm of the abdominal aorta in Western Australia: relevance for endoluminal treatment of aneurysm disease

Background. Increased life expectancy in men during the last thirty years is largely due to the decrease in mortality from cardiovascular disease in the age group 29-69 yr. This change has resulted in a change in the disease profile of the population with conditions such as aneurysm of the abdominal aorta (AAA) becoming more prevalent. The advent of endoluminal treatment for AAA has encouraged prophylactic intervention and fuelled the argument to screen for the disease. The feasibility of inserting an endoluminal graft is dependent on the morphology and growth characteristics of the aneurysm. This study used data from a randomized controlled trial of ultrasound screening for AAA in men aged 65-83 yr in Western Australia for the purpose of determining the norms of the living anatomy in the pressurized infrarenal aorta. Aims. To examine (1) the diameters of the infra-renal aorta in aneurysmal and non-aneurysmal cases, (2) the implications for treatment modalities, with particular reference to endoluminal grafting, which is most dependent on normal and aneurysmal morphology, and (3) any evidence to support the notion that northern Europeans are predisposed to aneurysmal disease. Methods. Using ultrasound, a randomized control trial was established in Western Australia to assess the value of a screening program in males aged 65-83 yr, The infra-renal aorta was defined as aneurysmal if the maximum diameter was 30 mm or more. Aortic diameter was modelled both as a continuous tin mm) and as a binary outcome variable, for those men who had an infra-renal diameter of 30 mm or more. ANOVA and linear regression were used for modelling aortic diameter as a continuum, while chi-square analysis and logistic regression were used in comparing men with and without the diagnosis of AAA. Findings. By December 1998, of 19.583 men had been invited to undergo ultrasound screening for AAA, 12.203 accepted the invitation (corrected response fraction 70.8%). The prevalence of AAA increased with age from 4.8% at 65 yr to 10.8% at 80 yr (chi (2) = 77.9, df = 3, P<0.001). The median (IQR) diameter for the non-aneurysmal group was 21.4 mm (3.3 mm) and there was an increase (<chi>(2) = 76.0, df = 1, P<0.001) in the diameter of the infra-renal aorta with age. Since 27 mm is the 95th centile for the non-aneurysmal infra-renal aorta, a diameter of 30 mm or more is justified as defining an aneurysm. The risk of AAA was higher in men of Australian (OR = 1.0) and northern European origin (OR = 1.0, 95%CL: 0.9. 1.2) compared with those of Mediterranean origin (OR = 0.5, 99%CL: 0.4, 0.7). Conclusion. Although screening has not yet been shown to reduce mortality from AAA. these population-based data assist the understanding of aneurysmal disease and the further development and use of endoluminal grafts for this condition. (C) 2001 Published by Elsevier Science Ltd on behalf of The International Society for Cardiovascular Surgery.

Quasars from a complete spectroscopic survey

With the advent of multi-fibre spectrographs such as the 'Two-Degree Field' (2dF) instrument at the Angle-Australian Telescope, quasar surveys that are free of any preselection of candidates and any biases this implies have become possible for the first time. The first of these is that which is being undertaken as part of the Fornax Spectroscopic Survey, a survey of the area around the Fornax Cluster of galaxies, and aims to obtain the spectra of all objects in the magnitude range 16.5 < b(j) < 19.7. To date, 3679 objects in the central pi -deg(2) area have been successfully identified from their spectral characteristics. Of these, 71 are found to be quasars, 61 with redshifts 0.3 < z < 2.2 and 10 with redshifts z > 2.2. Using this complete quasar sample, a new determination of quasar number counts is made, enabling an independent check of existing quasars surveys. Cumulative counts per square degree at a magnitude limit of b(j) < 19.5 are found to be 11.5 +/- 2.2 for 0.3 < z < 2.2, 2.22 +/- 0.93 for z > 2.2 and 13.7 +/- 3.1 for z > 0.3. Given the likely detection of extra quasars in the Fornax survey, we make a more detailed examination of existing quasar selection techniques. First, looking at the use of a stellar criterion, four of the 71 quasars are 'non-stellar' on the basis of the automated plate measuring facility (APM) b(j) classification, however inspection shows all are consistent with stellar, but misclassified due to image confusion. Examining the ultraviolet excess and multicolour selection techniques, for the selection criteria investigated, ultraviolet excess would find 69 +/- 6 per cent of our 0.3 < z < 2.2 quasars and only 50(-18)(+14), per cent of our z > 2.2 quasars, while the completeness level for multicolour selection is found to be 90(-4)(+3) per cent for 0.3 < z < 2.2 quasars and 80(-12)(+14) per cent for z > 2.2 quasars. The extra quasars detected by our all-object survey thus have unusually red star-like colours, and this appears to be a result of the continuum shape rather than any emission features. An intrinsic dust extinction model may, at least partly, account for the red colours.

