Effects of Al:Si and (Al + Na):Si ratios on the properties of the international simple glass,part II: Structure

High-alumina containing high-level waste (HLW) will be vitrified at the Waste Treatment Plant at the Hanford Site. The resulting glasses, high in alumina, will have distinct composition-structure-property (C-S-P) relationships compared to previously studied HLW glasses. These C-S-P relationships determine the processability and product durability of glasses and therefore must be understood. The main purpose of this study is to understand the detailed structural changes caused by Al:Si and (Al + Na):Si substitutions in a simplified nuclear waste model glass (ISG, international simple glass) by combining experimental structural characterizations and molecular dynamics (MD) simulations. The structures of these two series of glasses were characterized by neutron total scattering and ²⁷Al, ²³Na, ²⁹Si, and ¹¹B solid-state nuclear magnetic resonance (NMR) spectroscopy. Additionally, MD simulations were used to generate atomistic structural models of the borosilicate glasses and simulation results were validated by the experimental structural data. Short-range (eg, bond distance, coordination number, etc) and medium-range (eg, oxygen speciation, network connectivity, polyhedral linkages) structural features of the borosilicate glasses were systematically investigated as a function of the degree of substitution. The results show that bond distance and coordination number of the cation-oxygen pairs are relatively insensitive to Al:Si and (Al + Na):Si substitutions with the exception of the B-O pair. Additionally, the Al:Si substitution results in an increase in tri-bridging oxygen species, whereas (Al + Na):Si substitution creates nonbridging oxygen species. Charge compensator preferences were found for Si-[NBO] (Na⁺), ^[3]B-[NBO] (Na⁺), ^[4]B (mostly Ca²⁺), ^[4]Al (nearly equally split Na⁺ and Ca²⁺), and ^[6]Zr (mostly Ca²⁺). The network former-BO-network former linkages preferences were also tabulated; Si-O-Al and Al-O-Al were preferred at the expense of lower Si-O-^[3]B and ^[3]B-O-^[3]B linkages. These results provide insights on the structural origins of property changes such as glass-transition temperature caused by the substitutions, providing a basis for future improvements of theoretical and computer simulation models.     

Effect of phosphate rock and triple superphosphate on soil phosphorus fractions and their plant-availability and downward movement in two volcanic ash soils under <Emphasis Type="Italic">Pinus radiata</Emphasis> plantations in New Zealand

Changes in phosphorus (P) fractions and their plant-availability and downward movement in two strongly P fixing acidic Andosols (Allophanic and Pumice Soils) under Pinus radiata plantations in New Zealand were studied 2 years after triple superphosphate (TSP) and a phosphate rock (BGPR, origin Ben Guerir, Morocco) application, each at four rates, to determine the fate and plant availability of fertilizer-derived P in these soils. The rate of increase of the concentrations of the P fractions was highest for NaOH-P_i (inorganic P associated with Fe and Al oxides and allophane) when TSP was applied and highest for H₂SO₄-P_i (predominantly calcium phosphates or apatite-type P minerals) when BGPR was applied. The largest pool of soil P, the NaOH-P_o (labile organic P), was unaffected by the P fertilizer applications. The rate of NaOH-P_i concentration increase was higher in the higher P fixing Allophanic Soil than in the Pumice Soil. Both types of fertilizers increased resin-P_i (Inorganic P freely available to the plant) and Bray-2 P concentrations but only the TSP application increased Olsen P concentration. Phosphorus derived from TSP and BGPR applications moved down to 10–20 cm soil depth within 2 years of application in the Pumice Soil, but did not move below 10 cm depth in the higher P fixing and less porous Allophanic Soil. The fertilizers significantly increased needle P concentrations 2, 3 and 4 years after fertilizer application, but did not have any significant effect on tree growth.     

Adsorption of hydrocarbons by ZSM-5 zeolites with different SiO2/Al2O3 ratios: a combined FTIR and gravimetric study

In metal-free ZSM-5, the decrease in the concentration of Bronsted and Lewis acid sites parallels the increase in the SiO₂/Al₂O₃ ratio. In the presence of residual moisture, the adsorption of small alkanes does not markedly depend on the SiO₂/Al₂O₃ ratio in the range from 30 to 150. The acidity is more important for the adsorption of alkenes (propene) which oligomerize following adsorption. The addition of 5 wt.% of La does not significantly affect the strength of the surface acid sites but does decrease their concentration. It causes a transformation, in a part, of the Bronsted acid sites. These new centers could perhaps be assigned to LaO(OH) or La(OH)₂⁺ species which may be formed on the surface in La-containing ZSM-5. La could exchange only the strongest acidic sites without inducing large changes in their total concentration. La addition has a very small effect on the adsorption of small hydrocarbons. The exchange of the protons by Cu²⁺ decreases the concentration of Bronsted acid sites. At a sufficient loading of the ZSM-5 by Cu²⁺, i.e. at an atomic ratio Cu/Al > 1.0, the exchange can almost totally suppress the Bronsted acidity. Another effect of the ion exchange is the suppression of the adsorption capacity of small hydrocarbons due to lowered surface area and internal pore volume. The lowered available internal pore volume also limits the extent of the oligomerization of propene.     

