Measurement uncertainty of selenium determination in the reference material Seronorm Trace Elements Serum by hydride generation atomic fluorescence spectrometry

 An analytical result is not considered to be complete without a statement of the measurement uncertainty associated with it. Evaluation of measurement uncertainty is therefore an essential part of every determination. In the present study the measurement uncertainty of the result of determination of selenium in the reference material Seronorm Trace Elements Serum was studied. The combination of a digestion procedure using sulfuric acid, V₂O₅ in H₂SO₄ and hydrogen peroxide and the continuous flow approach of hydride generation atomic fluorescence spectrometry (HG-AFS) detection was used for selenium determination. The total uncertainty budget was calculated with the help of the GUM Workbench program, in which computations follow the rules of the ’ISO guide to the expression of uncertainty in measurement’. The major sources of uncertainty were found to be due to the recovery of the procedure, measurement of peak heights and the purity of Na₂SeO₃. A selenium mass fraction of 77.1±4.8 ng/g (with a coverage factor of 2.1, 95% probability) was determined, which is comparable with the recommended value of 80 ng/g. Received: 13 September 2002 Accepted: 23 December 2002 Acknowledgements We would like to thank Tinkara Buˇcar, B.Sc. for useful discussions and the IAEA Vienna, for financial support of the project 11553/RO. Presented at CERMM-3, Central European Reference Materials and Measurements Conference: The function of reference materials in the measurement process, May 30–June 1, 2002, Rogaška Slatina, Slovenia Correspondence to V. Stibilj     

On the dynamic electromechanical loading of dielectric elastomer membranes

Dielectric elastomer actuators (DEAs) have received considerable attention recently due to large voltage-induced strains, which can be over 100%. Previously, a large deformation quasi-static model that describes the out-of-plane deformations of clamped diaphragms was derived. The numerical model results compare well with quasi-static experimental results for the same configuration. With relevance to dynamic applications, the time-varying response of initially planar dielectric elastomer membranes configured for out-of-plane deformations has not been reported until now. In this paper, an experimental investigation and analysis of the dynamic response of a dielectric elastomer membrane is reported. The experiments were conducted with prestretched DEAs fabricated from 0.5 mm thick polyacrylate films and carbon grease electrodes. The experiments covered the electromechanical spectrum by investigating membrane response due to (i) a time-varying voltage input and (ii) a time-varying pressure input, resulting in a combined electromechanical loading state in both cases. For the time-varying voltage experiments, the membrane had a prestretch of three and was passively inflated to various predetermined states, and then actuated. The pole strains incurred during the inflation were as high as 25.6%, corresponding to slightly less than a hemispherical state. On actuation, the membrane would inflate further, causing a maximum additional strain of 9.5%. For the time-varying pressure experiments, the prestretched membrane was inflated and deflated mechanically while a constant voltage was applied. The membrane was cycled between various predetermined inflation states, the largest of which was nearly hemispherical, which with an applied constant voltage of 3 kV corresponded to a maximum polar strain of 28%. The results from these experiments reveal that the response of the membrane is a departure from the classical dynamic response of continuum membrane structures. The dynamic response of the membrane is that of a damped system with specific deformation shapes reminiscent of the classical membrane mode shapes but without same-phase oscillation, that is to say all parts of the system do not pass through the equilibrium configuration at the same time. Of particular interest is the ability to excite these deformations through a varying electrical load at constant mechanical pressure.     

Synthesis and optical properties of tetraphenylmethane-based tetrahedral fluorescent compounds and their water-soluble PEG-linked polymers

The synthesis and optical properties of tetrahedral fluorescent compounds comprising of tetraphenylmethane as the core and oligothiophenes as the chromophoric arms, and their water-soluble poly(ethylene glycol)-linked polymers are reported.     

Structural and electrical properties of crystalline (1−x)Ta2O5−xTiO2 thin films fabricated by metalorganic decomposition

Polycrystalline (1−x)Ta₂O₅−xTiO₂ thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO₂ layer was formed at the (1−x)Ta₂O₅−xTiO₂/Si interface. Thin films with 0.92Ta₂O₅–0.08TiO₂ composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×10¹¹ cm⁻² eV⁻¹, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm² was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10⁻⁹ A/cm² up to an applied electric field of 6 MV/cm.     

Mössbauer study on LiFePO4 cathode material for lithium ion batteries

Crystalline LiFePO₄ has been synthesized using solid-state, spray pyrolysis, and wet chemical methods. The crystal parameters were obtained from Rietveld’s refinement methods of the X-ray diffraction patterns. A detailed investigation of the Fe valency carried out using Mössbauer spectroscopy at room temperature indicates that Fe is predominantly present in its bivalent state.     

Numerical analysis of a model of cure process for composites

We consider a composite material composed of fibres included in a resin which becomes solid when it is heated up (reaction of reticulation). The mathematical modelling of the cure process is given by a kinetic equation describing the evolution of the reaction of reticulation coupled with the heat equation. In this paper, we are interested in the computation of approximate solutions. We propose a family of discretized problems depending on two parameters (β₁, β₂) ε [0, 1]² which split the linear and non‐ linear terms in implicit and explicit parts. We prove the stability and convergence of the discretization for any (β₁, β₂) ε [½, 1 ] × [0, 1]. We present also some numerical results. Copyright © 2006 John Wiley & Sons, Ltd.     

