Numerical and experimental investigations of phase segragation effects in binary brazing solders

Solder materials occupy many of fields for technical application (e.g. solder joints in automotive control units or in microelectronic packages). They are required to provide electrical and mechanical connections between different components. Due to their wide range of applications solder alloys are subject to a great variety of microstructural changes such as phase separation and coarsening processes. The micromorphological variations influence strength and life expectation of solder materials, in particular, in very small components such as solder joints in microelectronic packages. In order to analyze the microstructural evolution with a diffusion theory of heterogeneous solid mixtures we employ an extended Cahn-Hilliard phase field model. The diffusion equation under consideration constitutes a partial differential equation involving spatial derivatives of fourth order. Thus, the variational formulation of the problem requires approximation functions which are piecewise smooth and globally C1-continuous. In our contribution we fulfil the continuity requirement by means of rational B-spline finite element basis functions. To illustrate the versatility of this approach numerical simulations of phase decomposition and coarsening controlled by diffusion and by mechanical loading are discussed and compared with experimental results. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Silver(I) complexation of linked 2,2'-dipyridylamine derivatives. Synthetic, solvent extraction, membrane transport and X-ray structural studies

Synthesis of the 2,2'-dipyridylamine derivatives di-2-pyridylaminomethylbenzene 1, 1,2-bis(di-2-pyridylaminomethyl)benzene 2, 1,3-bis(di-2-pyridylaminomethyl)benzene 3, 2,6-bis(di-2-pyridylaminomethyl)pyridine 4, 1,4-bis(di-2-pyridylaminomethyl)benzene 5, and 1,3,5-tris(di-2-pyridylaminomethyl)benzene 6 are reported together with the single-crystal X-ray structures of 2, 3, and 5. Reaction of individual salts of the type AgX (where X = NO(3)(-), PF(6)(-), ClO(4)(-), or BF(4)(-)) with the above ligands has led to the isolation of thirteen Ag(I) complexes, nine of which have also been characterised by X-ray diffraction. In part, the inherent flexibility of the respective ligands has resulted in the adoption of a range of coordination arrangements. A series of liquid-liquid (H(2)O/CHCl(3)) extraction experiments of Ag(I) with varying concentrations of 1-6 in the organic phase have been undertaken, with the counter ion in the aqueous phase being respectively picrate, perchlorate and nitrate. In general, extraction efficiencies for a given ionophore followed the Hofmeister order of picrate > perchlorate > nitrate; in each case the tris-dpa derivative 6 acting as the most efficient extractant of the six systems investigated. Competitive seven-metal bulk membrane transport experiments (H(2)O/CHCl(3)/H(2)O) employing the above ligands as the ionophore in the organic phase and equimolar concentrations of Co(II), Ni(II), Zn(II), Cu(II), Cd(II), Pb(II) and Ag(I) in the aqueous source phase were also undertaken, with transport occurring against a pH gradient. Under the conditions employed 1 and 5 yielded negligible transport of any of the metals present in the source phase while sole transport selectivity for Ag(I) was observed for 2-4 and 6.     

Zeros of Jacobi polynomials Pn( α, β)$ P_{n}^{(\alpha ,\beta)} $, − 2 < α, β < − 1

The sequence of Jacobi polynomials \(\{P_{n}^{(\alpha ,\beta )}\}_{n = 0}^{\infty }\) is orthogonal on (??1,1) with respect to the weight function (1 ? x)^α(1 + x)^β provided α > ??1,β > ??1. When the parameters α and β lie in the narrow range ??2 < α, β < ??1, the sequence of Jacobi polynomials \(\{P_{n}^{(\alpha ,\beta )}\}_{n = 0}^{\infty }\) is quasi-orthogonal of order 2 with respect to the weight function (1 ? x)^α+?1(1 + x)^β+?1 and each polynomial of degree n,n ≥?2, in such a Jacobi sequence has n real zeros. We show that any sequence of Jacobi polynomials \(\{P_{n}^{(\alpha ,\beta )}\}_{n = 0}^{\infty }\) with ??2 < α, β < ??1, cannot be orthogonal with respect to any positive measure by proving that the zeros of Pn??1(α,β) do not interlace with the zeros of Pn(α,β) for any \(n \in \mathbb {N},\)n ≥?2, and any α,β lying in the range ??2 < α, β < ??1. We also investigate interlacing properties satisfied by the zeros of equal degree Jacobi polynomials Pn(α,β),Pn(α,β+?1) and Pn(α+?1,β+?1) where ??2 < α, β < ??1. Upper and lower bounds for the extreme zeros of quasi-orthogonal order 2 Jacobi polynomials Pn(α,β) with ??2 < α, β < ??1 are derived.     

P-31 Solid State Nuclear Magnetic Resonance Investigations on Cyclophosphazenes

Abstract

The present study deals with solid state NMR investigations on cyclophosphazeaes wah the following substituents: -NH₂, -OMe, -F, -Cl, -Br, at which the substituent atoms are elements of the 2^nd period (N, O, and F) or elements of the 7^th main group (F, Cl, and Br). The NMR spectra were obtained by a BRUKER MSL 300 spectrometer using a resonance frequenacy of 121.496 MHz. With each compound a static powder spectrum, a hgh speed MAS spectrum, and several side band spectra were recorded.     

