GCMC-surface area of carbonaceous materials with N-2 and Ar adsorption as an alternative to the classical BET method

In this paper we apply a new method for the determination of surface area of carbonaceous materials, using the local surface excess isotherms obtained from the Grand Canonical Monte Carlo simulation and a concept of area distribution in terms of energy well-depth of solid–fluid interaction. The range of this well-depth considered in our GCMC simulation is from 10 to 100 K, which is wide enough to cover all carbon surfaces that we dealt with (for comparison, the well-depth for perfect graphite surface is about 58 K). Having the set of local surface excess isotherms and the differential area distribution, the overall adsorption isotherm can be obtained in an integral form. Thus, given the experimental data of nitrogen or argon adsorption on a carbon material, the differential area distribution can be obtained from the inversion process, using the regularization method. The total surface area is then obtained as the area of this distribution. We test this approach with a number of data in the literature, and compare our GCMC-surface area with that obtained from the classical BET method. In general, we find that the difference between these two surface areas is about 10%, indicating the need to reliably determine the surface area with a very consistent method. We, therefore, suggest the approach of this paper as an alternative to the BET method because of the long-recognized unrealistic assumptions used in the BET theory. Beside the surface area obtained by this method, it also provides information about the differential area distribution versus the well-depth. This information could be used as a microscopic finger-print of the carbon surface. It is expected that samples prepared from different precursors and different activation conditions will have distinct finger-prints. We illustrate this with Cabot BP120, 280 and 460 samples, and the differential area distributions obtained from the adsorption of argon at 77 K and nitrogen also at 77 K have exactly the same patterns, suggesting the characteristics of this carbon.

Simulation of galvanic corrosion of magnesium coupled to a steel fastener in NaCl solution

The galvanic corrosion of magnesium alloy AZ91D coupled to a steel fastener was studied using a boundary element method (BEM) model and experimental measurements. The BEM model used the measured polarization curves as boundary conditions. The experimental program involved measuring the total corrosion rate as a function of distance from the interface of the magnesium in the form of a sheet containing a mild steel circular insert (5 to 30 mm in diameter). The measured total corrosion rate was interpreted as due to galvanic corrosion plus self corrosion. For a typical case, the self corrosion was estimated typically to be similar to 230 mm/y for an area surrounding the interface and to a distance of about I cm from the interface. Scanning Kelvin Probe Force Microscopy (SKPFM) revealed microgalvanic cells with potential differences of approximately 100 mV across the AZ91D surface. These microgalvanic cells may influence the relative contributions of galvanic and self corrosion to the total corrosion of AZ91D.

A study on transition of iron from active into passive state

An investigation was carried out on the transition of an iron electrode from active to passive state in a sulphuric acid solution. It was found that the active-passive transition was an auto-catalytic process in which a pre-passive film grew on the electrode surface. The growing pre-passive film had a fractal edge whose dimension was affected by the applied passivating potential and the presence of chlorides in the solution. Applying a more positive passivating potential led to a faster active-passive transition and resulted in a more irregular pre-passive film. If chlorides were introduced into the sulphuric acid solution, the active-passive transition became more rapid and the pre-passive film more irregular. Apart from the influence on the growth of the pre-passive film, the presence of chlorides in the passivating solution was found to deteriorate the stability of the final passive film. All these phenomena can be understood if the passivating iron electrode is regarded as a dissipative system. To explain these results, a fractal pre-film model is proposed in this paper. (C) 2004 Elsevier Ltd. All rights reserved.

Time-resolved photoluminescence spectroscopy of ligand-capped PbS nanocrystals

PbS nanocrystals are synthesized using colloidal techniques and have their surfaces capped with oleic acid. The absorption band edge of the PbS nanocrystals is tuned between 900 and 580 nm. The PbS nanocrystals exhibit tuneable photoluminescence with large non-resonant Stokes shifts of up to 500 mcV. The magnitude of the Stokes shift is found to be dependent upon the size of PbS nanocrystals. Time-resolved photoluminescence spectroscopy of the PbS nanocrystals reveals that the photouminescence has an extraordinarily long lifetime of 1 mus. This long fluorescence lifetime is attributed to the effect of dielectric screening similar to that observed in other IV-VI semiconductor nanocrystals.

