An electron microscopic study of nickel sulfide inclusions in toughened glass

It has been known since the early sixties that nickel sulfide inclusions cause spontaneous fracture of toughened (thermally tempered) glass, but despite the considerable amount of work done on this problem in the last four decades, failures still occur in the field with regularity. In this study we have classified (by viewing through a 60x optical microscope) inclusions into two groups, which are classic and atypical nickel sulfides. The classics look like the nickel sulfide inclusions found at the initiation-of-fracture of windows that have broken spontaneously. We have compared the structure and composition of the atypical inclusions with the structure and composition of the classics. All of the classic and atypical nickel sulfide inclusions studied in this work were found to have a composition in the range of Ni52S48 to Ni48S52. Inclusions on the nickel rich side of stoichiometric NiS were found to be two-phase assemblies, and inclusions on the sulphur rich side of NiS were single phase. It had been proposed that the atypicals were passive, and of a different composition to the classics. However, we found that the difference between passive and dangerous nickel sulfide inclusions was not a difference in composition but rather a difference in the type of material in the internal pore space. The passive's had carbon char in their internal pore space, whereas the pore space of dangerous inclusions contained Na2O. The presence of Na2O and carbon char with the inclusions indicates that the formation of the inclusions results from a reaction of a nickel-rich phase with sodium sulphate and carbon. (C) 2001 Kluwer Academic Publishers.

Flexural waves transmitted by rectangular piezoceramic transducers

Rectangular piezoceramic transducers are widely used in ultrasonic evaluation and health monitoring techniques and structural vibration control applications. In this paper the flexural waves excited by rectangular transducers adhesively attached to isotropic plates are investigated. In view of the difficulties in developing accurate analytical models describing the transfer characteristics of the transducer due to the complex electromechanical transduction processes and transducer-structure interactions involved, a combined theoretical-experimental approach is developed. A multiple integral transform method is used to describe the propagation behaviour of the waves in the plates, while a heterodyne Doppler laser vibrometer is employed as a non-contact receiver device. This combined theoretical-experimental approach enables the efficient characterization of the electromechanical transfer properties of the piezoelectric transducer which is essential for the development of optimized non-destructive evaluation systems. The results show that the assumption of a uniform contact pressure distribution between the transducer and the plate can accurately predict the frequency spectrum and time domain response signals of the propagating waves along the main axes of the rectangular transmitter element.

Molecular Lego (R): non-centrosymmetric alignment within interdigitating layers

(E)-N-Hexadecyl-4-[2-(4-octadecyloxynaphthyl) ethenyl] quinolinium bromide, which has a wide-bodied chromophore and terminal n-alkyl groups, adopts a U-shape when spread at the air-water interface but a stretched conformation when compressed to ca. 35 mN m(-1). The high-pressure phase has a narrow stability range prior to collapse but may be extended from 40 to 60 mN m(-1) by co-spreading the dye in a 1 : 1 ratio with docosanoic acid. The mixed Langmuir-Blodgett (LB) film has a monolayer thickness of 4.6 +/- 0.2 nm which decreases to 2.5 +/- 0.1 nm layer(-1) in the bulk, the reduction arising from an interdigitating layer arrangement, both top and bottom. It is the first example of LB-Lego(R) and, in addition, represents the only fully interdigitating structure with non-centrosymmetrically aligned chromophores. They are tilted 38 degrees from the substrate normal. The second-harmonic intensity increases quadratically with the number of layers, i.e. as I-(N)(2 omega) = (I(1)N2)-N-2 omega, with a second-order susceptibility of chi ((2))(zzz) = 30 pm V-1 at 1064 nm for refractive indices of n(omega) = 1.55 and n(2 omega) = 1.73, d = 2.5 nm layer(-1) and phi = 38 degrees. Angle resolved X-ray photoelectron spectra (XPS) of these films provide no evidence of the bromide counterion, which suggests that it is replaced by OH 2 or HCO3-, which occur naturally in the aqueous subphase, or C21H43COO- from the co-deposited fatty acid. This probably applies to all cationic dyes deposited by the LB technique.

