Softening during and after the hot deformation of the AISI 321 steel with respect to practical applications

The softening processes during and after the hot deformation (850–1180 C) in AISI 321 stainless steel were studied with respect to true strains _D and true strain rates . The analysis of deformation curves indicates the occurrence of dynamic recrystallization for values of Zener-Hollomon parameterZ10¹⁵ s^–1. The retardation of static recrystallization by fine Ti(N, C) precipitates is documented by microstructure studies and by variations of annealing conditions.     

Observation and analysis ofE mesons in\bar p p annihilation at rest in H2 gas

Antiproton-proton annihilation at rest in a gaseous H₂ target at NTP into the final state π⁺ π^? K ^± π^? (K ⁰) with an undetectedK ⁰ or \(\bar K^0 \) has been investigated. We observe theE(1420) resonance in the invariant mass spectrum (K ⁰)_miss K ^± π^? with massM _E =1413±8 MeV/c² and widthГ ^E =62 ± 16MeV/c² and find evidence for the production of thef ₁(1285). The absolute branching ratio of \(\bar p\) p → π⁺ π^? E ⁰,E ⁰ →K ₀ ^L K ^± π ^? at (61±6)%P wave annihilation is (3.0±0.9)·10^?4 of all annihilations. The observed suppression of theE production fromP wave with respect to theS wave together with some simple selection rules suggest that the quantum numbers of theE(1420) areJ ^pc=0^?+ and not I⁺⁺.     

The Büttiker-Landauer model generalized

Büttiker and Landauer studied scattering off an oscillating rectangular barrier in order to shed light on the time aspects of tunneling. The expression for the traversal time resulting from this study is controversial. In addition, doubts have recently been expressed on technical aspects of their work. In an attempt to clarify these issues, we investigate a generalization of their model to arbitrary oscillating barriers,V(x, t)=V ₀(x)+V ₁(x)cos t. In the process, we confirm that Büttiker and Landauer's work is technically sound. However, we show, by several examples, that no direct general relation exists between the characteristic frequency of an oscillating barrier and the duration of the tunneling process. For a wide range of realistic parameters this characteristic frequency does not even exist.This paper is dedicated to E. G. D. Cohen.     

Ozone production in oxygen by means of F2-laser irradiation at λ=157.6 nm

Ozone is generated in pure oxygen (p5 kPa), synthetic air (p7 kPa) and oxygen-argon mixtures (p3 kPa) by irradiation of these gases with the VUV light of a repetitively pulsed (f _L15 Hz) F₂-laser at =157.6 nm with maximum about 4 mJ/pulse. An absorption photometer measurement operating at 253.7 nm (Hg line) determines the ozone concentration as a function of oxygen and/or additive gas pressure, the repetition frequency of the laser and the wall temperature of the reaction chamber. The temporal development of the ozone concentration as a function of these parameters is calculated by means of rate equations for the species O(³ P), O₂(X ³ _g ^– ), O₃(¹ A ₁), O(¹ D), O₂(a ¹_g), O₂(b ¹ _g ⁺ ) and vibrationally excited O ₃ ^* (¹ A ₁) and the photon distribution. The maximum concentration of O₃ in the sealed-off chamber reaches 1.6% in pure O₂, 4.1% in air and 1.2% in a 1:5 O₂-Ar mixture at 3 kPa. The annihilation of O₃ by the wall and temperature dependent volume processes (300 KT395 K) is studied and the experimental and theoretical results are compared.     

Maskierung mit Kaliumjodid bei direkten Titrationen von Kupfer(II) mit Äthylendiamintetraessigsäure

Zusammenfassung Die Jodidoxydation durch Cu(II) wird in Anwesenheit von Ammoniak, Natriumtartrat, citrat oder -oxalat infolge Komplexbildung verhindert. Daher kann man z. B. Quecksüber(II) in Anwesenheit der genannten Komplexbildner mit Kaliumjodid maskieren und Kupfer(II) durch direkte Titration mit ÄDTA gegen Murexid, Brenzcatechinviolett, Chromazurol S, PAN oder PAR als Indikator bestimmen.

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Masking with potassium iodide in direct titrations of copper(II) with ethylenediamine tetraacetic acid

Summary The formation of a complex prevents the iodide oxidation by Cu(II) in the presence of ammonia, sodium tartrate, citrate, or oxalate. Hence mercury(II) for instance, can be masked against potassium iodide in the presence of these complex formers, and Cu(II) can be determined by direct titration with EDTA in the presence of murexide, pyrocatechol violet, chromazurol, PAN or PAR as indicator.

