Cavitation and morphological changes in polypropylene deformed at elevated temperatures

Polypropylene (PP) thick films were subjected to tensile drawing at various temperatures from the room temperature to 100 °C. Morphological alterations during drawing were followed by wide‐angle X‐ray scattering, small‐angle X‐ray scattering, and scanning electron microscopy (SEM) of sectioned and etched samples, volume strain measurement, and light transparency measurement at various level of strain. The morphological observations were paralleled with stress–strain determination. Samples drawn at 25 and 40 °C undergo severe cavitation contributing to their volume increase up to 90–95%. The volume increase contributes greatly to the engineering strain. PP drawn at 70 and 100 °C does not cavitate. At the strain up to 1.2, a high lamellae orientation is observed in SEM, whereas the 2D WAXS patterns show in contrary circular diffraction rings indicating low orientation of crystals. The rotation of lamellae toward drawing direction is associated with reverse rotation of chains in crystals due to fine chain slips. These two rotations in opposite directions counterbalance resulting in a much weaker crystal orientation than expected from the SEM images. Noncavitating samples retain their translucency up to a high strain. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1271–1280, 2010     

Atom-type assignment in molecules and clusters by perturbation theory-A complement to X-ray structure analysis

An approach to distinguish elements with similar atomic numbers in molecules and clusters is presented and applied to experimentally synthesized and structurally characterized mixed-metallic compounds. By first treating a homogenized reference system constructed from the original compound and applying first-order perturbation theory it is possible to find the most stable distribution of the atom types to the atomic sites in a very efficient way. This work is focused on the appropriate choice of homogenized reference systems and on applications treating experimentally synthesized compounds. With these examples is shown that the method is a helpful complement to X-ray crystal structure analysis.     

Dipole moment enhancement in molecular crystals from X-ray diffraction data.

Although reliable determination of the molecular dipole moment from experimental charge density analyses on molecular crystals is a challenging undertaking, these values are becoming increasingly common experimental results. We collate all known experimental determinations and use this database to identify broad trends in the dipole moment enhancements implied by these measurements as well as outliers for which enhancements are pronounced. Compelling evidence emerges that molecular dipole moments from X-ray diffraction data can provide a wealth of information on the change in the molecular charge distribution that results from crystal formation. Most importantly, these experiments are unrivalled in their potential to provide this information in such detail and deserve to be exploited to a much greater extent. The considerable number of experimental determinations now available has enabled us to pinpoint those studies that merit further attention, either because they point unequivocally to a considerable enhancement in the crystal (of 50 % or more), or because the experimental determinations suggest enhancements of 100 % or more--much larger than independent theoretical estimates. In both cases further detailed experimental and theoretical studies are indicated.     

FTIR spectroscopic characterization of structural changes in polyamide‐6 fibers during annealing and drawing

First, we report the development of Fourier transform infrared (FTIR) spectroscopic methods to determine the α/γ‐crystalline phase ratio of polyamide‐6 fibers and, in combination with density measurements, the total crystallinity. Using density determinations of the crystallinity of pure α and pure γ samples, we found the absorption coefficient ratio for the 930 (α) and 973 cm⁻¹ (γ) bands to be 4.4, from which we could obtain the α/γ ratio for any polyamide‐6 sample. The application of this FTIR method to the quantitative analysis of phase changes during thermal treatment and the drawing of polyamide‐6 was then made. We confirmed that crystallization during thermal treatments involved increases in both phases and did not involve crystal‐to‐crystal transformation, whereas drawing involved both crystallization of the amorphous phase in the α form and γ→α transformation. Finally, we revisited the band assignments for the amorphous phase of polyamide‐6 and found that the band at 1170 cm⁻¹ was not an amorphous band but, because its absorbance was independent of crystallinity, could be used as an internal reference band. The band at 1124 cm⁻¹ was reliably attributed to the amorphous phase. © 2001 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 536–547, 2001     

Formation of Crystalline CdSe Particles from a Single‐Source‐Precursor according to Ostwald's Rule

The formation of crystalline CdSe particles in the thermal degradation of Cd(SePh)₂·TMEDA (TMEDA = tetramethylethylenediamine) as a single‐source‐precursor was investigated by in‐situ powder X‐ray diffraction. It was shown that the primary grains were formed in the cubic zinc blende modification. After an increase in particle size by further annealing a phase transition to the thermodynamically favored hexagonal wurtzite type was detected. This behaviour indicates that, according to Ostwald's rule, the primary grains consist of the less stable polymorph due to the lower activation barrier of its formation. When the volume energy of the particles gets dominant over the surface energy, the metastable form is transformed and the system adopts the modification of lowest energy.     

