Real-time image analysis and numerical simulation of isothermal spherulite nucleation and growth in polyoxymethylene

A method of analysing nucleation and crystallization kinetics, based on real time image analysis and hot stage optical microscopy, has been used to investigate the isothermal crystallization of different grades polyoxymethylene. The data were compared with results from differential scanning calorimetry (DSC), using a simple numerical simulation to model the effects of finite smaple thickness on the form of the isothermal DSC curves. This simulation was then used to predict the microstructural development in a bulk sample for different boundary conditions, taking into account latent heat evolution and diffusion during crystallization.     

Molecular mechanisms contributing to the strength and toughness of glassy polymers

In this short summary reference will be made to some recent molecular level studies of strength. Especially the role of chains and of their entanglements in stress transfer and energy dissipation and the influence of rate of loading will be referenced.     

The influence of network structure on the macroscopic mechanical properties of crosslinked polymers

Neat and rubber-toughened epoxy resin systems EPN/BA and EPN/DDS with significantly different crosslink densities and glass transition temperatures were tested under widely different experimental conditions ranging from impact to long-term loading. The resulting deformation mechanisms were examined in order to ascertain the effects of network structure and toughening modifiers. Different toughening mechanisms were observed in low- and high-crosslink-density epoxy systems, modified with the same core-shell rubber particles.     

Molecular coils and their deformation

The study of stress-effects on chain conformation has always been a fruitful - and sometimes highly controversial - issue in macromolecular science. In this paper chain scission in transient elongational flow is investigated. Particular attention is given to the possible nature of stress transfer from the deforming highly dilute polymer solution to the embedded molecular (PS) chain. The dependencies of the measured degradation efficiency on molecular weight, solvent viscosity, nozzle geometry and flow rate exclude the classical mechanism of chain loading through strain-rate dependent viscous friction. On the basis of their findings the authors propose a model where the loading of hairpin-like segments in almost static friction works against the internal relaxation of these structures.     

Effect of binding of an oligomeric cationic fluorosurfactant on the dilational rheological properties of gelatin adsorbed at the air-water interface

The effect of binding of an oligomeric cationic fluorooxetane surfactant on the interfacial properties of adsorbed gelatin-fluorooxetane complexes has been studied using dynamic surface tension and dilational rheological measurements. Adsorption kinetics of gelatin-fluorooxetane complexes are reminiscent of a mixed (barrier/diffusion limited) process, while the dilational rheological properties of the interface exhibit a strong dependence on surfactant concentration. At low surfactant concentrations, dilational surface moduli as well as phase angles are relatively insensitive to the presence of the fluorooxetane. However, at the critical aggregation concentration of the polymer-surfactant system, there is a sharp increase in the complex modulus. Further increase in the fluorooxetane concentration does not significantly affect the complex modulus. The phase angle, however, does increase with increasing fluorooxetane concentration due to the transport of bound fluorooxetane from the subsurface to the solution-air interface. These results indicate that, at fluorooxetane concentrations exceeding the critical aggregation concentration, the polymer-surfactant complexes adsorb to form cross-linked multilayers at the solution-air interface.     

Moessfit

A free data analysis program for Mössbauer spectroscopy was developed to solve commonly faced problems such as simultaneous fitting of multiple data sets, Maximum Entropy Method and a proper error estimation. The program is written in C++ using the Qt application framework and the Gnu Scientific Library. Moessfit makes use of multithreading to reasonably apply the multi core CPU capacities of modern PC. The whole fit is specified in a text input file issued to simplify work flow for the user and provide a simple start in the Mössbauer data analysis for beginners. However, the possibility to define arbitrary parameter dependencies and distributions as well as relaxation spectra makes Moessfit interesting for advanced user as well.     

Synthesis, characterization, and interfacial properties of an oligomeric, cationic fluorooxetane

The synthesis and characterization of a cationic oligo(fluorooxetane) surfactant with pendant -C4F9 groups are reported. Molecular area demand at saturation was determined to be 55.6 +/- 0.3 angstroms2/molecule and characteristic of an oligomer. The adsorption of the cationic oligo(fluorooxetane) to the air-water interface appears to be diffusion-limited, and dilational rheological properties of the adsorbed molecules are representative of a "soluble" monolayer. Adsorption dynamics have been measured yielding diffusion coefficients that are dependent on concentration and in the 10(-7)-10(-8) cm2/s range. Complex moduli from dilational interfacial rheological measurements as a function of oscillation frequency were well fitted to the Lucassen-van den Tempel equation, providing an estimate of the Gibbs elasticity. The combination of the oligomeric nature of the fluorosurfactant, short perfluoroalkyl chain and its interfacial properties suggests that this synthetic approach is an attractive route to the development of fluorinated surfactants that avoid the environmental concerns of small-molecule, long perfluoroalkyl-chain surfactants.     

Carbon-13 NMR spectra of heterocycles. Sultones and sultams.

The ¹³C NMR spectra of 1,3-propanesultam, 2,4-butanesultam, 1,4-butanesultam, 1,3-propanesultone and 1,4-butanesultone, as well as some of their unsaturated analogs 2,4-dimethylbuta-1,3-diene-1,4-sultone and 2,4-dimethylbuta-1,3-diene-1,4-sultam, have been recorded. The observed chemical shift data for the sultams and sultones can be explained mainly on the basis of inductive effects. The δ values of the dienesultone and the dienesultam are mainly affected by M-effects. ¹H NMR as well as mass spectra have.