Preparation and evaluation of sufficiently homogeneous and stable reference materials for priority hazardous substances in whole water

We have prepared and evaluated three whole water test materials containing eight polycyclic aromatic hydrocarbons (PAHs), six polybrominated diphenyl ethers (PBDEs) and tributyltin (TBT) with respect to homogeneity and short-term stability. The test materials were used as samples in two inter-laboratory comparisons. The materials were composed of natural mineral water and model suspended particulate matter (SPM) containing the target compounds at ng L^?1 levels. The expanded uncertainty of the estimated mass concentrations in the final test materials was obtained by combining contributions from the homogeneity, the stability and the model SPM characterization. The whole water materials were sufficiently homogeneous and stable at 4 °C for their intended use. In total, 12 out of 15 investigated target parameters could be assessed to be present with a relative combined expanded uncertainty below 25 %. The outcome of the two inter-laboratory comparisons confirmed the good quality of the test materials and the level of uncertainties associated with the estimated mass concentrations. These findings are an important contribution towards the development of whole water matrix reference materials certified for PAH, PBDE and TBT in support of the Water Framework Directive of the European Union.     

Multiscale modeling for ferroelectric materials: a transition from the atomic level to phase-field modeling

To link the atomic level and the mesoscale within a knowledge-based multiscale modeling approach for ferroelectric materials, a method is suggested to transfer results from first-principles calculations into a phase-field model. DFT calculations and atomistic simulations are applied and provide a set of intrinsic and extrinsic material properties for PbTiO₃ and tetragonal Pb(Zr_0.5Ti_0.5)O₃. The Helmholtz free energy of the phase-field model that contains all crystallographic and domain wall information is discussed in detail, and a sensitivity analysis is performed to identify the coefficients of the energy function. Then, a method is developed to adjust the coefficients of the Helmholtz free energy solely based on results from first-principles calculations. Full sets of adjusted energy coefficients for PbTiO₃ and Pb(Zr_0.5Ti_0.5)O₃ are presented and discussed, as well the limits of the suggested adjustment method.     

Ab-Initio Investigation of Metal-Ceramic Bonding: M(001)/MgAl2O4(001), M = Al, Ag

The optimised adhesion geometry and the work of adhesion were determined for the interface systems Al(001)/MgAl₂O₄(001) and Ag(001)/MgAl₂O₄(001) by ab-initio density-functional calculations. Al is bound strongly on-top of oxygen at reduced lattice spacing, whereas weak adhesion and no unique optimum structure are obtained for Ag. An analysis of the electronic structure shows that in both systems the metal-ceramic interaction is spatially confined to a narrow range along the interface layers. The weak adhesion of Ag on spinel is mediated by a polarisation of the metal film, which may be classified as an image-charge interaction. In the case of Al a weak image-charge contribution is dominated by a strong electron-density redistribution perpendicular to the interface, which leads to the formation of directional Al—O bonds.     

Calibration of granular material parameters for DEM modelling and numerical verification by blade-granular material interaction

The discrete element method (DEM) is a promising approach to model blade-granular material interactions. The accuracy of DEM models depends on the model parameters. In this study, a calibration process was developed to determine the parameter values. The particle size was the same as the real material and the particle shape was modelled using two spherical particles rigidly clumped together to form a single grain. Laboratory shear tests and compressions tests were used to determine the material internal friction angle and stiffness, respectively. These tests were replicated numerically using DEM models with different sets of particle friction coefficients and particle stiffness values. The shear test results are found to be dependent on both the particle friction coefficient and the particle stiffness. The compression test results show that it is only dependent on the particle stiffness. The combination of shear test and compression test results can be used to determine a unique set of particle friction and particle stiffness values. The calibration process was validated experimentally and numerically by modelling a blade moving through granular material. Results show that the forces acting on the blade can be accurately modelled with DEM and the maximum error is found to be 26%. The relative particle-blade displacements were used to predict the position and shape of the shear lines in front of the blade. A good qualitative correlation was achieved between the experiments and the DEM simulations.     

Photophysics and Fluorimetric Titrations of Fluorescent Ion Indicators

A test based on time-resolved fluorescence experiments (Anal. Biochem. 245, 28–37, 1997) allows one to assess the interference of the excited-state association with the fluorimetric determination of the ground-state dissociation constant K _d of fluorescent ion:indicator complexes. If an inflection point occurs in the plot of the fluorescence signal vs – log[ion] in the ion concentration range where both decay times are invariant, this inflection point can be associated with the correct K _d. Here we apply this test to the fluorescent ion indicators SBFO (for Na⁺), Mag-fura-2 (for Mg²⁺), and APTRA-BTC (for Ca²⁺). In all three cases the decay times are invariant in the concentration ranges of the respective ions where the fluorescence titrations show unique inflection points, indicating that the fluorimetrically determined K _d values are the true K _d values.     

