Co-tunneling enhancement of the electrical response of nanoparticle networks

A co-tunneling charge-transfer process dominates the electrical properties of a nanometer-sized "slice" in a nanoparticle network, which results in universal scaling of the conductance with temperature and bias voltage, as well as enhanced spintronics properties. By designing two large (10 μm) electrodes with short (60 nm) separation, access is obtained to transport dominated by charge transfer involving "nanoslices" made of three nanoparticles only. Magnetic iron oxide nanoparticle networks exhibit a magnetoresistance ratio that is not reachable by tunneling or hopping processes, thereby illustrating how such a size-matched planar device with dominant co-tunneling charge-transfer process is optimal for realizing multifunctional devices with enhanced change of conductance under external stimulus.     

Size-dependent multispectral photoacoustic response of solid and hollow gold nanoparticles

Photoacoustic (PA) imaging attracts a great deal of attention as an innovative modality for longitudinal, non-invasive, functional and molecular imaging in oncology. Gold nanoparticles (AuNPs) are identified as superior, NIR-absorbing PA contrast agents for biomedical applications. Until now, no systematic comparison of the optical extinction and PA efficiency of water-soluble AuNPs of various geometries and small sizes has been performed.Here spherical AuNPs with core diameters of 1.0, 1.4 and 11.2?nm, nanorods with longitudinal/transversal elongation of 38/9 and 44/12?nm and hollow nanospheres with outer/inner diameters of 33/19, 57/30, 68/45 and 85/56?nm were synthesized. The diode laser set-up with excitations at 650, 808, 850 and 905?nm allowed us to correlate the molar PA signal intensity with the molar extinction of the respective AuNPs. Deviations were explained by differences in heat transfer from the particle to the medium and, for larger particles, by the scattering of light. The molar PA intensity of 1.0?nm AuNPs was comparable to the commonly used organic dye methylene blue, and rapidly increased with the lateral size of AuNPs.     

Modeling delamination growth in composites under fatigue loadings of varying amplitudes

A numerical model was developed to simulate the progressive delamination of a composite subjected to mode I fatigue loading regimes of varying amplitude. The model employs a cohesive zone approach, which combines damage mechanics and fracture mechanics, and requires only standard material data as input, namely the delamination toughness and the fatigue delamination growth curve. The proposed model was validated against delamination growth data obtained from a fatigue test conducted on a DCB specimen. The model predictions agree very well with the experimental results. This model is an initial step toward life prediction of composite structures subjected to complex fatigue regimes.     

Filtration performance at high temperatures and analysis of ceramic filter elements during biomass gasification

During the CHRISGAS project, various experimental campaigns were performed with the aim to study the hot gas filtration process during steam-O₂ biomass gasification at Delft University of Technology. The test-rig consists of a 100 kW thermal atmospheric circulating fluidized-bed gasifier and a high temperature filter unit which contains 3 rigid ceramic candles with an outer diameter of 60 mm, 10 mm wall thickness and a length of 1520 mm. This paper gives an overview of tests performed with different fuels (A-wood, B-wood, miscanthus) and with sand and magnesite used as bed materials. Dia-Schumalith¹ candles were operated in the temperature range between 600 °C and 800 °C for more than 50 h. The filtration performance was studied through continuous observation of the increasing differential pressure while the filter cake formed on the surface of the candles. Gas face velocities ranged between 3 cm s^?1 and 5 cm s^?1. Stable filtration was achieved during some tests. Dust cake analysis indicated formation of calcium phosphates and silicates and potassium silicates.     

Coupling of finite element and boundary integral methods for a capsule in a Stokes flow

We introduce a new numerical method to model the fluid–structure interaction between a microcapsule and an external flow. An explicit finite element method is used to model the large deformation of the capsule wall, which is treated as a bidimensional hyperelastic membrane. It is coupled with a boundary integral method to solve for the internal and external Stokes flows. Our results are compared with previous studies in two classical test cases: a capsule in a simple shear flow and in a planar hyperbolic flow. The method is found to be numerically stable, even when the membrane undergoes in‐plane compression, which had been shown to be a destabilizing factor for other methods. The results are in very good agreement with the literature. When the viscous forces are increased with respect to the membrane elastic forces, three regimes are found for both flow cases. Our method allows a precise characterization of the critical parameters governing the transitions. Copyright © 2010 John Wiley & Sons, Ltd.     

