Curing kinetics and chemorheology of epoxy/anhydride system

The curing kinetics and chemorheology of a low‐viscosity laminating system, based on a bisphenol A epoxy resin, an anhydride curing agent, and a heterocyclic amine accelerator, are investigated. The curing kinetics are studied in both dynamic and isothermal conditions by means of differential scanning calorimetry. The steady shear and dynamic viscosity are measured throughout the epoxy/anhydride cure. The curing kinetics of the thermoset system is described by a modified Kamal kinetic model, accounting for the diffusion‐control effect. A chemorheological model that describes the system viscosity as a function of temperature and conversion is proposed. This model is a combination of the Williams–Landel–Ferry equation and a conversion term originally used by Castro and Macosko. A good agreement between the predicted and experimental results is obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3012–3019, 2003     

Numerical simulation of ammonia/methane/air combustion using reduced chemical kinetics models

Ammonia appears to be a potential alternative fuel that can be used as a hydrogen vector and fuel for gas turbines and internal combustion engines. Chemical mechanisms of ammonia combustion are important for the development of ammonia combustion systems, but also as a mean of investigation of harmful NOx emissions, so they can be minimized. Despite of large body of experimental and modelling work on the topic of ammonia combustion, there is still need for additional investigation of combustion kinetics.The object of this work is further numerical study of ammonia combustion chemistry under conditions resembling industrial ones. After literature review, three mechanisms of ammonia combustion that also include carbon chemistry are used for simulation of experimental premixed swirl burner with the aim of evaluating their performance. San Diego mechanism, that was also the most detailed one, proved to be the best in terms of emissions, but neither one of the models was able to accurately reproduce CO emission after equivalence ratio went beyond 0.81. It was also observed that oxygen is excessively consumed. This study contributes to the current knowledge by providing new insights in ammonia burning conditions closely resembling those in industrial applications, and consequently is expected that insights obtained will help in the design of real industrial burning systems.     

Commentary to: An exact schedulability test for fixed-priority preemptive mixed-criticality real-time systems

Real-Time Systems - In this paper we point to some errors in recent paper by Asyaban et al. in which they devise an exact schedulability test. These errors are critical for the correct operation of...     

Coherent phonon anisotropy in aligned single-walled carbon nanotubes

By time-resolved reflectivity measurements with sub-10 fs laser pulses at 395 nm, the coherent phonons of aligned bundles of single-walled carbon nanotubes are observed for various polarization directions of the pump and probe pulses. In the isotropic reflectivity measurement, we observe the radial breathing modes, G, and even D modes, while in the anisotropic reflectivity mode, only the G mode appears. A complex polarization dependence of the G band phonon amplitude in the isotropic reflectivity is explained by the superposition of G band phonons with different symmetries.     

Femtosecond microscopy of surface plasmon polariton wave packet evolution at the silver/vacuum interface

A movie of the dispersive and dissipative propagation of surface plasmon polariton (SPP) wave packets at a silver/vacuum interface is recorded by the interferometric time-resolved photoemission electron microscopy with 60 nm spatial resolution and 330 as frame interval. The evolution of SPP wave packets is imaged through a two-path interference created by a pair of 10 fs phase correlated pump-probe light pulses at 400 nm. The wave packet evolution is simulated using the complex dielectric function of silver.     

Hemolymph amino acid analysis of individual Drosophila larvae

One of the most widely used transgenic animal models in biology is Drosophila melanogaster, the fruit fly. Chemical information from this exceedingly small organism is usually accomplished by studying populations to attain sample volumes suitable for standard analysis methods. This paper describes a direct sampling technique capable of obtaining 50-300 nL of hemolymph from individual Drosophila larvae. Hemolymph sampling performed under mineral oil and in air at 30 s intervals up to 120 s after piercing larvae revealed that the effect of evaporation on amino acid concentrations is insignificant when the sample was collected within 60 s. Qualitative and quantitative amino acid analyses of obtained hemolymph were carried out in two optimized buffer conditions by capillary electrophoresis with laser-induced fluorescence detection after derivatizing with fluorescamine. Thirteen amino acids were identified from individual hemolymph samples of both wild-type (WT) control and the genderblind (gb) mutant larvae. The levels of glutamine, glutamate, and taurine in the gb hemolymph were significantly lower at 35%, 38%, and 57% of WT levels, respectively. The developed technique that samples only the hemolymph fluid is efficient and enables accurate organism-level chemical information while minimizing errors associated with possible sample contaminations, estimations, and effects of evaporation compared to the traditional hemolymph-sampling techniques.     

