Carbon-13 spin–lattice relaxation in some polyfluoroaromatic compounds

Carbon-13 chemical shifts, spin-lattice relaxation times and nuclear Overhauser enhancement factors are reported for five polyfluoroaromatic compounds at 28°C. In all cases the relaxation of the fluorine bearing carbon is predominantly dipolar. Effective correlation times are smaller than those of the analogous benzene derivatives by a factor of 3–4, in qualitative agreement with predictions from the Stokes–Einstein diffusion theory. The T₁ values for the para-carbon of monosubstituted fluorobenzenes is clearly shorter than the T₁ values for the ortho- and meta-carbons. This phenomenon was traced to anisotropic tumbling, and D∥ and D⊥ diffusion coefficients were computed using Woessner's equations for molecules assumed to behave like symmetric rotors about their C₂ in-plane principal symmetry axis. Equal tumbling ratios, D∥/D⊥, were found in this way for toluene and perfluorotoluene.     

Development of the hot wire technique for finite geometry samples

The hot wire technique is widely used to determine the thermal properties of materials. Commonly, this technique is developed for considered infinite radius of cylindrical mediums. Here, we propose an analytical solution of the heat conduction problem in an insulated finite sample. The derived temperature solution is found mathematically to be non-regular convergent series, and lead to avoid the assumption of infinite geometries, difficult to realize in practice. The first part of this paper concerns the study of the calculability of this series. The second one deals with the thermal properties estimation. The sensitivity study shows that the estimation procedure is feasible either using the concept of the time of the maximum rising temperature or, when exploring large time measurements, using the least squares minimisation that has an equivalent pure graphical procedure.     

Thermophysical analysis and modeling of the crystallization and melting behavior of PLA with talc

The crystallization kinetics and the melting behavior of PLA and PLA with talc are investigated by dynamic scanning calorimeter and optical microscopy. The polymorphic aspect of PLA was highlighted by analyzing the melting process throughout heating after isothermal crystallization. The melting process of PLA with 5 mass% talc (PLAT5) shows the same thermal transitions as for PLA alone. The thermodynamic melting temperature of PLA and PLAT5 is determined to be 167.7 °C. The effects of the temperature and the cooling rate on the crystallization kinetics of PLA are analyzed. Finally, a simple and efficient protocol is defined to model the isothermal and the non-isothermal crystallization taking into account the polymorphism of PLA. Good agreement is found between the predictions of the proposed model and the experimental results under isothermal and non-isothermal conditions.     

Process of selective laser sintering of polymer powders: Modeling,simulation, and validation

Selective laser sintering (SLS) of polymer powders involves multiphysical transient phenomena. A numerical tool for simulating such a process is developed on the basis of the reliable modeling of the corresponding thermo-physical transient phenomena and appropriate numerical methods. The present paper addresses modeling, simulation, and validation aspects that are indispensable for studying and optimizing SLS process. The coupled multiphysical models are detailed, and the numerical tool based on the finite volume method is presented, with validations in terms of numerical and physical accuracy, by considering the shrinkage involved in the process and the successive layers deposition. A parametric analysis is finally proposed in order to test the reliability of the model in terms of representing real physical phenomena and thermal history experienced by the material during the process.     

Experimental and theoretical study on 3,5‐(oxo/thioxo) derivatives of 2,7‐dimethyl‐1,2,4‐triazepines–iodine molecular complexes

Intermolecular charge‐transfer (CT) spectra of 3‐thioxo‐5‐oxo‐, 5‐thioxo‐3‐oxo‐, and 3,5‐dithioxo‐ derivatives of 2,7‐dimethyl‐[1,2,4]‐triazepine 1:1 molecular complexes with molecular iodine were studied in the UV‐visible region. Equilibrium constants and free energy changes of the formed complexes were determined in solution. Ab initio calculations at HF/LANL2DZ* and MP2/LANL2DZ* were carried out to establish the nature of the complexation site, to determine the complex structures, and to examine the basicity of these compounds toward molecular iodine. The 3,5‐dithioxo‐2,7‐dimethyl‐[1,2,4]‐triazepine is the most basic one toward molecular iodine. In all cases, the complexation takes place at the heteroatom attached to position 3 of the triazepine. Hence, although in general, thiocarbonyls are stronger bases than carbonyls in the gas phase, 5‐thioxo‐2,7‐dimethyl‐[1,2,4]‐triazepin‐3‐one behaves as an oxygen base towards I₂. Experimental free energies in solution and gas‐phase computational values are linearly correlated. Copyright © 2009 John Wiley & Sons, Ltd.     

Simulation of crystallization evolution of polyoxymethylene during microinjection molding cycle

A mathematical model coupled with a numerical investigation of the evolving material properties due to thermal and flow effects and in particular the evolution of the crystallinity during the full microinjection molding cycle of poly (oxymethylene) POM is presented using a multi‐scale approach. A parametric analysis is performed, including all the steps of the process using an asymmetrical stepped contracting part. The velocity and temperature fields are discussed. A parabolic distribution of the velocity across the part thickness, and a temperature rise in the thin zone toward the wall have been obtained. It is attributed to the viscous energy dissipation during the filling phase, but also to the involved characteristic times for the thermal behavior of the material. Depending on the molding conditions and the locations within the micro‐part, different evolution of crystallization rates are obtained leading to at least three to five morphological layers, obtained in the same part configuration of a previously work, allowing a clear understanding of the process‐material interaction.     

Acid catalyzed α-alkylation of β-aminothiophenes with aldehydes. synthesis of 2-alkyl 3-thiophenamines,bis(3-amino-2-thienyl)-methane derivatives and dithieno[3,2-b:2′,3′-e]pyridines

The acid catalyzed reaction of 3-thiophenamines with aldehydes in the presence of selenophenol as the reducing agent, gives 2-alkyl-3-miophenamines. Without reduction, bis(3-amino-2-thienyl)methane derivatives have been obtained and transformed into dithieno[3,2-b:2′,3′-e]pyridines by thermal and acidic treatment when the substrates are primary amines. These new tricyclic heterocycles can be synthesized in a one-pot procedure from 3-thiophenamine.