Physical aging and deformation kinetics of polycarbonate

Considering the current view that physical aging of glasses results in an increase of activation barriers to plastic deformation, it is surprising that, until now, no influence of physical aging was observed experimentally on the temperature dependence of plastic deformation in polymeric glasses. This study evaluates why such an influence has not been found, and it is shown that detailed analysis of a set of uniaxial compression data on polycarbonate (PC) at different strain rates and temperatures leads to the conclusion that a significant influence indeed exists. As a consequence, the Eyring activation energy depends on the aging history of the material. These experimental observations are rationalized in terms of a simple physical interpretation of the aging phenomenon. The article also contains a discussion of the apparent deaging of amorphous polymers induced by large‐strain plastic deformation. This discussion is of key importance here, because this study compares yield stresses of aged PC with those of mechanically deaged, or rejuvenated, PC. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012     

Influence of fullerene photodimerization on the PCBM crystallization in polymer: Fullerene bulk heterojunctions under thermal stress

For an increased lifetime of polymer:fullerene bulk heterojunction (BHJ) solar cells, an understanding of the chemical and morphological degradation phenomena taking place under operational conditions is crucial. Phase separation between polymer and fullerene induced by thermal stress has been pointed out as a major issue to overcome. While often the effect of thermal stress on the morphology of polymer:fullerene BHJ is investigated in the darkness, here we observe that light exposure slows down fullerene crystallization and phase separation induced at elevated temperatures. The observed photo‐stabilizing effect on active layer morphology is quite independent on the polymer and is attributed to light‐induced dimerization of the fullerene. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2013 , 51, 1209–1214     

Salimabromide: Unexpected Chemistry from the Obligate Marine Myxobacterium Enhygromxya salina

Marine myxobacteria (Enhygromyxa, Plesiocystis, Pseudoenhygromyxa, Haliangium) are phylogenetically distant from their terrestrial counterparts. Salimabromide is the first natural product from the Plesiocystis/Enhygromyxa clade of obligatory marine myxobacteria. Salimabromide has a new tetracyclic carbon skeleton, comprising a brominated benzene ring, a furano lactone residue, and a cyclohexane ring, bridged by a seven‐membered cyclic moiety. The absolute configuration was deduced from experimental and calculated CD data. Salimabromide revealed antibiotic activity towards Arthrobacter cristallopoietes.     

The effect of pressure on pericyclic rearrangements (intramolecular Diels-Alder reaction,Cope rearrangement,and electrocyclic reaction)

Abstract

The pressure-dependence of the pericyclic rearrangements mentioned in the title uncovers a simple relation between volumes of activation and the number of new cyclic interactions in the transition state. Each new ring formed in the transition state of these pencyclic rearrangements contributes to the volume of activation by roughly ?10 to ?12 cm³mol^?1. Therefore, volumes of activation provide an important information on the geometry of transition states.     

Model based optimization of a statistical simulation model for single diamond grinding

We present a model for simulating normal forces arising during a grinding process in cement for single diamond grinding. Assuming the diamond to have the shape of a pyramid, a very fast calculation of force and removed volume can be achieved. The basic approach is the simulation of the scratch track. Its triangle profile is determined by the shape of the diamond. The approximation of the scratch track is realized by stringing together polyhedra. Their sizes depend on both the actual cutting depth and an error implicitly describing the material brittleness. Each scratch track part can be subdivided into three three-dimensional simplices for a straightforward calculation of the removed volume. Since the scratched mineral subsoil is generally inhomogeneous, the forces at different positions of the workpiece are expected to vary. This heterogeneous nature is considered by sampling from a Gaussian random field. To achieve a realistic outcome the model parameters are adjusted applying model based optimization methods. A noisy Kriging model is chosen as surrogate to approximate the deviation between modelled and observed forces. This deviation is minimized and the results of the modelled forces and the actual forces from conducted experiments are rather similar.     

Near-Surface Structure of Plasma Polymer Films Affects Surface Behavior in Water and its Interaction with Proteins

Using low pressure plasma polymerization, nano-scaled oxygen-rich plasma polymer films (CO) were deposited onto pristine silicon wafers as well as on nitrogen-containing plasma polymer (CN) model surfaces. We investigate the influence of the nature of the substrate as well as a potential sub-surface effect emerging from the buried CO/CN interface, just nanometers below the surface. X-ray Photoelectron Spectroscopy and Time-of-Flight Secondary Ion Mass Spectrometry revealed two important phenomena that occurred during the deposition of the terminal CO layer: (1) a strong degree of oxidation, already for 1 nm nominal thickness, and (2) a gradual transition in chemical composition between the two layers, clearly indicating that effectively a vertical chemical gradient results, even when a two-step coating process was applied. Such terminal gradient film structures were used to study film stability in aqueous environments. Molecular rearrangements were scrutinized in the top-surface in contact with water and we found that the top-surface chemistry and wetting properties of the oxygen-rich termination layer matched those of thick CO reference coatings. Nevertheless, the adsorption of green fluorescent protein (GFP) was observed to be sensitive to the CO terminal layer thickness. Namely, an enhanced protein adsorption was observed for 1–2 nm thick CO layers on CN, whereas a significantly reduced protein adsorption was seen on ≥?3 nm thick CO terminal layers. We conclude that both, surface and sub-surface conditions significantly affect protein adsorption as opposed to the traditional consideration of surface properties alone.