Thermal analysis as a quality tool for assessing the influence of thermo-mechanical degradation on recycled poly(ethylene terephthalate)

Mechanical recycling of poly(ethylene terephthalate) (PET) was simulated by multiple processing to assess the effects of thermo-mechanical degradation, and characterized using rheological and thermal analysis techniques. Thermo-mechanical degradation under repeated extrusion induces chain scission reactions in PET, which result in a dramatic loss in the deformation capabilities and an increase in the fluidity of the polymer under reprocessing, reducing its recycling possibilities after four extrusion cycles. Multiple reprocessing severely affects the storage modulus and the microstructure of recycled PET, both in the amorphous and crystalline regions. Multimodal melting behavior is observed for reprocessed PET, indicating heterogeneous and segregated crystalline regions. A deconvolution procedure has been applied to individually characterize each crystalline population in terms of lamellar thickness distribution and partial crystallinity. Thermal analysis techniques such as differential scanning calorimetry (DSC) and dynamic-mechanical analysis (DMA) have proved to be suitable techniques for the quality assessment of recycled PET, giving unequivocal information about its degree of degradation compared to the common technological measurements of melt-mass flow rate (MFR) or oxidative stability (T_Ox).     

Oxidation of Ethers,Alcohols, and Unfunctionalized Hydrocarbons by the Methyltrioxorhenium/H2O2 System: A Computational Study on Catalytic C?H Bond Activation

A concerted mechanism that does not involve an ionic intermediate was revealed by a DFT study on oxidation of ethers, alcohols, and unfunctionalized hydrocarbons by methyltrioxorhenium/H₂O₂. Instead, C? H insertion occurs through hydride transfer and then turns into a hydroxide transfer/rebound in a concerted fashion. The picture shows selected frames from an intrinsic reaction coordinate scan from the transition state to the product for the oxidation of cis‐1,2‐dimethylcyclohexane.

     

On establishing elastic–plastic properties of a sphere by indentation testing

Instrumented indentation is a popular technique for determining mechanical properties of materials. Currently, the evaluation techniques of instrumented indentation are mostly limited to a flat substrate being indented by various shaped indenters (e.g., conical or spherical). This work investigates the possibility of extending instrumented indentation to non-flat surfaces. To this end, conical indentation of a sphere is investigated where two methodologies for establishing mechanical properties are explored. In the first approach, a semi-analytical approach is employed to determine the elastic modulus of the sphere utilizing the elastic unloading response (the “unloading slope”). In the second method, reverse analysis based on finite element analysis is used, where non-dimensional characteristic functions derived from the force–displacement response are utilized to determine the elastic modulus and yield strength. To investigate the accuracies of the proposed methodologies, selected numerical experiments have been performed and excellent agreement was obtained.     

Conformation of the glycosidic linkage in a disaccharide investigated by double-quantum solid-state NMR.

Double-quantum heteronuclear local field NMR is performed on a sample of a 13C2-labeled disaccharide, in which the two 13C spins are located on opposite sides of the glycosidic linkage. The evolution of the double-quantum coherences is found to be consistent with the solid-state conformation of the molecule, as previously determined by X-ray diffraction. The dependence of the double-quantum evolution on the glycosidic torsional angles is examined by using a graphical molecular manipulation program interfaced to a numerical spin simulation module.     

Enhanced rigidity of recycled polypropylene from packaging waste by compounding with talc and high‐ crystallinity polypropylene

Polypropylene (PP) constituted 30% of the collected material in a Swedish collection system for rigid plastic packaging waste. The PP fraction was however a complex mixture of grades with widely different properties. In order to enhance the rigidity of the recycled PP, modified grades were prepared by compounding with talc and/or a virgin high‐crystallinity PP grade. Adding 20–40% of high‐crystallinity PP enhanced the stiffness and yield strength without impairing the impact resistance. A composite material consisting of 20% of this grade, 20% talc and 60% recycled PP gave mechanical properties similar to those of a commercial talc‐filled PP compound used for demanding engineering applications. The present study demonstrates that recycled PP derived from post‐consumer packaging waste can also be made useful for demanding engineering applications. Copyright © 2001 John Wiley & Sons, Ltd.     

Evaluation of methods aimed at complete removal of template from molecularly imprinted polymers.

Polymers imprinted with clenbuterol were used to study the influence of various post-polymerization treatments [e.g., thermal annealing, microwave assisted extraction (MAE), Soxhlet extraction and supercritical fluid template desorption] on the bleeding of residual template. The aim of the study was to reduce the bleeding to levels that would allow the use of the materials as affinity phases for extraction of clenbuterol from bovine urine at concentrations below 1 ng ml-1. After treatment, the clenbuterol imprinted polymers were packed into solid-phase extraction columns and the bleeding was estimated by quantifying the amount of template released in 10 ml of methanol-acetic acid (9 + 1 v/v). This was followed by an assessment of selectivity and recovery in comparison with non-treated material. The lowest bleeding level was found after MAE using 100% trifluoroacetic acid for 3 x 20 min at 100 degrees C. The collected eluate contained in this case 3 ng ml-1 of clenbuterol. The same material was subsequently used for the extraction of clenbuterol from spiked bovine urine. The resulting selectivity and recovery were lower compared with those obtained using the untreated material. A milder but still efficient method to reduce the bleeding level was found to be MAE with formic acid. In this case a bleeding level of 14 ng ml-1 was found after only a 1 h extraction time. In a second model system, using a polymer imprinted with L-phenylalanine anilide, the bleeding was reduced to a similar level by extensive on-line washing in good swelling solvents containing acid or base additives and after thermal annealing of the polymers in the dry state.     

Crystal field effects on the magnetic fluctuations in RAl2 and RNi2

Zero-field μSR spectra have been recorded for some ferromagnetic Laves phase compounds. A comparison of the temperature dependence of the exponential damping rate, λ(T), for our samples shows that λ(T) is strongly influenced by crystal field effects.