Hydrogen storage of magnesium-based nanocomposites system

Hydrogen storage in traditional metallic hydrides can deliver about 1.5 to 2.0 wt pct hydrogen but magnesium hydrides can achieve more than 7 wt pct. However, these systems suffer from high temperature release drawback and chemical instability problems. Recently, big improvements of reducing temperature and increasing kinetics of hydrogenation have been made in nanostructured Mg-based composites. This paper aims to provide an overview of the science and engineering of Mg materials and their nanosized composites with nanostructured carbon for hydrogen storage. The needs in research including preparation of the materials, processing and characterisation and basic mechanisms will be explored. The preliminary experimental results indicated a promising future for chemically stable hydrogen storage using carbon nanotubes modified metal hydrides under lower temperatures.

Hydrogen storage properties of MgH2/SWNT composite prepared by ball milling

A systematic investigation was performed on the hydrogen storage properties of mechano-chemically prepared MgH2/Single-walled carbon nanotube (SWNT) composites. It is found that the hydrogen absorption capacity and hydriding kinetics of the composites were dependent on the addition amount of SWNTs as well as milling time. A 5 wt.% addition of SVVNTs is optimum to facilitate the hydrogen absorption and desorption of MgH2. The composite MgH2/5 wt.% SWNTs milled for 10h can absorb 6.7 wt.% hydrogen within about 2 min at 573 K, and desorb 6 wt.% hydrogen in about 5 min at 623 K. Prolonging the milling time over 10 h leads to a serious degradation on hydrogen storage property of the MgH2/SWNT composite, and property/structure investigations suggest that the property degradation comes from the structure destruction of the SWNTs. (c) 2005 Elsevier B.V. All rights reserved.

Effect of carbon/noncarbon addition on hydrogen storage behaviors of magnesium hydride

Various Mg/carbon and Mg/noncarbon composite systems were prepared by mechanical milling and their hydrogen storage behaviors were investigated. It was found that all the carbon additives exhibited prominent advantage over the noncarbon additives, such as BN nanotubes (BNNTs) or asbestos in improving the hydrogen capacity and dehydriding/hydriding kinetics of Mg. And among the various carbon additives, purified single-walled carbon nanotubes (SWNTs) exhibited the most prominent catalytic effect on the hydrogen storage properties of Mg. The hydrogen capacities of all Mg/C composites at 573 K reached more than 6.2 wt.% within 10 min, about 1.5 wt.% higher than that of pure MgH2 at the identical operation conditions. Under certain operation temperatures, H-absorption/desorption rates of Mg/carbon systems were over one order of magnitude higher than that of pure Mg. Furthermore, the starting temperature of the desorption reaction of MgH2 has been lowered to 60 K by adding SWNTs. On the basis of the hydrogen storage behavior and structure/phase investigations, the possible mechanism involved in the property improvement of Mg upon adding carbon materials was discussed. (c) 2005 Elsevier B.V. All rights reserved.

A novel method for the production of aluminium nitride

A method has been developed to produce thick (> 400 mu m) AlN surface layers oil aluminium plates at 540 degrees C, under nitrogen at atmospheric pressure. A critical element of the process is the use of Mg powder placed in close proximity to the Al plate surface. The Mg reduces/disrupts the natural, protective oxide film on the Al surface. The nitride layers form through two distinct modes, one growing outward from the Al plate surface and the other growing into the Al. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Fatigue crack propagation in a sintered 2xxx series aluminium alloy

Many potential applications for sintered aluminium are limited by the poor fatigue properties of the material. In order to increase understanding of the fatigue mechanisms in sintered aluminium, fatigue tests were carried out on a sintered 2xxx series aluminium alloy, AMB-2712. The alloy has a fatigue endurance strength of approximately 145 MPa (R = 0.1). Three regions were identified on the fatigue fracture surfaces. Region I contains the initiation site and transgranular crack propagation. When the size of the cyclic plastic zone ahead of the crack becomes comparable to the grain size, microstructural damage at the crack tip results in a transition to intergranular propagation. Region 2 mainly contains intergranularly fractured material, whilst the final fracture area makes up Region 3, in the form of dimple coalescence and intergranular failure. Transgranular fractographic features observed on fatigued specimens include fissure-type striations, cross-hatched grains, furrowed grains and grains containing step-like features. (c) 2006 Elsevier B.V. All rights reserved.

