Degradation of a polyester‐urethane coating: Physical properties

In this article we studied the evolution of thermomechanical properties of a polyester‐urethane coating during degradation under different degradation conditions, i.e., aerobic and anaerobic conditions with and without dry/wet cycling during degradation. Dynamic mechanical and thermal analyses show that under aerobic conditions the coatings become stiffer and more brittle in the glassy state. This stiffening is probably due to the increase in the amount of hydrogen bonding and the formation of oxidized groups which increase the polarity of the material and enhance the interactions of the polymer segments. However, oxidation reactions result in a considerable decrease in cross‐link density and stiffness in the rubbery state. Both changes, in the glassy and rubbery states, give rise to development of internal stresses. These stresses increase as the degradation process proceeds. Nevertheless, for samples exposed to anaerobic conditions, the stiffness remains constant in the glassy state and the cross‐link density slightly increases as a result of degradation. This reconfirms the dominance of the effect of oxidation reactions on the mechanical failure of the coatings. Oxygen permeation measurements show a more‐or‐less time‐independent diffusion coefficient and a gradual decrease in solubility of oxygen as a function of exposure time. This results in a slight decrease in oxygen permeation (mainly in the early stage of the degradation) as degradation proceeds. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 659–671     

An Efficient Synthesis of Dicarbonyl (η5—Cyclopentadien—YL)Iron(II) Complexes of Two Cyclic Enol Ethers

An efficient synthesis of dicarbonyl(η⁵—cyclopentadienyl)iron—(II)—complexes of 2,3—dihydrofuran and 3,4—dihydro—2H—pyran from 3—bromo—2—methoxytetrahydrofuran and—pyran, respectively, is described.     

Electron density decay measurements using the 447.1 nm line of neutral helium

The 447.1 nm line of neutral helium has been used to measure the time-dependent decay of the electron density in the afterglow of a pulsed, atmospheric pressure helium discharge. The technique involves using a shutter which consists of a Pockels cell combined with crossed polarizers to gate the light pulse, allowing observation of the spectrum during various time windows in the discharge.     

The outermost atomic layer of thin films of fluorinated polymethacrylates

In this paper, we investigate the surface properties of a series of copolymers of perfluoroalkyl methacrylate (CH2 = C(CH3)COOCH2CnF(2n + 1), n = 1, 6, or 10) and methyl methacrylate (MMA) and of blends of perfluorooctyl-end-capped poly(methyl methacrylate) (PMMA) and pure PMMA. The introduction of perfluoroalkyl groups significantly lowers the polymer surface energy as determined by the acid-base approach. X-ray photoelectron spectroscopy (XPS) confirms a higher fluorine concentration in the surface region (the outer 3.8 nm) as compared to in the bulk. The fluorine density in the outermost atomic layer is quantitatively determined by low-energy ion scattering (LEIS). A linear relationship is found between the fluorine density in the outermost atomic layer and the surface energy of the partially fluorinated polymethacrylates, irrespective of the length of the perfluoroalkyl chain. This linearity confirms Langmuir's "principle of independent surface action". Deviation from this linear relationship exists for both highly and sparsely fluorinated polymethacrylates and can be ascribed to the local (surface) ordering of the fluorinated tails and MMA units, respectively. This study may offer one further step toward a deeper understanding of the correlations between macroscopic surface properties and microscopic surface chemical composition.     

Steady shear rate rheology of suspensions, as described by the giant floc model

The break-down of a particle network by shear is described as the development of shear planes: a region able to withstand low shear stresses may break down under a larger stress; thus with increasing shear stress and shear rate, the mutual distance (A) between successive shear planes decreases until, at very high shear rates, A approaches the particle diameter. The shear planes are idealised as flat planes. Energy dissipation during shear is predominantly due to the energy dissipated through the movement of the particles; the energy dissipation due to breakage and renewed formation of bonds between particles is relatively small. A consideration of the energy dissipated during the encounters of particles during shear, including that dissipated by entrained particles, then leads to a relation between this energy dissipation and the average fraction L, over which a moving particle entrains a neighbour. L includes the effect of parts of the network which are rotating under the influence of the shear. In the limit of large shear rates, L is found to depend only to a small extent on whether the suspension is coagulated or not.     

The Electroviscous Behavior of Aqueous Dispersions of Amorphous Silica (Ludox)

The electroviscous effects in very dilute aqueous dispersions of amorphous silica (Ludox) were investigated at various levels of salt, pH, and volume fraction (<0.01) of solids. Viscosities were much higher than predicted from existing theories, which is ascribed to the formation of a thick, gel-like surface layer on the particle. The volume of a particle adjusts itself almost reversibly to the salt and pH levels of the liquid and can grow up to four times the dry volume. This explains the apparent discrepancy between published dry and wet particle sizes and also the reported anomalously large number of bound water layers around a particle. The existence of a gel layer leads to an abnormally large amount of surface conductance; this may explain the anomalities found in electrophoresis. The validity of the model is also supported by published results of the amount of nonbulk water as found with NMR. Copyright 2001 Academic Press.     

Incompatibility of polymer solutions. II. Concentration and angle dependence of the light scattering in the system polystyrene + polyisobutylene + toluene

Light scattering experiments are described on the system polystyrene (PS) + polyisobutylene (PIB) + toluene at constant temperature. At a fixed concentration of the nearly “invisible” PIB the light scattering at various angles was measured as a function of varying PS concentration up to the region of incompatibility. For interpretation of the results use is made of an extension of the classical fluctuation theory for multicomponent systems to finite scattering angles. The experimental data can be described qualitatively with this theory. Addition of a second polymer has little influence on the size of the other polymer. The variation of the light scattering with the wavelength can be explained in terms of the (negative) adsorption of one polymer by the other.     

Shear thickening in electrically-stabilized colloidal suspensions

A theory is presented for the onset of shear thickening in colloidal suspensions of particles, stabilized by an electrostatic repulsion. Based on an activation model, a critical shear stress can be derived for the onset of shear thickening in dense suspensions for a constant potential and a constant charge approach of the spheres. Unlike previous models, the total interaction potential is taken into account (sum of attraction and repulsion). The critical shear stress is related to the maximum of the total interaction potential scaled by the free volume per particle. A comparison with experimental investigations shows the applicability of the theory.     

Spatially resolved surface-charge measurement in a planar dielectric-barrier discharge system

We investigate a laterally extended dielectric helium discharge system with plane electrodes. The system is operated in the glow mode and is known to exhibit a rich variety of self-organized lateral patterns in the current distribution, most of them being filamentary. It is known from theory that surface charges on the dielectrics play a major role for the emerging patterns. In this work we present a method to measure the spatial charge distribution on the dielectrics via the Pockels effect of a bismuth-silicon-oxide crystal. The experimental results of the surface-charge distribution measurements are in good agreement with previous numerical solutions of the corresponding transport equations.