Variation of the specific surface area and porosity of anhydrous zinc oxalate with water vapour pressure

Specific surface areas and pore structure studies were carried out on two sets of samples of anhydrous zinc oxalate prepared from the dihydrate by heating at 130 and 180°C in various atmospheres of differing water vapour pressure. The two sets of samples were freshly prepared and aged samples. The variation of specific surface areas with water vapour pressure was found to behave in accordance with the Smith-Topley effect, with a minimum S_BET value located at 3.0 mmHg of water vapour. Analysis of the nitrogen adsorption isotherms by the t-method revealed the existence of both micropores and mesopores in the freshly prepared samples heated both at 130 and 180°C in 8.0 mmHg water vapour, and also in the aged samples prepared at 130°C in vacuo, and at 180°C in 8.0 mmHg water vapour. The rest of the samples possess only wide pores. Complete pore structure analysis for both micro- and mesopores was carried out for all samples investigated, and an attempt was made to correlate the factors affecting the development of surface area and pore structure, both in the presence and absence of water vapour, with those affecting the dehydration rate, and which occasionally lead to the Smith-Topley effect.     

Hardened slag–cement pastes of various porosities. II. Water and nitrogen adsorption

Specific surface areas and pore structure studies were carried out on hardened slag-cement pastes. Water and nitrogen adsorption isotherms were measured, and the derived parameters were critically compared. Nitrogen areas and total pore volumes were found to be much smaller than water values. For water vapour adsorption, the specific surface areas derived from the adsorption branches are found to be lower than those derived from the resorption isotherms. Some evidence is presented in this paper that the surface area values derived along the adsorption branches are underestimated values, and that the resorption values might be considered to be nearer to the actual areas of the various pastes. Calculations of the hydraulic radii refute the hypothesis that the areas inaccessible to nitrogen are interlayer areas.     

Efficient Policy Analysis for Evolving Administrative Role Based Access Control

Role Based Access Control (RBAC) has been widely used for restricting resource access to only authorized users. Administrative Role Based Access Control (ARBAC) specifies permissions for administrators to change RBAC policies. Due to complex interactions between changes made by different administrators, it is often difficult to comprehend the full effect of ARBAC policies by manual inspection alone. Policy analysis helps administrators detect potential flaws in the policy specification. Prior work on ARBAC policy analysis considers only static ARBAC policies. In practice, ARBAC policies tend to change over time in order to fix design flaws or to cope with the changing requirements of an organization. Changes to ARBAC policies may invalidate security properties that were previously satisfied. In this paper, we present incremental analysis algorithms for evolving ARBAC. Our incremental algorithms determine if a change may affect the analysis result, and if so, use the information of the previous analysis to incrementally update the analysis result. To the best of our knowledge, these are the first known incremental algorithms in literature for ARBAC analysis. Detailed evaluations show that our incremental algorithms outperform the non-incremental algorithm in terms of execution time at a reasonable cost of increased disk space consumption.     

Hardened alite pastes of various porosities. I. Degree of hydration,compressive strength and total porosity

The alite used in this investigation was synthesised from the stoichiometric mixture at 1550°C. The hardened alite pastes were made using initial water/alite ratios of 0.20, 0.30, 0.45 and 0.60. Degree of hydration, compressive strength and total porosity were estimated at various hydration time intervals of 0.5 h, 2 h, 6 h, 1 day, 3 days, 7 days and 28 days. A meaningful relation between compressive strength and water/alite ratio was established at constant values of degree of hydration, total porosity and Powers' gel-space ratio.     

Detoxication of water containing 1,1-dimethylhydrazine by catalytic oxidation with dioxygen and hydrogen peroxide over Cu- and Fe-containing catalysts

A number of Cu- and Fe-hydroxide containing catalysts, supported on oxide carriers, were prepared to provide the removal of 1,1-dimethylhydrazine from aqueous solutions via its oxidation by hydrogen peroxide and air oxygen. The Cu-containing samples as well as Fe/ZSM-5 are the most active catalysts in this reaction. The reaction products were analyzed by gas chromatography and UV–Vis spectroscopy. The effect of nature of the oxidizer and catalyst, pH and temperature on both the reaction rate and product composition was studied.     