Yield criterion of porous materials subjected to complex stress states

Finite-element simulations are used to obtain many thousands of yield points for porous materials with arbitrary void-volume fractions with spherical voids arranged in simple cubic, body-centred cubic and face-centred cubic three-dimensional arrays. Multi-axial stress states are explored. We show that the data may be fitted by a yield function which is similar to the Gurson-Tvergaard-Needleman (GTN) form, but which also depends on the determinant of the stress tensor, and all additional parameters may be expressed in terms of standard GTN-like parameters. The dependence of these parameters on the void-volume fraction is found. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Yield functions for porous materials with cubic symmetry using different definitions of yield

Plastic yield criteria for porous ductile materials are explored numerically using the finite-element technique. The cases of spherical voids arranged in simple cubic, body-centred cubic and face-centred cubic arrays are investigated with void volume fractions ranging from 2 % through to the percolation limit (over 90 %). Arbitrary triaxial macroscopic stress states and two definitions of yield are explored. The numerical data demonstrates that the yield criteria depend linearly on the determinant of the macroscopic stress tensor for the case of simple-cubic and body-centred cubic arrays - in contrast to the famous Gurson-Tvergaard-Needleman (GTN) formula - while there is no such dependence for face-centred cubic arrays within the accuracy of the finite-element discretisation. The data are well fit by a simple extension of the GTN formula which is valid for all void volume fractions, with yield-function convexity constraining the form of the extension in terms of parameters in the original formula. Simple cubic structures are more resistant to shear, while body-centred and face-centred structures are more resistant to hydrostatic pressure. The two yield surfaces corresponding to the two definitions of yield are not related by a simple scaling.

Effects of carbon nanotubes and metal catalysts on hydrogen storage in magnesium nanocomposites

This paper reports a study on nanostructured magnesium composites with carbon nanotubes (CNTs) and catalytic transition metals with high H-2 adsorption capacity and fast adsorption kinetics at reduced hydrogenation temperatures. Nanostructures in such a composite are shown to be responsible for improvements in both adsorption capacity and kinetics. It is found that the carbon nanotubes significantly increase the hydrogen storage capacity, and the catalytic transition metals (Fe and Ti) greatly improve the kinetics. This could be understood from the enhancement of diffusion by CNTs and decrease in energy barrier of hydrogen dissociation at the magnesium surface.

The effect of Cu addition and milling contaminations on the microstructure evolution of ball milled Al-Pb alloy during sintering

Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu (x = 0-7.0) bulk alloys were prepared by sintering the mechanically alloyed powders at various temperatures. The microstructure changes of the as consolidated powders in the course of sintering were analyzed by differential scanning calorimetry, scanning electron microscopy, X-ray diffraction analysis and transmission electron microscopy. It has been found that, with respect to the Al-10 wt.%Pb-x wt.%Cu alloy, CuAl2 and Cu9Al4 phases formed in the milling process, and the amount of CuAl2 phase increased while the Cu9Al4 phase disappeared gradually in the sintering process. In both Al-10 wt.%Pb and Al-10 wt.%Pb-x wt.%Cu alloys, the sintering process results in the coarsening of Pb phase and the growth rate of Pb phase fulfills the Lifshitz-Slyozov-Wagner equation even though the size of the Pb phase was in nanometer range. The Pb particle exhibits cuboctahedral morphology and has a cubic to cubic orientation relationship with the Al matrix. The addition of Cu strongly depressed the growth rate of Pb. Contamination induced by milling has apparent influence on the microstructure of the sintered alloys. Al7Cu2Fe and aluminium oxide phases were identified in the sintered alloys. The cuboctahedral morphology of Pb particles was broken up by the presence of the oxide phase. (c) 2006 Elsevier B.V. All rights reserved.