Characterization of activated carbons using liquid phase adsorption

A modification of the Dubinin-Radushkevich pore filling model by incorporation of the repulsive contribution to the pore potential, and of bulk non-ideality, is proposed in this paper for characterization of activated carbon using liquid phase adsorption. For this purpose experiments have been performed using ethyl propionate, ethyl butyrate, and ethyl isovalerate as adsorbates and the microporous-mesoporous activated carbons Filtrasorb 400, Norit ROW 0.8 and Norit ROX 0.8 as adsorbents. The repulsive contribution to the pore potential is incorporated through a Lennard-Jones intermolecular potential model, and the bulk-liquid phase non-ideality through the UNIFAC activity coefficient model. For the characterization of activated carbons, the generalized adsorption isotherm is utilized with a bimodal gamma function as the pore size distribution function. It is found that the model can represent the experimental data very well, and significantly better than when the classical energy-size relationship is used, or when bulk non-ideality is neglected. Excellent agreement between the bimodal gamma pore size distribution and DFT-cum-regularization based pore size distribution is also observed, supporting the validity of the proposed model. (C) 2001 Elsevier Science Ltd. All rights reserved.

Application of heterogeneous vacancy solution theory to characterization of microporous solids

The vacancy solution theory of adsorption is re-formulated here through the mass-action law, and placed in a convenient framework permitting the development of thermodynamic ally consistent isotherms. It is shown that both the multisite Langmuir model and the classical vacancy solution theory expression are special cases of the more general approach when the Flory-Huggins activity coefficient model is used, with the former being the thermodynamically consistent result. The improved vacancy solution theory approach is further extended here to heterogeneous adsorbents by considering the pore-width dependent potential along with a pore size distribution. However, application of the model to numerous hydrocarbons as well as other adsorptives on microporous activated carbons shows that the multisite model has difficulty in the presence of a pore size distribution, because pores of different sizes can have different numbers of adsorbed layers and therefore different site occupancies. On the other hand, use of the classical vacancy solution theory expression for the local isotherm leads to good simultaneous fit of the data, while yielding a site diameter of about 0.257 nm, consistent with that expected for the potential well in aromatic rings on carbon pore surfaces. It is argued that the classical approach is successful because the Flory-Huggins term effectively represents adsorbate interactions in disguise. When used together with the ideal adsorbed solution theory the heterogeneous vacancy solution theory successfully predicts binary adsorption equilibria, and is found to perform better than the multisite Langmuir as well as the heterogeneous Langmuir model. (C) 2001 Elsevier Science Ltd. All rights reserved.

Probabilistic modelling of CO2 corrosion laboratory data using neural networks

The present paper addresses two major concerns that were identified when developing neural network based prediction models and which can limit their wider applicability in the industry. The first problem is that it appears neural network models are not readily available to a corrosion engineer. Therefore the first part of this paper describes a neural network model of CO2 corrosion which was created using a standard commercial software package and simple modelling strategies. It was found that such a model was able to capture practically all of the trends noticed in the experimental data with acceptable accuracy. This exercise has proven that a corrosion engineer could readily develop a neural network model such as the one described below for any problem at hand, given that sufficient experimental data exist. This applies even in the cases when the understanding of the underlying processes is poor. The second problem arises from cases when all the required inputs for a model are not known or can be estimated with a limited degree of accuracy. It seems advantageous to have models that can take as input a range rather than a single value. One such model, based on the so-called Monte Carlo approach, is presented. A number of comparisons are shown which have illustrated how a corrosion engineer might use this approach to rapidly test the sensitivity of a model to the uncertainities associated with the input parameters. (C) 2001 Elsevier Science Ltd. All rights reserved.