Semi-active rotary damper for a heavy off-road wheeled vehicle

The development, simulation and laboratory testing of two-state discrete adjustable semi-active rotary dampers for heavy off-road wheeled vehicles, which is a joint venture between the South African based company Reumech Ermetek and Horstman Defence Systems from the UK, is described. A brief history of semi-active damping and rotary dampers is given, after which the working principle and features of combining the two technologies is outlined. Three dimensional simulation is used to determine the ride comfort gains achievable with semi-active rotary dampers compared to the conventional translational dampers currently used on the vehicle under consideration. Simulations are performed over different terrains, including the APG track and discrete obstacles. Semi-active rotary dampers were integrated on the 6×6 GV6 Self-propelled Gun Howitzer in order to quantify the improvements in ride comfort, transient response and handling of the vehicle as indicated by the simulation results. The control system, control strategies and characterisation tests, which includes determination of on and off characteristics as well as valve response times, are discussed.     

The ride comfort vs. handling compromise for off-road vehicles

When designing vehicle suspension systems, it is well-known that spring and damper characteristics required for good handling on a vehicle are not the same as those required for good ride comfort. Any choice of spring and damper characteristic is therefore necessarily a compromise between ride comfort and handling. The compromise is more pronounced on off-road vehicles, as they require good ride comfort over rough off-road terrain, as well as acceptable on-road handling. In this paper, the ride comfort vs. handling compromise for off-road vehicles is investigated by means of three case studies. All three case studies indicate that the spring and damper charcteristics required for ride comfort and handling lie on opposite extremes of the design space. Design criteria for a semi-active suspension system, that could significantly reduce, or even eliminate the ride comfort vs. handling compromise, are proposed. The system should be capable of switching safely and predictably between a stiff spring and high damping mode (for handling) as well as a soft spring and low damping mode (for ride comfort). A possible solution to the compromise, in the form of a four state, semi-active hydropneumatic spring-damper system, is proposed.     

Time delay in a semi-active damper: modelling the bypass valve

Ride comfort and handling of off-road vehicles can be significantly improved by replacing the normal passive dampers in the vehicle suspension system with controllable, two-state, semi-active dampers. The hydraulic valve, which enables the semi-active damper characteristics to be controlled, is a critical component of a semi-active damper and has a marked influence on suspension performance. Models of the dynamics of a hydraulic bypass valve used on semi-active suspension systems for heavy vehicles were investigated. It is envisaged that similar models will eventually be incorporated into a full vehicle, three-dimensional simulation study. Valve response time (or time delay) is used as a measure of model accuracy because it is an important parameter in the performance of a semi-active damper. Models were created with AMESim, a commercial fluid power simulation environment, and MATLAB. AMESim was found to be capable of dealing with detailed and complex fluid power models. Attempts to solve models of similar complexity in the MATLAB environment were unsuccessful due to numerical stiffness. Experimental work was conducted to obtain dynamic performance data with which to validate model integrity. Several external factors influenced the valve behaviour during experiments. Test bench dynamics significantly influences results and obscures the absolute accuracy of the models and the experimental data. The investigation demonstrated an approach to creating fluid power models for this application that can be used in simulation, but also indicated that substantial effort is required in the process. The accuracy of the current model is not sufficient for design purposes.     

Modeling of mass and charge transfer in an inverted rotating disk electrode (IRDE) reactor

In this work, the validation of a newly constructed inverted rotating disk electrode (IRDE) reactor is reported. Compared to the rotating disk electrode (RDE) reactor, the working electrode is changed in position from the top to the bottom of the electrochemical cell. The IRDE reactor is designed to facilitate the actual study of gas evolution reactions. It is studied whether the first-order analytical expression for the velocity field in an RDE reactor is also acceptable for an IRDE configuration. To that purpose, the kinetic parameters of the well-known ferri/ferro cyanide redox system are determined in both configurations and compared. This is done qualitatively by comparing the polarization curves obtained in the inverted and the conventional RDE configuration. Additionally, a statistically founded fitting algorithm is used to quantitatively determine the model parameters of the oxidation and reduction reaction. Not only the diffusion coefficients of Fe²⁺ and Fe³⁺ are calculated, but also the rate constants (k_ox and k_red) and the transfer coefficients (α_ox and α_red) are quantified and compared together with their respective standard deviation. It is found that the parameters of mass and charge transfer in both configurations agree well. So it is concluded that the same analytical equations of mass and charge transfer can be used in both the RDE and the IRDE reactor.