Microscopic Theory of Blue Phases Ⅰ and Ⅱ of Liquid Crystal

The microscopic theory of the blue phases of chiral liquid crystal is proposed. Beginning with the potential between two molecules, by using the cell model of liquid, applying statistical physical method, the distribution function and the free energy of the system are obtained. By using variational approach and zero-order approximation, the differential equation that the order parameter tensor of the blue phase can satisfy is obtained. Then we change the differential equation to the eigenequation problem in quantum mechanics. Considering the symmetry of the blue phases,the order parameter tensors of blue phases Ⅰ and Ⅱ can be made up of the eigenvectors. Our results are the same as the results of Ginzberg-Landau‘s phenomenological theory. The parameters in the order parameter tensors that we calculate in the located system are close to the predecessors‘ results.     

Syntheses,crystal structures and blue emission of three zinc(II) coordination polymers with a 4,4′‐dicarboxybiphenyl sulfone ligand

Three novel zinc complexes [Zn(dbsf)(H₂O)₂] ( 1 ), [Zn(dbsf)(2,2′‐bpy)(H₂O)]·(i‐C₃H₇OH) ( 2 ) and [Zn(dbsf)(DMF)] ( 3 ) (H₂dbsf = 4,4′‐dicarboxybiphenyl sulfone, 2,2′‐bpy = 2,2′‐bipyridine, i‐C₃H₇OH = iso‐propanol, DMF = N,N‐dimethylformamide) were first obtained and characterized by single crystal X‐ray crystallography. Although the results show that all the complexes 1–3 have one‐dimensional chains formed via coordination bonds, unique three‐dimensional supramolecular structures are formed due to different coordination modes and configuration of the dbsf^2? ligand, hydrogen bonds and π–π interactions. Iso‐propanol molecules are in open channels of 2 while larger empty channels are formed in 3 . As compared with emission band of the free H₂dbsf ligand, emission peaks of the complexes 1–3 are red‐shifted, and they show blue emission, which originates from enlarging conjugation upon coordination. Copyright © 2006 John Wiley & Sons, Ltd.     

Chiral discrimination of a helically organized crown ether array parallel to the helix axis of polyisocyanate

The asymmetric polymerization of 4′‐isocyanatobenzo‐18‐crown‐6 with the lithium amide of (S)‐(2‐methoxymethyl)pyrrolidine successfully proceeded to afford end‐functionalized poly(4′‐isocyanatobenzo‐18‐crown‐6) with (S)‐(2‐methoxymethyl)pyrrolidine (polymer 2 ). In the circular dichroism (CD) spectrum of 2 , a clear positive Cotton effect was observed in the range of 240–350 nm corresponding to the absorption of the polymer backbone, indicating that 2 partially formed a one‐handed helical structure, which was preserved by the chirality of (S)‐(2‐methoxymethyl)pyrrolidine bonding to the terminal end in 2 . In the titration experiments for the CD intensity of 2 in the presence of D ‐ and L ‐Phe·HClO₄ (where Phe is phenylalanine), a small but remarkable difference was observed in the amount of the chiral guest needed for saturation of the CD intensity and in the saturated CD intensity, indicating that the extremely stable, one‐handed helical part should exist in the main chain of 2 , which was not inverted even when the unfavorable chiral guest for the predominant helical sense, L ‐Phe·HClO₄, was added. In addition, helical polymer 2 exhibited a chiral discrimination ability toward racemic guests; that is, the guests were extracted from the aqueous phase into the organic phase with enantiomeric excess. The driving force of the chiral discrimination ability of 2 should certainly be attributed to the one‐handed helical structure in 2 . © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 325–334, 2006     

The nanogranular nature of C-S-H

Despite its ubiquitous presence as binding phase in all cementitious materials, the mechanical behavior of calcium-silicate-hydrates (C-S-H) is still an enigma that has deceived many decoding attempts from experimental and theoretical sides. In this paper, we propose and validate a new technique and experimental protocol to rationally assess the nanomechanical behavior of C-S-H based on a statistical analysis of hundreds of nanoindentation tests. By means of this grid indentation technique we identify in situ two structurally distinct but compositionally similar C-S-H phases heretofore hypothesized to exist as low density (LD) C-S-H and high density (HD) C-S-H, or outer and inner products. The main finding of this paper is that both phases exhibit a unique nanogranular behavior which is driven by particle-to-particle contact forces rather than by mineral properties. We argue that this nanomechanical blueprint of material invariant behavior of C-S-H is a consequence of the hydration reactions during which precipitating C-S-H nanoparticles percolate generating contact surfaces. As hydration proceeds, these nanoparticles pack closer to center on-average around two characteristic limit packing densities, the random packing limit (η=64%) and the ordered face-centered cubic (fcc) or hexagonal close-packed (hcp) packing limit (η=74%), forming a characteristic LD C-S-H and HD C-S-H phase.