How cracks in SiOx-coated polyester films affect gas permeation

In this paper theoretical models have been established that can account for the gas transmission through nanocomposite laminates, consisting of an oxide layer of finite permeability containing defects, on a polymer sheet of finite thickness. The defect shapes can either be in the form of long cracks or rectangular holes. The models offer a choice of exact numerical calculations or fast and intuitive analytical approximations. The experimental measurements of oxygen permeation through four different SiOx/poly (ethylene terephthalate) samples that were strained to produce distributions or cracks showed good agreement when compared with predicted results from the approximate analytic model. As a consequence of this observation, a key practical conclusion is that, because of the logarithmic dependence of transmission on the width of a crack, for a given strain it is better to have a small number of large cracks rather than a large number of small cracks. (C) 2001 Elsevier Science B.V. All rights reserved.

Recent advances in the preparation and utilization of carbon nanotubes for hydrogen storage

Recent progress in the production, purification, and experimental and theoretical investigations of carbon nanotubes for hydrogen storage are reviewed. From the industrial point of view, the chemical vapor deposition process has shown advantages over laser ablation and electric-arc-discharge methods. The ultimate goal in nanotube synthesis should be to gain control over geometrical aspects of nanotubes, such as location and orientation, and the atomic structure of nanotubes, including helicity and diameter. There is currently no effective and simple purification procedure that fulfills all requirements for processing carbon nanotubes. Purification is still the bottleneck for technical applications, especially where large amounts of material are required. Although the alkali-metal-doped carbon nanotubes showed high H-2 Weight uptake, further investigations indicated that some of this uptake was due to water rather than hydrogen. This discovery indicates a potential source of error in evaluation of the storage capacity of doped carbon nanotubes. Nevertheless, currently available single-wall nanotubes yield a hydrogen uptake value near 4 wt% under moderate pressure and room temperature. A further 50% increase is needed to meet U.S. Department of Energy targets for commercial exploitation. Meeting this target will require combining experimental and theoretical efforts to achieve a full understanding of the adsorption process, so that the uptake can be rationally optimized to commercially attractive levels. Large-scale production and purification of carbon nanotubes and remarkable improvement of H-2 storage capacity in carbon nanotubes represent significant technological and theoretical challenges in the years to come.

Hydrophobicity of Templated Silica Xerogels for Molecular Sieving Applications

Silica xerogels were prepared by a sol-gel process catalyzed by acid with tetraethylorthosilicate, and using an organic covalent ligand template (methyltriethoxysilane) or a noncovalent template C6 surfactant (triethylhexylammonium bromide). The influence of hydrotreatment on the structure of templated xerogels is examined in terms of surface area, micropore volume, average pore size, and pore size distribution, and compared against a blank xerogel (nontemplated). The role of surface functional groups was evaluated using Si-29 nuclear magnetic resonance. The structural integrity of the xerogel was maintained to a large extent in samples that had a high contribution of Q(4) species (siloxane groups). Xerogel matrix densification occurred when there was a large concentration of Q(3) and Q(2) species (silanol groups), which also were responsible for increased hydrophilicity. The templated xerogels resulted in up to a 25% concentration of methyl functional groups (T-3 and T-2 species), leading to hydrophobic xerogels. The best results in terms of structural integrity and hydrophobicity were obtained with templated xerogels prepared with the C6 surfactant. The results in this study suggest that surfactant-enhanced condensation reactions lead to structures with a high contribution of Q(4) groups, which are not susceptible to water attack, but are strong enough to oppose matrix densification during rehydration.

Coupled experimental and thermodynamic study of the Zn-Fe-Si-O system

Experimental and thermodynamic modeling studies have been carried out on the Zn-Fe-Si-O system. This research is part of a wider program to characterize zinc/lead industrial slags and sinters in the PbO-ZnO-SiO2-CaO-FeO-Fe2O3 system. Experimental investigations involve high-temperature equilibration and quenching techniques followed by electron probe X-ray microanalysis (EPMA). Liquidus temperatures and solid solubilities of the crystalline phases were measured in the temperature range from 1200 °C to 1450 °C (1473 to 1723 K) in the zinc ferrite, zincite, willemite, and tridymite primary-phase fields in the Zn-Fe-Si-O system in air. These equilibrium data for the Zn-Fe-Si-O system in air, combined with previously reported data for this system, were used to obtain an optimized self-consistent set of parameters of thermodynamic models for all phases.

