Structural changes in discotic samples during transition from crystal to discotic mesophase as revealed by electron microscopy and diffraction

Classical methods of structural analysis cannot be applied to liquid crystals because higher order reflections disappear during the transition from crystal to liquid crystal due to the reduction in long range orientational and translational correlations. However, in order to relate physical properties to the molecular architecture, it is essential to have information about molecular positions and orientations in the crystalline state as well as in the liquid crystalline state. In this work, the transition from crystalline to liquid crystalline phase is carefully monitored and the relationship between the original lattice and the new molecular positions found using electron diffraction. In addition to this, a new high resolution electron-microscopic technique is described in which the positions of molecules in the crystalline and the quenched discotic phase are directly imaged and the defects observed in the crystalline and LC phase compared and quantitatively analysed.     

Trace determination of Tl, Cu, Pb, Cd, and Zn in specimens of the limnic environment using isotope dilution mass spectrometry with thermal ionization

Within the framework of the German Environmental Specimen Bank program, Tl, Cu, Pb, Cd and Zn were determined in homogenized materials from the limnic environment using Isotope Dilution Mass Spectrometry (IDMS) with thermal ionization. The analytical procedures which were developed for the trace metal analysis of bioindicator and sediment samples are described in detail. Results obtained in bream, mussels (Dreissena polymorpha) and sediments of Lake Constance/Estuary of Constance in the sampling years 1981, 1985, 1988, 1990, 1992 and 1993 are discussed and compared with those of bream from the lakeland district of Born-hoeved/Lake Belau and from the River Saar as well as from reference materials.     

The influence of the liquid crystalline core geometry on the mesogenicity of novel chiral 2-(4-substituted-phenoxy)propanonitriles

The synthesis and characterization of seven novel (R)-2-(4-substituted-phenoxy)propanonitriles are described. The propanonitriles were prepared to evaluate their potential use as thermochromics and ferroelectric dopants, as well as to determine their twist sense properties. The materials exhibit smectic and chiral nematic phases of high thermal stability; the mesogenic behaviour of the nitriles is directly related to the type of two-ring core unit employed. The effects of the different molecular geometries and polarizabilities of the liquid crystalline cores on mesophase stability are discussed, particularly in relation to other members of this series. The chiral nematic phase of the propanonitriles is assigned as having a left-handed twist sense from contact preparation studies, and this is in agreement with rules relating absolute configuration and molecular structure to helical twist sense.     

The Properties of Voronoi Tessellations for 2D Ising Fluid Near the Second-Order Magnetic Phase Transition

The topological and geometrical properties of Voronoi cells generated for 2D fluid of hard disks with Ising-like spins near the second-order phase transition from the paramagnetic to ferromagnetic phase are described for different disk densities. The comparison with Voronoi cells generated for the random hard disk system is given.     

Distribution of melamine in polyester–melamine surface coatings cured under nonisothermal conditions

The influence of experimental cure parameters on the diffusion of reactive species in polyester–melamine thermoset coatings during curing has been investigated with X‐ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared. The diffusion of melamine plays a vital role in the curing process and, therefore, in the ultimate properties of coatings. At a low (<20%) hexamethoxymethylmelamine (HMMM) crosslinker concentration, the matrix composition is uniform, but at high HMMM concentrations, excess HMMM rapidly segregates to the air–coating interface. The rate of migration is governed by the difference in the surface free energies of polyester and HMMM and the concentration gradient of HMMM between the bulk and the surface. An increased rate of energy absorption also increases the rate of migration of HMMM to the surface. A physical model has been proposed to explain this surface segregation phenomenon in terms of cocondensation and self‐condensation reactions. It suggests that an appropriate amount of melamine can be segregated on the surface and allowed to self‐condense to form a desired thickness of a melamine topcoat through the control of the binder composition and cure conditions. This technique can be implemented to apply a melamine topcoat during cure. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 83–91, 2004     

Elevation of the glass transition temperature in flexible‐chain semicrystalline polymers

In the idealized two‐phase model of a semicrystalline polymer, the amorphous intercrystalline layers are considered to have the same properties as the fully‐amorphous polymer. In reality, these thin intercrystalline layers can be substantially influenced by the presence of the crystals, as individual polymer molecules traverse both crystalline and amorphous phases. In polymers with rigid backbone units, such as poly(etheretherketone), PEEK, previous work has shown this coupling to be particularly severe; the glass transition temperature (T_g) can be elevated by tens of degrees celsius, with the magnitude of the elevation correlating directly with the thinness of the amorphous layer. However, this connection has not been explored for flexible‐chain polymers, such as those formed from vinyl‐type monomers. Here, we examine T_g in both isotactic polystyrene (iPS) and syndiotactic polystyrene (sPS), crystallized under conditions that produce a range of amorphous layer thicknesses. T_g is indeed shown to be elevated relative to fully‐amorphous iPS and sPS, by an amount that correlates with the thinness of the amorphous layer; the magnitude of the effect is severalfold less than that in PEEK, consistent with the minimum lengths of polymer chain required to make a fold in the different cases. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1198–1204, 2007     

Miscibility of polyester/nitrocellulose blends: A DSC and FTIR study

The miscibility of polyester/nitrocellulose blends was investigated by differential scanning calorimetry and Fourier-transform infrared (FTIR) spectroscopy. Two nitrocelluloses (NC) derived from wood and having different nitrogen contents (12.62 and 13.42%) were used. On the basis of the glass transition temperature criterion, poly(?-caprolactone) (PCL), poly(valerolactone), poly(ethylene adipate), and poly(butylene adipate) are miscible with nitrocellulose, whereas poly(α-methyl α-propyl β-propiolactone) and poly(α-methyl β-proiolactone) are immiscible. The T_g versus composition curves of PCL/NC blends do not follow a monotone function but exhibit a singular point at a critical PCL volume fraction of 0.51 for NC-1342 and 0.45 for NC-1262 in agreement with Kovacs' theory. A shift of 17 cm^-1 of the carbonyl stretching band was observed with PCL/NC blends and is taken as evidence for hydrogen bonding interaction between the PCL carbonyl group and NC hydroxyl group. The frequency difference between the free hydroxyl absorbance and the absorbances of the hydrogen-bonded species was found to be 85 cm^-1 in pure NC and 125 cm^-1 in PCL/NC blends; it indicates that the average strength of this interaction is stronger than the corresponding self-associated hydrogen bonding in pure NC. The presence of a dipole-dipole interaction between the nitrate-ester groups of NC and the carbonyl groups of the polyesters is reported. The relative strength of the hydrogen bonding and dipole-dipole interactions is discussed and correlated with polymer miscibility.     

Band structures in73Se

Excited states of⁷³Se have been investigated up to spin, 21/2 using techniques of in-beamγ-ray spectroscopy in connection with the⁷⁰Ge(α, n) reaction. Mean lifetimes of 12 levels have been determined applying Doppler-shift andγ-RF-methods. Five different bands have been identified that reflect a variety of different excitation modes. The decoupled 9/2⁺ band is likely to correspond to an oblate deformation while the 5/2⁺ band is interpreted as a strongly coupled prolate band built on the Nilsson configuration [422] 5/2⁺. The 3/2^? band is a strongly coupled band built on the [301] 3/2^} configuration.Nuclear reactions:⁷⁰Ge(α,n),E=14, 16, 18, 19, 20MeV; measuredE _γ,I _γ,σ(E _γ,θ),γγ-coin, linear polarization, DSA,γ(t).⁷⁵Se deduced levels,I, π, τ, δ(E2/M1), B(σλ). Enriched targets, Ge detectors.