Energy and averages in the mechanics of granular materials

We derive a general thermo-mechanical theory for particulate materials consisting of granules of arbitrary whose material points possess three translational and three independent rotational degrees of freedom. Additional field variables are the translational and rotational granular temperatures, the kinetic energies shape and size. The kinematics of granulate is described within the framework of a polar continuum theory of the velocity and spin fluctuations respectively and the usual thermodynamic temperature. We distinguish between averages over particle categories (averages in mass/velocity and moment of inertia/spin space, respectively) and particle phases where the average extends over distinct subsets of particle categories (multi phase flows). The relationship between the thermal energy in the granular system and phonon energy in a molecular system is briefly discussed in the main body of the paper and discussed in detail in the Appendix A. (C) 2001 Elsevier Science B.V. All rights reserved.

A numerical study of flexural buckling of foliated rock slopes

The occurrence of foliated rock masses is common in mining environment. Methods employing continuum approximation in describing the deformation of such rock masses possess a clear advantage over methods where each rock layer and each inter-layer interface (joint) is explicitly modelled. In devising such a continuum model it is imperative that moment (couple) stresses and internal rotations associated with the bending of the rock layers be properly incorporated in the model formulation. Such an approach will lead to a Cosserat-type theory. In the present model, the behaviour of the intact rock layer is assumed to be linearly elastic and the joints are assumed to be elastic-perfectly plastic. Condition of slip at the interfaces are determined by a Mohr-Coulomb criterion with tension cut off at zero normal stress. The theory is valid for large deformations. The model is incorporated into the finite element program AFENA and validated against an analytical solution of elementary buckling problems of a layered medium under gravity loading. A design chart suitable for assessing the stability of slopes in foliated rock masses against flexural buckling failure has been developed. The design chart is easy to use and provides a quick estimate of critical loading factors for slopes in foliated rock masses. It is shown that the model based on Euler's buckling theory as proposed by Cavers (Rock Mechanics and Rock Engineering 1981; 14:87-104) substantially overestimates the critical heights for a vertical slope and underestimates the same for sub-vertical slopes. Copyright (C) 2001 John Wiley & Sons, Ltd.

The spectra of red quasars

We measure the spectral properties of a representative sub-sample of 187 quasars, drawn from the Parkes Half-Jansky, Flat-radio-spectrum Sample (PHFS). Quasars with a wide range of rest-frame optical/UV continuum slopes are included in the analysis: their colours range over 2 < B-K < 7. We present composite spectra of red and blue sub-samples of the PHFS quasars. and tabulate their emission line properties. The median Hbeta and [0 111] emission line equivalent widths of the red quasar sub-sample are a factor of ten weaker than those of the blue quasar sub-sample. No significant differences are seen between the equivalent width distributions of the C IV, C III] and Mg 11 lines. Both the colours and the emission line equivalent widths of the red quasars can be explained by the addition of a featureless red synchrotron continuum component to an otherwise normal blue quasar spectrum. The red synchrotron component must have a spectrum at least as red as a power-law of the form F-nu proportional to nu(-2.8). The relative strengths of the blue and red components span two orders of magnitude at rest-frame 500 nm. The blue component is weaker relative to the red component in low optical luminosity sources. This suggests that the fraction of accretion energy going into optical emission from the jet is greater in low luminosity quasars. This correlation between colour and luminosity may be of use in cosmological distance scale work. This synchrotron model does not, however, fit similar to10% of the quasars, which have both red colours and high equivalent width emission lines. We hypothesise that these red, strong-lined quasars have intrinsically weak Big Blue Bumps. There is no discontinuity in spectral properties between the BL Lac objects in our sample and the other quasars. BL Lac objects appear to be the red, low equivalent width tail of a continuous distribution. The synchrotron emission component only dominates the spectrum at longer wavelengths, so existing BL Lac surveys will be biased against high redshift objects. This will affect measurements of BL Lac evolution. The blue PHFS quasars have significantly higher equivalent width C IV, Hbeta and [0 111] emission than a matched sample of optically selected QSOs.