<i>In situ</i> EPR and Raman spectroscopy in the curing of bis-methacrylate-styrene resins

The curing of bis-methacrylate-styrene resins initiated by the cobalt catalyzed decomposition of cumyl hydroperoxide is monitored at ambient temperatures in situ by EPR and Raman spectroscopy. EPR spectroscopy shows the appearance of organic radicals after ca. 1 h from initiation with an increase in intensity from both polystyrene and methacrylate based radical species over a further ca. 2 h period to reach a maximum spin concentration of ca. 2-3 mM. Alkene conversion to polymer was monitored by Raman spectroscopy in real time in situ with EPR spectroscopy and reveals that the appearance of the radical signals is first observed only as the conversion approaches its maximum extent (70% at room temperature), i.e., the resin reaches a glass-like state. The radicals persist for several months on standing at room temperature. Flash frozen samples (77 K) did not show EPR signals within 1 h of initiation. The nature of the radicals responsible for the EPR spectra observed were explored by DFT methods and isotope labelling experiments (D8-styrene) and correspond to radicals of both methacrylate and polystyrene. Combined temperature dependent EPR and Raman spectroscopy shows that conversion increases rapidly upon heating of a cured sample, reaching full conversion at 80 °C with initially little effect on the EPR spectrum. Over time (i.e. subsequent to reaching full conversion of alkene) there was a small but clear increase in the EPR signal due to the methacrylate based radicals and minor decrease in the signal due to the polystyrene based radicals. The appearance of the radical signals as the reaction reaches completion and their absence in samples flash frozen before polymerization has halted, indicate that the observed radicals are non-propagating. The formation of the radicals due to stress within the samples is excluded. Hence, the observed radicals are a representative of the steady state concentration of radicals present in the resin over the entire timespan of the polymerization. The data indicate that the lack of EPR signals is most likely due to experimental aspects, in particular spin saturation, rather than low steady state concentrations of propagating radicals during polymerization.</p

Reaching a Double-Digit Dielectric Constant with Fullerene Derivatives

The dielectric constant (ϵr) of organic semiconductors is a key material parameter for improving device performance in the field of organic electronics. However, the effect of the dielectric constant on the electronic and optoelectronic properties of materials remains unclear due to the scarcity of known organic semiconductors with an ϵr value higher than 6. Herein, the optical and electronic properties of a homologous series of fullerene derivatives with high ϵr are studied. The low frequency (<106 Hz) ϵr is extracted from the capacitance measured using impedance spectroscopy, and the effect of length (n) and geometrical arrangement of the polar ethylene glycol (EG) side chains is investigated. The ϵr is found to correlate with length for the symmetrical Bingel adducts, whereas for the unsymmetrical branched-EG chain adducts there is no significant difference between the two EG chain lengths. For BTrEG-2, the ϵr reaches 10, which is an unprecedented value in monoadduct fullerene derivatives. These materials open up new possibilities of studying the effect of ϵr in organic electronic devices such as organic photovoltaics, organic thermoelectrics, and organic field-effect transistors

Goal-Adaptive Meshing of Isogeometric Kirchhoff-Love Shells

International audienceMesh adaptivity is a technique to provide detail in numerical solutions without the need to refine the mesh over the whole domain. Mesh adaptivity in isogeometric analysis can be driven by Truncated Hierarchical B-splines (THB-splines) which add degrees of freedom locally based on finer B-spline bases. Labeling of elements for refinement is typically done using residual-based error estimators. In this paper, an adaptive meshing workflow for isogeometric Kirchhoff-Love shell analysis is developed. This framework includes THB-splines, mesh admissibility for combined refinement and coarsening and the Dual-Weighted Residual (DWR) method for computing element-wise error contributions. The DWR can be used in several structural analysis problems, allowing the user to specify a goal quantity of interest which is used to mark elements and refine the mesh. This goal functional can involve, for example, displacements, stresses, eigenfrequencies etc. The proposed framework is evaluated through a set of different benchmark problems, including modal analysis, buckling analysis and non-linear snap-through and bifurcation problems, showing high accuracy of the DWR estimator and efficient allocation of degrees of freedom for advanced shell computations

Stretch-Based Hyperelastic Material Formulations for Isogeometric Kirchhoff-Love Shells with Application to Wrinkling

International audienceModelling nonlinear phenomena in thin rubber shells calls for stretch-based material models, such as the Ogden model which conveniently utilizes eigenvalues of the deformation tensor. Derivation and implementation of such models have been already made in Finite Element Methods. This is, however, still lacking in shell formulations based on Isogeometric Analysis, where higher-order continuity of the spline basis is employed for improved accuracy. This paper fills this gap by presenting formulations of stretch-based material models for isogeometric Kirchhoff-Love shells. We derive general formulations based on explicit treatment in terms of derivatives of the strain energy density functions with respect to principal stretches for (in)compressible material models where determination of eigenvalues as well as the spectral basis transformations is required. Using several numerical benchmarks, we verify our formulations on invariant-based Neo-Hookean and Mooney-Rivlin models and with a stretch-based Ogden model. In addition, the model is applied to simulate collapsing behaviour of a truncated cone and it is used to simulate tension wrinkling of a thin sheet

