Behaviour of unfilled and filled rubbers in shear in the glass-rubber transition region

Summary Rubbers filled with high amounts of a hard inorganic filler still show the typical mechanical properties of a high polymer, viz. a glass-rubber transition region, a glassy state and a rubbery state. The influence of filler characteristics on the glass-rubber transition is discussed, chiefly on the basis of the course of shear modulus at constant frequency as a function of temperature.The influence of volume content of filler on the glass-rubber transition of composite materials consists chiefly in a change of the levels of the shear modulus in the glassy and in the rubbery state. This change may be described by a simple macroscopic model due toVan der Poel. Predictions by this theory could be confirmed for rubbers filled with single filler fractions in the range of filler size between 30–500 m, and in the range of filler content between 0–50 vol.%.At smaller particle sizes, an influence of filler size was observed, which points to an increase in the transition temperature and to an increase in the level of modulus in the rubbery state with decreasing filler size.The preparation of composite materials with high filler contents (> 55 vol.%) is only possible by using a filler with a bimodal size distribution.In this case, moduli depend on filler content and mixing ratio of coarse to fine filler fraction; theVan der Poel theory then gives predictions which are too high in comparison with experimental results.     

Solution equilibria of aromatic dinitroso compounds: a combined NMR and DFT study

Solution-state nitroso monomer-azodioxide equilibria and conformational freedom of several aromatic dinitroso derivatives, differing in the spacer group between the aromatic rings, were studied by one- and two-dimensional variable temperature ¹H NMR spectroscopy and by quantum chemical calculations. The proton signals of nitroso monomer-azodioxide mixtures revealed by low-temperature NMR were assigned and validated using B3LYP-D3/6-311+G(2d,p)/SMD level of theory. In almost all cases, a preference towards the formation of only one azodioxy isomer of aromatic dinitroso compounds was found, which was assigned to Z-dimer according to computational data. Nevertheless, the computed small energy difference between the Z- and E-isomer could not account for the extreme preference for Z-dimer formation, indicating an influence of entropic or solvent effects. The formation of shorter oligomers in solution was excluded based on integrated ¹H NMR signal intensities. The experimental results indicated an average dimerization Gibbs energy of about ??5 kJ/mol at 223 K and were found to be in very good correlation with dimerization energies obtained by solution-phase optimization.

     

New Editor-in-Chief

Accreditation and Quality Assurance -     

On Characters and Superdimensions of Some Infinite-Dimensional Irreducible Representations of osp(m|n)

Physics of Atomic Nuclei - Chiral spinors and self dual tensors of the Lie superalgebra osp(m|n) are infinite-dimensional representations belonging to the class of representations with Dynkin...     

Ultrafast gas chromatography coupled to electronic nose to identify volatile biomarkers in exhaled breath from chronic obstructive pulmonary disease patients: A pilot study

An analytical method to identify volatile organic compounds (VOCs) in the exhaled breath from patients with a diagnosis of chronic obstructive pulmonary disease (COPD) using a ultrafast gas chromatography system equipped with an electronic nose detector (FGC eNose) has been developed. A prospective study was performed in 23 COPD patients and 33 healthy volunteers; exhalation breathing tests were performed with Tedlar bags. Each sample was analyzed by FCG eNose and the identification of VOCs was based on the Kovats index. Raw data were reduced by principal component analysis (PCA) and canonical discriminant analysis [canonical analysis of principal coordinates (CAP)]. The FCG eNose technology was able to identify 17 VOCs that distinguish COPD patients from healthy volunteers. At all stages of PCA and CAP the discrimination between groups was obvious. Chemical prints were correctly classified up to 82.2%, and were matched with 78.9% of the VOCs detected in the exhaled breath samples. Receiver operating characteristic curve analysis indicated the sensitivity and specificity to be 96% and 91%, respectively. This pilot study demonstrates that FGC eNose is a useful tool to identify VOCs as biomarkers in exhaled breath from COPD patients. Further studies should be performed to enhance the clinical relevance of this quick and ease methodology for COPD diagnosis.     

QUANTIS: Data quality assessment tool by clustering analysis

Automatically generated kinetic networks are ideally validated against a large set of accurate, reproducible, and easy-to-model experimental data. However, although this might seem simple, it proves to be quite challenging. QUANTIS, a publicly available Python package, is specifically developed to evaluate both the precision and accuracy of experimental data and to ensure a uniform, quick processing, and storage strategy that enables automated comparison of developed kinetic models. The precision is investigated with two clustering techniques, PCA and t-SNE, whereas the accuracy is probed with checks for the conservation laws. First, the developed tool processes, evaluates, and stores experimental yield data automatically. All data belonging to a given experiment, both unprocessed and processed, are stored in the form of an HDF5 container. The demonstration of QUANTIS on three different pyrolysis cases showed that it can help in identifying and overcoming instabilities in experimental datasets, reduce mass and molar balance closure discrepancies, and, by evaluating the visualized correlation matrices, increase understanding in the underlying reaction pathways. Inclusion of all experimental data in the HDF5 file makes it possible to automate simulating the experiment with CHEMKIN. Because of the employed InChI string identifiers for molecules, it is possible to automate the comparison experiment/simulation. QUANTIS and the concepts demonstrated therein is a potentially useful tool for data quality assessment, kinetic model validation, and refinement.