A new non-enzymatic tracer for time-resolved fluoroimmunoassay of triazine herbicides

Summary The synthesis, characterization and application of a new kind of conjugate as tracer for use in time-resolved fluoroimmunoassay of triazine herbicides is described. Bovine serum albumin (BSA) served as carrier molecule, to which a triazine herbicide derivative and the Eu(III)-chelate W8044-Eu were subsequently coupled. The conjugate was characterized after each synthesis step by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS). The total composition was 1 BSA : 5.2 (±0.7) haptens : 5.1 (±0.4) fluorophores as calculated from the MALDI-MS data. The conjugate was successfully applied in competitive fluoroimmunoassays with sequential or simultaneous incubation of herbicide and tracer. With the sequential assay, the lowest detection limit was 0.1 g/l for terbutryn. Results of assays performed with microtiter strips were compared with those obtained with commercial micro affinity columns.     

An Experimental and Mechanistic Investigation of the Complexities Arising During Inhibition of the Briggs?Rauscher Reaction by Antioxidants

A method to determine the relative antioxidant capacity of radical scavengers based on the inhibition of the oscillations of the Briggs? Rauscher (BR) oscillating reaction was previously reported. A semiquantitative mechanistic interpretation of the inhibitory effects required two steps to obtain simulated inhibition times in very good agreement with the experimental ones. The first step is inhibitory, involving H‐atom transfer from antioxidant to the HOO^. radical; the second step is a first‐order degradation of the antioxidant to unspecified products. Since the degradation may be due to oxidation and/or iodination of the antioxidant, we studied the kinetics of the subsystems IO (H⁺)+antioxidant and I₂(H⁺)+antioxidant. We used 2,5‐ and 2,6‐dihydroxybenzoic acids, caffeic acid (=3‐(3,4‐dihydroxyphenyl)prop‐2‐enoic acid), ferulic acid (=3‐(4‐hydroxy‐3‐methoxyphenyl)prop‐2‐enoic acid), pyrocatechol (=benzene‐1,2‐diol), and hydroquinone (=benzene‐1,4‐diol) as antioxidants. Spectra in the wavelength range 500–250 nm were repeated at given time intervals to follow the peaks of the iodine and oxidation products, which were mainly quinones. For the iodination of the above diphenols (=benzenediol derivatives) the substitution and/or addition reactions with I₂ or HOI were found to be relatively slow compared to oxidation by IO . Approximate rate constants for oxidation were obtained on the basis of a reasonable kinetic model by using a suitable numerical integration program. Although these complexities can arise also in the completely inhibited BR oscillator, we believe that the inhibitory effects are due to the HOO^. scavenging action by diphenols or by quinones since HOO^. radicals are also potential reducing agents. We propose two steps that could maintain a small reservoir of diphenol, while both quinone and diphenol deplete HOO^. radicals. In short, the complexities do not affect the method for monitoring the relative activity of antioxidants based on the BR oscillating reaction. The effects of temperature on the inverse of the oscillatory time in the BR‐uninhibited system, on the inverse of inhibition times, and on the time length of the resumed oscillations for four antioxidants were also investigated. Apparent average activation energies were obtained.     

A First Approach to the cis‐trans‐cis‐Photocyclodimers of 1,2‐Naphthoquinone

On irradiation (λ=350 nm), 1,2‐naphthoquinone (=naphthalene‐1,2‐dione) monoacetals 1 are converted quantitatively to mixtures of the cis‐trans‐cis‐photocyclodimers 2 and 3 . Careful hydrolysis of each of the (parent) pentacyclic diacetals 2a and 3a affords the – rather unstable – compounds 4 and 5 , respectively.     

Potentiometric stripping analysis for zinc,cadmium. lead and copper in sea water

Analytical procedures for the determination of zinc(II), cadmium (II), lead(II) and copper(II) in sea water by potentiometric stripping analysis are described. The results are compared with those obtained by a combined solvent extraction-atomic absorption method both in the laboratory and on-board ship. The detection limits for zinc, cadmium, lead and copper are 0.03, 0.03, 0.01 and 0.02 μg l^-1, respectively, for a total analysis time of about 75 min. A very thin mercury film is useful in the determination of lead and copper.     

Recycling of process streams in ethanol production from softwoods based on enzymatic hydrolysis

In ethanol production from lignocellulose by enzymatic hydrolysis and fermentation, it is desirable to minimize addition of fresh-water and waste-water streams, which leads to an accumulation of substances in the process. This study shows that the amount of fresh water used and the amount of waste water thereby produced in the production of fuel ethanol from softwood, can be reduced to a large extent by recycling of either the stillage stream or part of the liquid stream from the fermenter. A reduction in fresh-water demand of more than 50%, from 3 kg/kg dry raw material to 1.5 kg/kg dry raw material was obtained without any negative effects on either hydrolysis or fermentation. A further decrease in the amount of fresh water, to one-fourth of what was used without recycling of process streams, resulted in a considerable decrease in the ethanol productivity and a slight decrease in the ethanol yield