Quantitative determination of chloride by means of flow injection analysis with spectrophotometric detection in the UV/VIS range

Chloride is determined indirectly by Spectrophotometric flow injection analysis. Two systems are compared, both based on the principle of ion exchange of easily detectable anions versus chloride from suitable mercury salts. The first method is based on the exchange of chloride with chloranilate which is detected at 332 nm or at 306 nm in neutral or in acidic medium respectively. In the second case, chloride reacts with Hg(SCN)₂. The liberated thiocyanate forms a strongly coloured complex with Fe(III) in acidic solution with an absorption maximum at 460 nm. Both methods have a detection limit of about 5 mol Cl^–/l (175 ng/ml). In the case of the thiocyanate method, the relative standard deviation is about 2% (7 measurements) in the range of 5 to 150 mol/l and decreases significantly to a value of approximately 0.2% at higher concentrations; for the chloranilate method it is 10% for lower and about 1% for higher concentrations respectively.     

The Gaussian and augmented-plane-wave density functional method for ab initio molecular dynamics simulations

A new algorithm for density-functional-theory-based ab initio molecular dynamics simulations is presented. The Kohn–Sham orbitals are expanded in Gaussian-type functions and an augmented-plane-wave-type approach is used to represent the electronic density. This extends previous work of ours where the density was expanded only in plane waves. We describe the total density in a smooth extended part which we represent in plane waves as in our previous work and parts localised close to the nuclei which are expanded in Gaussians. Using this representation of the charge we show how the localised and extended part can be treated separately, achieving a computational cost for the calculation of the Kohn–Sham matrix that scales with the system size N as O(NlogN). Furthermore, we are able to reduce drastically the size of the plane-wave basis. In addition, we introduce a multiple-cutoff method that improves considerably the performance of this approach. Finally, we demonstrate with a series of numerical examples the accuracy and efficiency of the new algorithm, both for electronic structure calculations and for ab initio molecular dynamics simulations. Received: 15 December 1998 /Accepted: 18 February 1999 /Published online: 14 July 1999     

Particle image velocimetry in a foam-like porous structure using refractive index matching: a method to characterize the hydrodynamic performance of porous structures

We present a method to measure two-dimensional velocity fields inside an artificial foam-like porous structure using particle image velocimetry and a refractive index matching technique to avoid optical distortion. The porous structure is manufactured by stereolithography with the epoxy resin WaterShed^? XC 11122 as solid material, and anisole is used as refractive index-matched fluid. It was found that the direction of build-up of the stereolithographic structure plays an important role for the quality of the recorded images. The velocity fields measured in this study and the turbulent statistics derived thereof allow to characterize the hydrodynamic performance of the artificial foam-like structure and clarify the mechanisms of mixing. Results from this study compare well to results from a large eddy simulation reported by Hutter et?al. (Chem Eng Sci 66:519–529, 2011b) and hence reinforce these simulations.     

Theory of incremental motion in a body with initial elasto-plastic deformation

A theory of incremental deformation is developed for a body with initial stress and strain, valid for elastic and plastic pre-deformation. The superimposed motion is assumed hyperelastic. We present the constitutive equation, relating a measure of incremental stress to incremental strain, and the momentum equations referred to the prestrained initial configuration of the body. The latter is linearized with respect to the displacement field of the superimposed motion. For general nonlinear pre-deformation the constitutive theory of an anisotropic body may be based on the assumed strain energy that is an isotropic function of the Green strain tensor and a number of material directors of unit length. For bodies with elastoplastic prestrain and prestress, an elastic constitutive relation that depends on the plastic pre-deformation and the deformation from a relaxed state is postulated. Imposing the requirements of invariance with respect to rotations of the plastic pre-deformation and using the objectivity rule, we show that the constitutive function of stress must be an isotropic function of its arguments. This leads to a new theory of acoustoelasticity for an elasto-plastically prestrained material with anisotropic natural state by incorporating materially fixed unit directors as independent variables in the constitutive equations.

---

Zusammenfassung Es wird eine Theorie der inkrementellen Deformation für einen Körper mit Vorspannung und Vorverformung entwickelt, welche sowohl für elastische wie plastische Vorverformung Gültigkeit hat. Die überlagerte Bewegung wird als hyperelastisch angenommen. Wir leiten die Materialgleichung her, welche eine inkrementelle Spannung mit einer inkrementellen Verzerrung verknüpft und geben die Impulsgleichung in einer auf die anfängliche Verformung bezogenen Konfiguration. Diese Impulsgleichung wird bezüglich des überlagerten Verschiebungsfeldes linearisiert. Für eine allgemeine nichtlineare Vorverformung kann die Materialtheorie eines anisotropen Körpers auf der Basis einer postulierten Verzerrungsenergie gegründet werden, welche eine isotrope Funktion des Greenschen Verzerrungstensors und einer Zahl materieller Direktoren mit Länge 1 darstellt. Für elasto-plastisch vorgespannte und vorverformte Körper wird eine elastische Materialgleichung postuliert, die von der plastischen Vorverformung sowie der Deformation aus einer relaxierten Konfiguration abhängt. Es wird gezeigt, daß die Materialgleichung für den Spannungstensor eine isotrope Funktion ihrer Argumente sein muß, wenn man als übergeordnetes Prinzip das Objektivitätsprinzip fordert und Invarianz des Spannungsfunktionals gegenüber Rotationen der plastischen Vordeformation verlangt. Durch Einführen von materiellen Direktoren der Einheitslänge als unabhängige Konstitutivvariablen erhält man hieraus eine neue Theorie der Akusteolastizität für elasto-plastisch vorverformte Materialien mit anisotropen natürlichen Referenzzuständen.

