Shear-induced crystallization of polyamide 11

Shear-induced formation of crystal nuclei in polyamide 11 (PA 11) was studied using a conventional parallel-plate rheometer. Crystallization of PA 11 after shearing the melt at different rates for 60 s was followed by the evolution of the complex viscosity. The sheared samples showed in an optical microscope a gradient structure along the radius, due to the increasing shear rate from the center to the edge. The critical shear rate for shear-induced formation of nuclei was identified at the position where a distinct change of the semicrystalline superstructure is observed, being at around 1 to 2 s−1. Below this threshold, a space-filled spherulitic superstructure developed as in quiescent-melt crystallization. Above this value, after shearing at rates between 1 and 5 s−1, an increased number of point-like nuclei was detected, connected with formation of randomly oriented crystals. Shearing the melt at even higher rates led to a further increase of the nuclei number and growth of crystals oriented such that the chain axis is in parallel to the direction of flow. In addition, optical microscopy confirmed formation of long fibrillar structures after shearing at such condition. The critical specific work of flow of PA 11 was calculated to allow a comparison with that of polyamide 66 (PA 66). This comparison showed that in the case of PA 11 more work for shear-induced formation of nuclei is needed than in the case of PA 66, discussed in terms of the chemical structure of the repeat unit in the chains. Graphical abstract

Finite Length Effects on Switching Mechanisms in Chains of Magnetic Particles

Periodic systems of magnetic nanoparticles are now of interest as they support GHz spin waves. Their equilibrium configurations, switchable with the external magnetic field, are crucial for such applications. We study infinite and finite chains of particles of two shapes (i) ellipsoidal and (ii) rectangular stripes with long axes perpendicular to the chain axis. A variable magnetic field is applied parallel to the long axes. Micromagnetic simulations are compared with the corresponding discrete spin models (Stoner-Wohlfarth model, S-W). An antiferromagnetic configuration is the ground state for all the systems at vanishing field but a ferromagnetic configuration occurs when the field is strong enough. The switching of the infinite chains to the reversed ferromagnetic configuration proceeds directly for the ellipsoids and by an intermediate configuration, in which the magnetization within the particle is non-uniform, in the case of the stripes. The non-uniform configurations are well represented by tilted states in S-W model. Important differences are found in the finite analogs: the switching of ellipsoids becomes multistage and starts from the innermost particles relatively well reproduced with S-W model, whereas the reversal of the stripes, starts from the outermost particles and has no analog in S-W model. Practical consequences of the findings are discussed.

One molecule, three crystal structures: conformational trimorphism of N-[(1S)-1-phenylethyl]benzamide

The title compound, C15H15NO, is an enantiopure small molecule, which has been synthesized many times, although its crystal structure was never determined. By recrystallization from a variety of solvent mixtures (pure acetonitrile, ethanol–water, toluene–ethanol, THF–methanol), we obtained three unsolvated polymorphs, in space groups P21 and P212121. Form I is obtained from acetonitrile, without admixture of other forms, whereas forms II and III are obtained simultaneously by concomitant crystallizations from alcohol-based solvent mixtures. All forms share the same supramolecular structure, based on infinite C 1 1(4) chain motifs formed by N—H...O intermolecular hydrogen bonds, as usual for non-sterically hindered amides. However, a conformational modification of the molecular structure, related to the rotation of the phenyl rings, alters the packing of the chains in the crystal structures. The orientation of the chain axis is perpendicular and parallel to the crystallographic twofold screw axis of space group P21 in forms I and II, respectively. As for form III, the asymmetric unit contains two independent molecules forming parallel chains in space group P212121, and the crystal structure combines features of monoclinic forms I and II.

Application of Magnetosomes in Magnetic Hyperthermia

Nanoparticles, specifically magnetosomes, synthesized in nature by magnetotactic bacteria, are very promising to be usedin magnetic hyperthermia in cancer treatment. In this work, using the solution of the stochastic Landau–Lifshitz equation, we calculate the specific absorption rate (SAR) in an alternating (AC) magnetic field of assemblies of magnetosome chains depending on the particle size D, the distance between particles in a chain a, and the angle of the applied magnetic field with respect to the chain axis. The dependence of SAR on the a/D ratio is shown to have a bell-shaped form with a pronounced maximum. For a dilute oriented chain assembly with optimally chosen a/D ratio, a strong magneto-dipole interaction between the chain particles leads to an almost rectangular hysteresis loop, and to large SAR values in the order of 400–450 W/g at moderate frequencies f = 300 kHz and small magnetic field amplitudes H0 = 50–100 Oe. The maximum SAR value only weakly depends on the diameter of the nanoparticles and the length of the chain. However, a significant decrease in SAR occurs in a dense chain assembly due to the strong magneto-dipole interaction of nanoparticles of different chains.

Morphological study of Chaetoceros wighamii Brightwell (Chaetocerotaceae, Bacillariophyta) from Lake Vrana, Croatia

Chaetoceros wighamii Brightwell is a planktonic diatom species originally described from brackish waters. Since its original description, the species has been reported in a wide variety of habitats, ranging from freshwater to marine. Varying descriptions exist in the taxonomic literature and several taxa have been considered as synonyms, including freshwater species Chaetoceros amanita. In this study we provide morphological and ultrastructural information on a cultured strain isolated from freshwater sample collected in the Lake Vrana (Vransko jezero) in Croatia, in April 2011. The cells form short and robust chains with very narrow apertures, often partially occluded by silica membranes. Other distinctive features observable in light microscopy are the shape and orientation of the setae which are very long, straight and robust, diverging in various directions from the chain axis and the single parietal chloroplast extending from valve to valve. Distinct ultrastructural characteristics are the absence of processes either in intercalary or terminal valves and the ornamentation of the valve face with densely distributed ribs spreading from an irregular eccentric hyaline area without a clearly defined annulus. The outer surface of the terminal valve is ornamented with small spines and setae are composed of fl at longitudinal filaments interconnected with short bars and ornamented with small spines tightly arranged around the setae. Our description agrees well with that reported for the freshwater morphotypes of C. wighamii (syn. C. amanita) and contributes for a reliable distinction of this intriguing taxon from similar morphotypes. This finding supports the interpretation of Chaetoceros wighamii as a freshwater/brackish species and represents the first report of a Chaetoceros species in lacustrine environment in Croatia and possibly in any Central European habitats.

Characterization of molecular orientation under tensile deformation by near infrared spectroscopy

We present a novel method for characterizing orientation behavior of typical polyethylene (PE) materials such as HDPE, LLDPE, and LDPE. The chain orientation to the stretching direction was examined under uniaxial deformation by near infrared spectroscopy. Then we obtained directly the orientation function of PE chain axis (c-axis) from the CH stretching vibration of NIR spectra as a function of extension time or strain. We compared the present method with the conventional infrared IR method where the orientation function of PE c-axis (chain-axis) has been indirectly obtained from the b-and a-axis’s assuming the orthogonal crystal form by using the CH2 rocking vibrations in IR spectra