Gas chromatography/electron ionization-mass spectrometry-selected ion monitoring screening method for a thorough investigation of polyhalogenated compounds in passive sampler extracts with quadrupole systems

Nontarget analysis and identification of unknown polyhalogenated compounds is important in acquiring a thorough picture of the present pollution status as well as for identifying emerging environmental problems. Such analyses usually require the application of electron ionization mass spectrometry because the resulting mass spectra frequently allow for compound identification. When quadrupoles are used as mass separators, the full scan technique often suffers from low sensitivity along with nonspecificity for polyhalogenated trace compounds which often result in interference by matrix compounds. We have developed a novel nontarget gas chromatography/electron ionization-mass spectrometry-selected ion monitoring (GC/EI-MS-SIM) method that overcomes these sensitivity and selectivity issues. Our method is based on the fact that the molecular ions and isotope patterns of polyhalogenated compounds involve the most relevant primary information with regard to the structure of polyhalogenated compounds. Additionally, the retention times of polyhalogenated compounds generally increase with increasing molecular weight. The retention time range of polyhalogenated compounds was divided in three partly overlapping segments of 112 u (segment A: m/z 300-412; segment B: m/z 350-462; segment C: m/z 450-562) that were screened in eight GC runs consisting of 15 consecutive SIM ions. This method was tested with a passive water sampler extract known to contain over 30 polyhalogenated compounds according to the sensitive analysis by GC/electron capture negative ion (ECNI)-MS. While none of these polyhalogenated compounds could be detected by GC/EI-MS in full scan mode, our nontarget GC/EI-MS-SIM method allowed for the detection of 38 polyhalogenated compounds. Only seven could be identified by means of reference standards while more than 15 of the unknowns could be traced back to at least the class of compounds based on the mass spectrometric data from the nontarget SIM runs. All compounds identified originated from halogenated natural products. The nontarget GC/EI-MS-SIM method combines the high sensitivity obtainable with quadrupole systems for trace analysis with the structural information essential for the identification of unknown pollutants.     

Elevated temperature cycling stability and electrochemical impedance of LiMn2O4 cathodes with nanoporous ZrO2 and TiO2 coatings

In this study, nanoporous zirconia (ZrO₂) and titania (TiO₂) coatings are shown to stabilize the cycling performance of lithium-ion batteries with LiMn₂O₄ spinel cathodes. The effect of firing temperature on the coating pore size is discussed and the resulting performance of the coated cathodes is evaluated. Stabilization mechanisms, such as neutralization of acidic electrolytes by ZrO₂ and TiO₂ coatings, are examined. It is proposed that the establishment of a complex nanoporous network for lithium-ion transport results in a more uniform current distribution at the particle surface, thereby suppressing capacity fade that may be associated with surface instabilities of the spinel electrode.     

Replication of liner collapse phenomenon observed in hyperbaric type IV hydrogen storage vessel by explosive decompression experiments

An experimental design based on representative sample is described in order to reproduce the detachment and deformation of the inner polymer layer (called liner) of hyperbaric hydrogen storage vessels during the emptying step. It is the first step of a better understanding of the mechanisms involved in the creation of a liner collapse. Results showed that a hydraulic testing machine fitted with a pressure hydrogen chamber enables to create a liner collapse on small samples by explosive decompression experiments. Tomographic observations have revealed that the collapse appears at the polymer liner/composite interface in areas that are not sufficiently bonded, nor consistently. Determination of liner collapse amplitudes, assessed by tomography, has underlined that, under some specific conditions, the deformation of the liner is permanent even when hydrogen has completely desorbed from the sample. In addition to liner collapses, composite cracks were also highlighted.     

Hydrogen storage in MgH2LaNi5 composites prepared by cold rolling under inert atmosphere

Mg-AB₅ composites are promising systems for hydrogen storage applications, due to their possibility of hydrogen cycling at relatively low temperatures. Traditionally, these composites are mainly processed by high-energy ball milling (HEBM) techniques employing longer processing times. In this study, cold rolling was applied to prepare MgH₂LaNi₅ composites and the hydrogen storage properties were investigated. The materials were processed using a vertical rolling mill under argon atmosphere, leading to a good homogeneity and no contamination at shorter processing times. The mixture of MgH₂-1.50 mol.% LaNi₅ showed the best hydrogen storage properties at 200 °C and 100 °C and the lowest desorption temperature even when compared to cold rolled MgH₂. The results indicate that the composite MgH₂LaNi₅ is transformed into a mixture of three phases MgH₂, Mg₂NiH₄ and LaH₃ upon hydrogen absorption/desorption cycles. The synergetic effect among these phases when in appropriate proportion in the sample seems to play a crucial role in the acceleration of hydrogen absorption/desorption kinetics at lower temperatures in comparison to MgH₂.