     

A viscoelastic damage model for polycrystalline ice,inspired by Weibull-distributed fiber bundle models. Part II: Thermodynamics of a rank-4 damage model

We consider a viscoelastic–viscoplastic continuum damage model for polycrystalline ice. The focus lies on the thermodynamics particularities of such a constitutive model and restrictions on the constitutive theory which are implied by the entropy principle. We use Müller’s formulation of the entropy principle, together with Liu’s method of exploiting it with the aid of Lagrange multipliers.     

A case study of algorithm selection for the traveling thief problem

Many real-world problems are composed of several interacting components. In order to facilitate research on such interactions, the Traveling Thief Problem (TTP) was created in 2013 as the combination of two well-understood combinatorial optimization problems. With this article, we contribute in four ways. First, we create a comprehensive dataset that comprises the performance data of 21 TTP algorithms on the full original set of 9720 TTP instances. Second, we define 55 characteristics for all TPP instances that can be used to select the best algorithm on a per-instance basis. Third, we use these algorithms and features to construct the first algorithm portfolios for TTP, clearly outperforming the single best algorithm. Finally, we study which algorithms contribute most to this portfolio.     

Characterization of the Element Distribution Within TiN Coatings with SIMS

 The distribution of the relevant elements within TiN coatings, made with two different physical deposition methods as the conventional dc vacuum arc method and the filtered high current pulsed arc method (Φ-HCA) are characterized and finally compared. Despite the rougher surface of the dc-arc produced TiN layer, which is due to accumulated droplets, there is no evidence of different stoechiometric composition of Ti and N on the surface. The interface of the dc-arc produced TiN layer (600 nm) is 10 times wider than the one made with the new filtered high current pulsed arc method (60 nm). However the TiN layer made by Φ-HCA shows an inhomogeneous distribution of aluminum and chlorine in the vertical direction, whereas the dc-arc sample is homogeneous. Furthermore, the TiN layer made by Φ-HCA shows vertically an obvious local maximum of chlorine at a depth of about 130 nm. This vertical local maximum has an homogeneous distribution in horizontal direction, which means that a thin, chlorine enriched layer has been incorporated inside the TiN layer. Nevertheless, quantification by SIMS shows that aluminum as well as chlorine concentrations of both samples are too low to influence any TiN properties. Received January 3, 2000. Revision April 4, 2000.     

Characterization of Two-Component Metal Coatings (Al/Sn) with SIMS

 Vacuum deposited films of immiscible metal–metal systems can be applied as tribological coatings for plain bearings in high performance diesel engines. These industrially manufactured coatings show higher lifetimes than conventional electroplated coatings. For our investigations we used aluminum-tin coatings of 1 μm thickness on a glass substrate produced by sequential deposition from two separate targets under working gas pressure of 0.4 Pa. The tough Al matrix takes high mechanical loads and the soft inclusions of Sn act as solid lubricant. While Sn is deposited it migrates on the Al surface and grows as islands. We characterized the conformation and the distribution of the Sn islands on the surface and to the interstitial area between the islands with 3-D secondary ion mass spectroscopy (SIMS). The existence of a Sn layer between the islands (“wetting layer”) has been detected by SIMS and verified by measurements with Auger electron spectroscopy (AES).     

Interfacial and self-assembly properties of bolaamphiphilic compounds derived from a multifunctional oil

The self-assembly characteristics in aqueous solutions of cationic bolaamphiphiles with systematic changes in their chemical structure is described with respect to their interfacial properties within water and at the air/water interface. Six cationic bolaamphiphiles were synthesized from multifunctional vernonia oil with the following variations: (a) two different alkyl chain lengths connecting the head groups, (b) polar ester or hydrogen bonding amide groups within the hydrophobic domain, and (c) an acetylcholine cationic head group with different conjugation sites to the alkyl chain. Surface tension measurements were used for determining critical aggregation concentration (CAC) values and air/water interfacial parameters such as 'effectiveness', surface excess concentration and area occupied by one molecule in the air/water interface. Fluorescent studies with pyrene were used to characterize CAC properties within the aqueous volume and transmission electron microscopy (TEM) for determining the aggregate structure's size, homogeneity and morphology. A bolaamphiphile molecular structure vs. interfacial property relationship was derived from this data which could be used to determine the molecular structure properties needed to generate interfacial forces to form either spherical vesicles or fibrous networks. The effects of the aliphatic chain length, head group orientation and functional groups within the hydrophobic domain on CAC, surface tension properties and self-aggregate morphology are described. Most bolaamphiphiles studied had CAC values in the 10-190 μM range, while two out of the six were found to assemble into MLM spherical vesicles with diameters ranging up to 120 nm suitable for drug delivery applications. Others formed a gelatinous network of fibers or multi-lamellar vesicles.