     

Photophysical properties of borondipyrromethene analogues in solution

The photophysical properties of seven new 8-(p-substituted)phenyl analogues of 4,4-difluoro-3,5-dimethyl-8-(aryl)-4-bora-3a,4a-diaza-s-indacene (derivatives of the well-known fluorophore BODIPY) in several solvents have been studied by means of absorption and steady-state and time-resolved fluorimetry. For each compound, the fluorescence quantum yield and lifetime are lower in solvents with higher polarity owing to an increase in the rate of nonradiative deactivation. Increasing the electron withdrawing strength of the p-substituent on the phenyl group in position 8 also leads to lower fluorescence quantum yields and lifetimes. When the p-substituent on the phenyl group in position 8 is a tertiary amine [8-(4-piperidinophenyl), 8-(4-N,N-dimethylaminophenyl), and 8-(4-morpholinophenyl)], the low quantum yields of these compounds in more polar solvents can be rationalized by the inversion of the energy levels of an apolar, highly fluorescent and a polar, nonfluorescent excited state, where charge transfer from the tertiary amine to the BODIPY unit occurs. These amine analogues can be protonated at low pH in aqueous solution. Fluorescence titrations yielded pK(a) values of their conjugate ammonium salts which are in agreement with the electron donating tendency of the amine group: piperidino (4.15) > dimethylamino (2.37) > morpholino (1.47), with the pK(a) values in parentheses. The rate constant of radiative deactivation (k(f)) is the same for all compounds in all solvents studied (k(f) = 1.4 x 10(8) s(-1)).     

Workshop on Sample Controlled Thermal Analysis

Journal of Thermal Analysis and Calorimetry -     

Thermolysis of 1,2-dithiolylium salts in the ion source of the mass spectrometer

1,2-Dithiolylium salts are thermolysed in the ion source of a mass spectrometer; some salts (group I) undergo thermolysis to give a stable dithiolyl radical where subsequent ionization gives rise to a mass spectrum in which the parent ion corresponds to the dithiolyl ion. The radical may be stabilized before ionization by expulsion of a hydrogen atom to form a neutral dithiole derivative, and then mass spectra exhibit abundant molecular ions corresponding to such dithiole derivatives.Other salts (group II) may expel a proton with formation of a carbene and subsequent dimerization to a tetrathiafulvalene.The thermolytic behaviour of 1,2-dithiolylium salts is compared with their electrochemical behaviour and several analogies are found.     

Z/E-photoisomerizations of olefins with 4npi- or (4n + 2)pi-electron substituents: zigzag variations in olefin properties along the T(1) state energy surfaces

[Figure: see text]. A quantum chemical study has been performed to assess changes in aromaticity along the T1 state Z/E-isomerization pathways of annulenyl-substituted olefins. It is argued that the point on the T1 energy surface with highest substituent aromaticity corresponds to the minimum. According to Baird (J. Am. Chem. Soc. 1972, 94, 4941), aromaticity and antiaromaticity are interchanged when going from S0 to T1. Thus, olefins with S0 aromatic substituents (set A olefins) will be partially antiaromatic in T1 and vice versa for olefins with S0 antiaromatic substituents (set B olefins). Twist of the C=C bond to a structure with a perpendicular orientation of the 2p(C) orbitals (3p*) in T1 should lead to regaining substituent aromaticity in set A and loss of aromaticity in set B olefins. This hypothesis is verified through quantum chemical calculations of T1 energies, geometries (bond lengths and harmonic oscillator measure of aromaticity), spin densities, and nucleus independent chemical shifts whose differences along the T1 PES display zigzag dependencies on the number of -electrons in the annulenyl substituent of the olefin. Aromaticity changes are reflected in the profiles of the T1 potential energy surfaces (T1 PESs) for Z/E-isomerizations because olefins in set A have minima at 3p* whereas those in set B have maxima at such structures. The proper combination (fusion) of the substituents of set A and B olefins could allow for design of novel optical switch compounds that isomerize adiabatically with high isomerization quantum yields.     

Interparticle interactions in agglomerates of alpha-Fe2O3 nanoparticles: influence of grinding

We have chemically prepared a sample of antiferromagnetic alpha-Fe2O3 nanoparticles by a gel-sol technique. M?ssbauer spectra of the as-prepared sample showed that superparamagnetic relaxation was suppressed due to strong magnetic interparticle interactions even at room temperature. However, subsequent grinding of the sample by hand in a mortar for some minutes resulted in fast superparamagnetic relaxation of some of the particles. The effect was even more dramatic if the alpha-Fe2O3 powder was ground for a longer time or together with nonmagnetic eta-Al2O3 nanoparticles. Similar effects were found after low-energy ball milling. Thus it is found that the agglomeration of the nanoparticles during preparation under wet conditions results in strong magnetic interparticle interaction, but a relatively gentle mechanical treatment is sufficient to break up the agglomerates, resulting in much weaker interactions. We show that these effects can also be seen when a soil sample containing magnetic nanoparticles is ground.