Activation of alkyl hydroperoxides by manganese complexes of tmtacn for initiation of radical polymerisation of alkenes

The activation of alkyl hydroperoxides to generate radicals is a key step in the initiation of radical polymerisations in many industrial applications, not least protective coatings. Cobalt soaps (Co(II) alkyl carboxylates) are highly effective catalysts under ambient conditions but viable alternatives based on less scarce catalysts are desirable, with especially iron and manganese catalysts showing potential. Manganese complexes of the ligand N,N′,N″-trimethyl-1,4,7-triazacyclononane (tmtacn) are long established as catalysts for organic oxidations with H2O2, however their reactivity with alkyl hydroperoxides is less studied especially in apolar solvents. Here we show that this family of complexes can be employed as catalysts for the decomposition of alkyl hydroperoxides in apolar solvents such as styrene/methyl methacrylate mixtures and resins based on styrene/bisphenol-A based diglycidyl ether bismethacrylate (BADGE-MA). The progress of alkene polymerisation in crosslinking resins is followed by Raman spectroscopy to establish its dependence on the oxidation state of the manganese catalyst used, as gelation time and onset of autoacceleration are of particular interest for many applications. We show, through reaction progress monitoring with UV/vis absorption and Raman spectroscopy, that the stability of the manganese complexes in the resin mixtures has a substantial effect on curing progress and that the oxidation state of the resting state of the catalyst is most likely Mn(II), in contrast to reactions with H2O2 as oxidant in which the oxidation state of the resting state of catalyst is Mn(III). Manganese complexes of tmtacn are shown to be capable initiators of alkene radical polymerisations, and their rich coordination and redox chemistry means that resin curing kinetics can potentially be tuned more readily than with cobalt alkyl carboxylates.</p

Characterisation and modelling of a compact multiwavelength ringlaser

Detailed spectral characteristics have been measured of an integrated compact multiwavelength ringlaser under a wide range of operating conditions. The laser consists of a single PHASAR and four semiconductor optical amplifiers. It can produce 7 different wavelengths in the 1.5micrometer region, three of which could be produced by driving two SOAs simultaneously. The frequency selective mechanism that led to these combination wavelengths was established and a rate equation model of the laser was written that reproduces the observed behaviour of the laser. Input parameters to the model were derived from the simulation of a number of integrated extended-cavity Fabry-Perot lasers

Activation of alkyl hydroperoxides by manganese com plexes of tmtacn for initiation of radical polymerisation of alkenes

The activation of alkyl hydroperoxides to generate radicals is a key step in the initiation of radical polymerisations in many industrial applications, not least protective coatings. Cobalt soaps are highly effective catalysts under ambient conditions but viable alternatives based on less scarce catalysts are desirable, with especially iron and manganese catalysts showing potential. Manganese complexes of the ligand N,N\u27,N"-trimethyl-1,4,7-triazacyclononane (tmtacn) are long established as catalysts for organic oxidations with H2O2, however their reactivity with alkyl hydroperoxides is less studied especially in low- or apolar solvents. Here we show that this family of complexes can be employed as catalysts for the decomposition of alkyl hydroperoxides in apolar solvents such as styrene/methyl methacrylate mixtures and resins based on styrene/bisphenol-A based diglycidyl ether bismethacrylate (BADGE-MA). The progress of alkene polymerisation in crosslinking resins is followed by Raman spectroscopy to establish its dependence on the oxidation state of the manganese catalyst used, as gelation time and onset of autoacceleration are of particular interest for many applications. We show, through reaction progress monitoring with UV/vis absorption and Raman spectroscopy, that the stability of the manganese complexes in the resin mixtures has a substantial effect on curing progress and that the oxidation state of the resting state of the catalyst is most likely Mn(II), in contrast to reactions with H2O2 as oxidant in which the oxidation state of the resting state of catalyst is Mn(III). Manganese complexes of tmtacn are shown to be capable initiators of alkene radical polymerisations, and their rich coordination and redox chemistry means that resin curing kinetics can potentially be tuned more readily than with cobalt soaps

Contact and Portuguese‐lexified creoles

Portuguese‐lexified creoles (PLCs) include some of the oldest of the European‐lexified creoles which developed out of the colonial expansion of the Early Modern Age. This chapter describes in detail the current and past distribution of the PLCs. It surveys diachronic proposals applicable within subgroups of PLCs. The chapter focuses on theories that imply the influence of a PLC or Portuguese‐lexified pidgin on contact languages currently not classified as Portuguese‐lexified. One of the most interesting effects of the inaugural role of Portuguese in the European global linguistic expansion of the Modern Age is that, for various reasons and to different degrees, Portuguese often came to impact the linguistic repertoire of the colonizers who followed and, on many occasions, occupied places where this language had already created roots. Wherever PLCs have remained in close contact with Portuguese, a number of different trajectories can be identified.info:eu-repo/semantics/draf