Mössbauer Spectroscopic Investigation of FeII and FeIII 3,4,5‐Trihydroxybenzoates (Gallates) – Proposed Model Compounds for Iron‐Gall Inks

Iron gallates with iron in the oxidation states Fe²⁺ and Fe³⁺ were prepared and studied by Mössbauer spectroscopy, X‐ray diffraction, and IR spectroscopy. Fe^III 3,4,5‐trihydroxybenzoate (gallate) Fe(C₇O₅H₄) · 2H₂O, whose structure was first determined by Wunderlich, was obtained by the reaction of gallic acid and metallic iron or by oxidation of the Fe^II gallate, which was obtained by the reaction of ferrous sulfate with 3,4,5‐trihydroxybezoic acid (gallic acid) under anoxic conditions. Trials to reproduce the hydrothermal preparation method of Feller and Cheetham show that the result depends crucially on the free gas volume in the reaction vessel. If there is no free volume one obtains the same Fe^III gallate as in the other preparation methods. With a large free volume another compound was found to form whose composition and structure could not be determined. It could be specified only by Mössbauer spectroscopy. Fe^III gallate, the Fe^II gallate, and the new phase show magnetic ordering at liquid helium temperature.     

The synthesis and characterization of all diastereomers of a linear symmetrically fused Tris-Tröger's base analogue: new chiral cleft compounds

The synthesis and characterization of all diastereomers of a linear symmetrically fused tris-Tr?ger's base analogue are described. The diastereomers are unambiguously assigned as syn-anti 1 a, anti-anti 1 b, and syn-syn 1 c isomers, by using X-ray diffraction analysis and NMR spectroscopy. For the first time, the anti-anti and the syn-syn diastereomers of a linear symmetrically fused tris-Tr?ger's base analogue have been synthesized. Molecules 1 a and 1 c are new cleft compounds and analysis of compound 1 a in the solid state shows inclusion of one molecule of CH(2)Cl(2) in the larger aromatic cleft, whereas in isomer 1 c disordered solvent molecules are trapped in the extended aromatic cleft. Furthermore, in the solid state, isomer 1 c forms infinite open channels along one of the crystallographic axes and perpendicular to this axis there are infinitely extending "wedged-ravines". Importantly, each of the diastereomers 1 a-c is resistant to inversion at the stereogenic nitrogen atoms under strongly and weakly acidic conditions in the range from room temperature (RT) to 95 degrees C. This observed configurational stability at the stereogenic nitrogens of 1 a-c is unique for analogues of Tr?ger's base in general to date. Finally, the ratio of cleft compounds 1 a and 1 c significantly increased relative to cavity compound 1 b when ammonium chloride was used as an additive in the Tr?ger's base condensation to 1 a-c suggesting a templating effect of the ammonium ion.     

A Joint Theoretical and Experimental Insight into the Electronic Structure of Chromophores Derived from 6H,12H‐5,11‐Methanodibenzo[b,f][1,5]diazocine

We report on the synthesis and electronic spectra of the chiral, donor‐acceptor (push‐pull) chromophores (±)‐ 4 and (±)‐ 5 with a 6H,12H‐5,11‐methanodibenzo[b,f][1,5]diazocine scaffold (Scheme 1 and Fig. 2). The electronic structures of these compounds were investigated at a quantum‐chemical level (Figs. 2 and 3). The chemical reactivity of 6H,12H‐5,11‐methanodibenzo[b,f][1,5]diazocine ((±)‐ 11 ) towards aromatic electrophilic substitution (Scheme 2 and Table) provided additional information about its electronic structure and confirmed nonnegligible delocalization of the lone pair of the bridge‐head N‐atoms in this heterocyclic system.     

Iron–sulfur bond covalency from electronic structure calculations for classical iron–sulfur clusters

The covalent character of iron–sulfur bonds is a fundamental electronic structural feature for understanding the electronic and magnetic properties and the reactivity of biological and biomimetic iron–sulfur clusters. Conceptually, bond covalency obtained from X‐ray absorption spectroscopy (XAS) can be directly related to orbital compositions from electronic structure calculations, providing a standard for evaluation of density functional theoretical methods. Typically, a combination of functional and basis set that optimally reproduces experimental bond covalency is chosen, but its dependence on the population analysis method is often neglected, despite its important role in deriving theoretical bond covalency. In this study of iron tetrathiolates, and classical [2Fe? 2S] and [4Fe? 4S] clusters with only thiolate ligands, we find that orbital compositions can vary significantly depending on whether they are derived from frontier orbitals, spin densities, or electron sharing indexes from “Átoms in Molecules” (ÁIM) theory. The benefits and limitations of Mulliken, Minimum Basis Set Mulliken, Natural, Coefficients‐Squared, Hirshfeld, and AIM population analyses are described using ab initio wave function‐based (QCISD) and experimental (S K‐edge XAS) bond covalency. We find that the AIM theory coupled with a triple‐ζ basis set and the hybrid functional B(5%HF)P86 gives the most reasonable electronic structure for the studied Fe? S clusters. 2014 Wiley Periodicals, Inc.