Functionalization of soluble polymers

Summary The synthesis of di-(4-formylphenyloxyethyl) poly(oxyethylene) and the corresponding oxime derivative are described. Kinetic aspects of the reaction of the dichloro telechelic with 4-hydroxy benzaldehyde are investigated and discussed.     

Conductive PE-carbon composites by elongation flow injection moulding

In Part 1 and Part 2 of this paper the preparation of linear polyethylene (PE)-carbon black processed composites with conducting electrical properties was examined by means of elongation flow injection moulding. Mould geometry was optimized in the form of oriented double-armed bars so as to give enhanced mechanical properties combined with a high degree of electrical homogeneity. The present paper deals with composites using a high molecular weight PE matrix. It is shown that the injection-moulded composite material exhibits not only a lower percolation threshold, _c, than the conventionally pressure-moulded isotropic sample, but also conductivities two to three orders of magnitude larger than the latter. The radial and axial conductivity profiles, for concentrations well above _c, are discussed in the light of the molecular orientation variations across the bars as determined by birefringence. A segregation of primary filler particles, during flow-induced orientation, into axial channels has been shown to explain the enhancement of conductivity detected in the injected mouldings. In addition, for filler concentrations near 7%, -profile analysis indicates the development of a uniform conductive-stiff inner cylinder, several millimetres wide, homogeneously extending along the full length of the injected material.     

Structure development in amorphous starch as revealed by X‐ray scattering: Influence of the network structure and water content

The evolution of the amorphous structure of starch was characterized during the drying process by real‐time X‐ray wide‐angle scattering. The X‐ray diffractograms of injection‐molded starch show two superposed, rather broad, scattering maxima indicative of noncrystalline structures. The location of the two peaks has been associated to disordered starch single helices. A third maximum that arises upon drying the material in vacuum is associated to the scattering emerging from regions containing double helices. A model for the starch network is proposed, assuming a primary and a secondary component. The wider, temperature stable component appearing first, is correlated to the entanglement network of the melt. The narrower network component, which is created later, at lower temperature (secondary network), is explained by the formation of double helix regions that densify the wider primary network. The secondary network is increased strongly by the drying process. X‐ray experiments performed during the penetration of water, provoking a higher molecular mobility, reveal a better‐packed helical structure that becomes the precursor of a double helix crystalline formation. When temperature increases, the secondary network is dissolved and water molecules arrange themselves in better‐organized crystals as strongly bound crystal water. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 1880–1886, 2006     

Capillary HPLC-NMR Coupling: High-Resolution (1)H NMR Spectroscopy in the Nanoliter Scale

Coupling HPLC and NMR is one of the most powerful techniques for simultaneous separation and structural elucidation of unknown compounds in mixtures. To date, however, minimizing the detection volume, as is required when coupling NMR with miniaturized separation techniques, has been accompanied by a dramatic loss in resolution of the NMR spectra. Here, we report on the coupling of gradient capillary HPLC with on-column, high-resolution NMR detection. On-line stopped-flow and static (1)H NMR spectra were acquired with capillary columns of 75-315 μm i.d. With detection over a length of 1.2 cm, cell volumes cover a range of 50-900 nL. An on-line-detected NMR separation of dansylated amino acids was carried out in a 315 μm i.d. fused silica capillary packed to a length of 12 cm with C(18) stationary phase. The low solvent consumption makes the use of fully deuterated solvents economically feasible. NMR spectra with resolution on the order of 3 Hz were obtained using a 50 nL detection cell to measure 1.1 nmol of dansylated γ-aminobutyric acid under static conditions in a 75 μm i.d. capillary.     

Correlation of microhardness and morphology in injection-moulded poly(ethylene terephtalate)

Microindentation hardness has been applied to a series of injection-moulded poly(ethylene terephtalate) samples prepared using a range of mould temperatures, T _c. The morphology of the samples was characterized by X-ray diffraction and differential scanning calorimetry. Depending on T _c, it is shown that microhardness is lower at the surface than in the core of the mouldings. Results are discussed in terms of the volume fraction of spherulites filling the mouldings which is shown to be dependent upon T _c. The influence of an annealing treatment on the properties of the mouldings is examined. The microhardness values are correlated with the thickness and with the surface free energy of the lamellar crystals. The results obtained indicate that increasing annealing temperatures first leads to an increase and then to a sudden decrease of hardness. The latter can be associated with the changes occurring in the number of defects on the crystal's surface.     

Acute kidney failure in hypothermia

Two cases with acute renal failure after prolonged hypothermia are presented. Both patients were found in come, became rapidly uremic and required hemodilaysis treatment. Although the laboratory findings were typical of severe muscle damage, e.g. elevated levels of serum creatinine phosphokinase, serum lactic dehydrogenase and serum aldolase activities, visible "crush-injuries" were not found. Acute renal failure was characterized by extreme catabolism and severe metabolic acidosis. After 4 and 10 hemodialyses respectively, the patients became polyuric and finally were discharges with normal renal and muscle function. Hypotension with diminished renal perfusion and nontraumatic rhabdomyolysis due to prolonged hypothermia are regarded as the dominant pathogenetic factors in the acute renal failure.     

Estimation of an unknown cartographic projection and its parameters from the map

This article presents a new off-line method for the detection, analysis and estimation of an unknown cartographic projection and its parameters from a map. Several invariants are used to construct the objective function ? that describes the relationship between the 0D, 1D, and 2D entities on the analyzed and reference maps. It is minimized using the Nelder-Mead downhill simplex algorithm. A simplified and computationally cheaper version of the objective function ? involving only 0D elements is also presented. The following parameters are estimated: a map projection type, a map projection aspect given by the meta pole K coordinates [φ _k , λ _k ], a true parallel latitude φ ₀, central meridian longitude λ ₀, a map scale, and a map rotation. Before the analysis, incorrectly drawn elements on the map can be detected and removed using the IRLS. Also introduced is a new method for computing the L ₂ distance between the turning functions Θ₁, Θ₂ of the corresponding faces using dynamic programming. Our approach may be used to improve early map georeferencing; it can also be utilized in studies of national cartographic heritage or land use applications. The results are presented both for the real cartographic data, representing early maps from the David Rumsay Map Collection, and for the synthetic tests.