A comparison between the finite element and frequency response methods in the assessment of thermal striping damage

When incompletely mixed, hot and cold fluid streams pass adjacent to the surface of a component or structure, and cause thermal striping on the surface. The existing methods of assessment of the consequent thermal fatigue damage have been implemented in the computer codes CLOUDBURST, TBL and STRIPE, and these have been shown to be in good agreement. Analysis of temporally random striping is possible in two of the methods, whereas use of the finite element method in such a fatigue analysis may lead to impractically long run times. However, for the special case of sinusoidal patterns of striping, comparison is made in this paper between TBL and the finite element method for the assessment of thermal striping damage.

A fully restrained, single edge cracked plate and a circumferentially cracked cylinder, axially restrained and unrestrained, have been subjected to sinusoidal surface striping for various representative temporal frequencies. The resulting stress intensity factor fluctuations have been determined for various crack depths using the finite element computer code ABAQUS and the analytical code TBL. Good comparisons have been obtained in all cases.     

Factors affecting in vitro formation of tannin-protein complexes

In interaction of condensed tannins from Desmodium intortum and Lotus pedunculatus and tannic acid (hydrolysable tannin) with salivary mucoproteins (from sheep and goats), plant leaf proteins and bovine serum albumin were evaluated. These studies were carried out over a pH range of 2-0-9-0 and different inorganic ion conditions to simulate conditions in which dietary proteins would interact with tannins in a ruminant digestive tract. Insoluble tannin-protein interactions were found at pH 4–5–5–5 for bovine serum albumin and 3–5–5–5 for plant leaf protein. The present study showed that pH alone was not the sole determinant for tannin-protein complex formation, since tannin-protein complexation was found in the pH range 6-0–6-5 when different inorganic ions were added to the solutions. Insoluble complexes were not formed with salivary proteins, although precipitation by tannic acid was achieved at 5°C. This suggests that tannins may form soluble rather than insoluble complexes with salivary proteins. It was concluded that purified F1 leaf protein (the major protei occurring in leaf tissue) ought to be used as the test protein for evaluating tannin-protein interactions for in vitro assay procedures. Using this method it was calculated that 27–43% and 19–40% of available plant protein may interact with condensed tannins from Desmodium intortum and Lotus pedunculatus, respectively.     

Water pollution in Ukraine: the search for possible solutions

In Ukraine, average and maximum concentrations of certain pollutants in inland water bodies are unacceptably high, while the number of heavy pollution accidents (one‐out effluent discharges capable of causing health hazards) is increasing. Meanwhile, the transition from a centrally planned to a free market economy is associated with severe economic downturn and a marked industrial decline. However, no comprehensive analyses related to issues linking water pollution and socio‐economic situation during the period 1991–2003 have been done. It is considered unlikely that much can be achieved to improve water quality, at the state level, in the near future. Some improvement can be achieved through changes in the system of pollution control and in public attitude, as well as obtaining relevant expertise and funds from abroad.     

Determination of added fat in meat paste using microwave and millimetre wave techniques

By evaluating the sensitivity of measurement parameters such as dielectric constant and microwave loss to fat content, several microwave and millimetre methods were compared to identify optimal frequency measurement bands. The results showed that the optimum frequency range lay between 8 and 20GHz where these parameters vary linearly, by up to a factor of 8, as fat is increased to 50% volume. A narrowband waveguide sensor cell was designed and constructed for this optimum range. The imaginary part (ε') of the complex permittivity demonstrated a better measurements resolution for determining fat content than the real part (ε'). The waveguide method has excellent repeatability as indicated by low relative standard deviation (RSD<4.88%). Temperature and sample density had minimal impact on the accuracy, repeatability and robustness of the final measurement system. A method of mixtures model for complex permittivity was shown to be a useful predictor of fat content.     

An efficient time scale model with tabulation of chemical equilibrium

The laminar and turbulent characteristic time-scale combustion model is extended for general reactive flows. In this model, energy and species compositions relax toward their corresponding local chemical equilibrium state over a characteristic time. Chemical equilibrium is efficiently evaluated using in situ adaptive tabulation (ISAT). The model is applied to a steady-state simulation of Sandia Flame D. The model is useful for simulations where kinetic mechanisms are not available, and also to provide good initial conditions for calculations with full chemical kinetics.     

Flour quality tests for selected wheat cultivars and their relationship to Arabic bread quality

Analytical and rheological parameters were established for flours from nine selected wheat cultivars, each covering a range of protein contents. Arabic and pan breads were baked from these flours and baking quality was determined. Wheat cultivars were found to differ in their suitability for Arabic bread production. Within cultivars the relationship between protein content and Arabic bread score was best described by a quadratic equation. Traditional flour quality tests do not adequately describe the flour quality requirements for Arabic bread as clearly as for pan bread. Ranges and optimum values for a number of parameters can be set to describe flours most likely to be suited to the production of Arabic bread. However, for reliable evaluation of baking quality for Arabic bread, flours fitting the prescribed range must be test baked.     

FINITE-ELEMENT SIMULATION OF A HEATED THIN FLUID LAYER

This investigation deals with finite-element modeling and numerical approximation of thermocapillary effects in long-wavelength evolution of inclined heated thin liquid layers. We consider several aspects, including model development, scaling and perturbation analysis, variational formulations, finite-element approximation, and application studies. A linear stability analysis of the thermocapillary problem for the layer at small inclination angle is also developed, and its implications are explored numerically over the related parameter space.