The effect of heat treatment on the toughness, hardness and microstructure of low carbon white cast irons

The effect of destabilisation and subcritical heat treatment on the impact toughness, hardness, and the amount and mechanical stability of retained austenite in a low carbon white cast iron have been investigated. The experimental results show that the impact energy constantly increases when the destabilisation temperature is raised from 950 degreesC to 1200 degreesC. Although the hardness decreases, the heat-treated hardness is still greater than the as-cast state. After destabilisation treatment at 1130 degreesC, tempering at 200 to 250 degreesC for 3 hours leads to the highest impact toughness, and secondary hardening was observed when tempering over 400 degreesC. The amount of retained austenite increased with the increase in the destabilisation temperature, and the treatment significantly improves the mechanical stability of the retained austenite compared with the as-cast state. Tempering below 400 degreesC does not affect the amount of retained austenite and its mechanical stability. But the amount of retained austenite is dramatically reduced when tempered above 400 degreesC. The relationship between the mechanical properties and the microstructure changes was discussed. (C) 2001 Kluwer Academic Publishers.

The Dubinin-Radushkevich equation and the underlying microscopic adsorption description

The Dubinin-Radushkevich (DR) equation is widely used for description of adsorption in microporous materials, especially those of a carbonaceous origin. The equation has a semi-empirical origin and is based on the assumptions of a change in the potential energy between the gas and adsorbed phases and a characteristic energy of a given solid. This equation yields a macroscopic behaviour of adsorption loading for a given pressure. In this paper, we apply a theory developed in our group to investigate the underlying mechanism of adsorption as an alternative to the macroscopic description using the DR equation. Using this approach, we are able to establish a detailed picture of the adsorption in the whole range of the micropore system. This is different from the DR equation, which provides an overall description of the process. (C) 2001 Elsevier Science Ltd. All rights reserved.

Determination of eutectic solidification mode in Sr-modified hypoeutectic Al-Si alloys by EBSD

The effect of eutectic modification by strontium on nucleation and growth of the eutectic in hypoeutectic Al-Si foundry alloys has been investigated by electron back-scattering diffraction (EBSD) mapping. Specimens were prepared from three hypoeutectic AlSi base alloys with 5, 7 and 10 mass%Si and with different strontium contents up to 740 ppm for modification of eutectic silicon. By comparing the orientation of the aluminium in the eutectic to that of the surrounding primary aluminium dendrites? the growth mode of the eutectic could be determined. The mapping results indicate that the eutectic grew from the primary phase in unmodified alloys. When the eutectic was modified by strontium, eutectic grains nucleated separately from the primary dendrites. However, in alloys with high strontium levels, the eutectic again grew from the primary phase. These observed effects of strontium additions on the eutectic solidification mode are independent of silicon content in the range between 5 and 10 mass%Si.

Eutectic growth mode in strontium, antimony and phosphorus modified hypoeutectic Al-Si foundry alloys

The effect of strontium (Sr), antimony (Sb) and phosphorus (P) on nucleation and growth mode of the eutectic in hypoeutectic Al-10 mass%Si alloys has been investigated by electron back-scattering diffraction (EBSD) mapping. Specimens were prepared from a hypoeutectic Al-10 mass%Si base alloy, adding different levels of strontium, antimony and phosphorus for modification of eutectic silicon. By comparing the orientation of the aluminium in the eutectic to that of the surrounding primary aluminium dendrites, the solidification mode of the eutectic could be determined. The results of these studies show that the eutectic nucleation mode, and subsequent growth mode, is strongly dependent on additive elements. The EBSD mapping results indicate that the eutectic grew from the primary phase in unmodified and phosphorus-containing alloys. When the eutectic was modified by strontium or antimony, eutectic grains nucleated and grew separately from the primary dendrites.