Hardened portland blast-furnace slag cement pastes: I. Effects of additives on surface area and on pore structure

Portland blast-furnace slag cement pastes were prepared with various water/cement ratios. Specific surface areas and pore structures of the hardened pastes were investigated by nitrogen adsorption. The “accessibility” of the nitrogen molecules to the pore structure is discussed in terms of degree of hydration and total porosities of the pastes. Effect of presence of CaCl₂, a typical steel reinforcement corrosive agent, was also studied, and results indicated that it alters the area and pore structure extensively, to a more “open structure,” thus facilitating its own accessibility. Lime and gypsum addition was also studied in presence and in absence of CaCl₂, and the effect of the Blaine surface area of the unhydrated cement is particularly emphasized in this investigation.     

Thermal decomposition of zinc oxalate dihydrate: Kinetics of dehydration and pyrolysis in various atmospheres

Thermogravimetric analysis has indicated that a convenient range for the study of Zn(COO)₂.2H₂O dehydration is 120–300 °C, while for pyrolysis it is 320–400 °C. Kinetics of isothermal dehydration and pyrolysis were studied as two consecutive steps in various atmospheres, namely in constant water vapour pressure of 4.8 and 8 mm Hg, in air saturated with water vapour at 25 °C and in vacuo. The kinetic data indicated that dehydration is a pseudo-first order reaction, which is highly dependent on the surrounding atmosphere. The mechanism of dehydration is either activated diffusion (alternatively surface diffusion) for dehydration in vacuo or in low water vapour pressures, or activated desorption for dehydration in presence of high water vapour pressure. On the other hand pyrolysis is independent of the prevailing atmosphere, and the energy of activation is of the order of the enthalpy change of the reaction. Earlier studies have involved contact of the dehydrated oxalate with air, or have obscured the influence of the prevailing atmosphere, by dehydrating the sample material at the pyrolysis temperature. These conditions are considered in the present investigation.     

Fuzzy set analyses of genetic determinants of health and disability status

Analyses of complex genotype-phenotype relations require new statistical procedures because of the potentially high dimensionability of those relations which are expressed with both measurement error and stochasticity in the correlation function. We propose modifying a multivariate procedure called grade of membership (GoM) analysis to deal with the special problems of such analyses. In doing so, we make clear some special features of the GoM model for multivariate analysis of high dimensional, discrete data. This is illustrated for apolipoprotein E (APOE) assessments made on 1805 people in the 1999 National Long Term Care Survey. A number of interesting relations with APOE polymorphism were found where disability profiles were more predictive than specific diagnoses because they implicitly contained information on chronicity and severity of disease processes.     

Electroluminescence of poly(phthalidylidene arylene)s

Electroluminescence of thin films of poly(3,3-phthalidylidene-4,4′-biphenylylene) (PPB) and poly(3,3-phthalidylidene-2,7-fluorenylylene) (PPF) was studied. In both cases, electroluminescene was found to be of a threshold origin. Emission maxima and quantum efficiencies for PPB and PPF are 490 and 525 nm, 0.01 and 0.1%, respectively. The electroluminescent characteristics were found to be strongly dependent on the polymer used.     

Influence of the Structure and Properties OF WC – Co Alloy Powders on the Structure and Wear-Resistance of Detonation Coatings

We have made comparative investigations of the structure, phase composition and abrasive wear resistance of WC – Co coatings sprayed by the detonation method using powders of identical chemical composition and different particle structure, because the powders are prepared by different technologies. The laws we have found that govern how the structure evolves from the initial powder to a coating allow us to predict the physicotechnical properties of the coating. The more porous the powders, the more they are affected by the gas atmosphere in the spraying process and thus, the more significant changes in the phase composition are observed in the powder – coating system. The use of powders with highly porous particles results in the formation of porous coatings with low wear resistance.