Cure modelling of polyester thermosets in a glass mould

The curing of unsaturated polyester was studied experimentally and using a model of the process. The kinetic parameters were calculated from the heat flow–time curves obtained by differential scanning calorimetry (Mettler Toledo DSC 823), operating in a non-isothermal mode. The temperature–time histories were studied in a cylindrical glass mould. A potential use of glass as a mould for polymer curing is found in the production of optical sensors. Here, glass was selected as a mould material because it is UV transparent, chemically inert and easy to clean. The thermal properties of glass moulds coupled with the intrinsic curing kinetics are of a significant interest in such investigations. Taking into account the heat transferred by the convection from the air to the mould surface and the conduction through the mould wall and resin, as well as the kinetics of the heat generated in the cure reaction, a numerical model has been constructed. The contributions to the rise in temperature from the heat conduction and chemical reaction are different in different parts of the composite, which can explain the temperature–time histories. The introduction of a carbonate based filler reduced the amount of heat released in the composite and, as a result, lowered the temperatures through the resin. A good agreement between experimental data and the predicted mathematical model of the curing process in the mould has been observed.     

The electronic properties of superatom states of hollow molecules

Electronic and optical properties of molecules and molecular solids are traditionally considered from the perspective of the frontier orbitals and their intermolecular interactions. How molecules condense into crystalline solids, however, is mainly attributed to the long-range polarization interaction. In this Account, we show that long-range polarization also introduces a distinctive set of diffuse molecular electronic states, which in quantum structures or solids can combine into nearly-free-electron (NFE) bands. These NFE properties, which are usually associated with good metals, are vividly evident in sp(2) hybridized carbon materials, specifically graphene and its derivatives. The polarization interaction is primarily manifested in the screening of an external charge at a solid/vacuum interface. It is responsible for the universal image potential and the associated unoccupied image potential (IP) states, which are observed even at the He liquid/vacuum interface. The molecular electronic properties that we describe are derived from the IP states of graphene, which float above and below the molecular plane and undergo free motion parallel to it. Rolling or wrapping a graphene sheet into a nanotube or a fullerene transforms the IP states into diffuse atom-like orbitals that are bound primarily to hollow molecular cores, rather than the component atoms. Therefore, we named them the superatom molecular orbitals (SAMOs). Like the excitonic states of semiconductor nanostructures or the plasmonic resonances of metallic nanoparticles, SAMOs of fullerene molecules, separated by their van der Waals distance, can combine to form diatomic molecule-like orbitals of C(60) dimers. For larger aggregates, they form NFE bands of superatomic quantum structures and solids. The overlap of the diffuse SAMO wavefunctions in van der Waals solids provides a different paradigm for band formation than the valence or conduction bands formed by interaction of the more tightly bound, directional highest occupied molecular orbitals (HOMOs) or the lowest unoccupied molecular orbitals (LUMOs). Therefore, SAMO wavefunctions provide insights into the design of molecular materials with potentially superior properties for electronics. Physicists and chemists have thought of fullerenes as atom-like building blocks of electronic materials, and superatom properties have been attributed to other elemental gas-phase clusters based on their size-dependent electronic structure and reactivity. Only in the case of fullerenes, however, do the superatom properties survive as delocalized electronic bands even in the condensed phase. We emphasize, however, that the superatom states and their bands are usually unoccupied and therefore do not contribute to intermolecular bonding. Instead, their significance lies in the electronic properties they confer when electrons are introduced, such as when they are excited optically or probed by the atomically sharp tip of a scanning tunneling microscope. We describe the IP states of graphene as the primary manifestation of the universal polarization response of a molecular sheet and how these states in turn define the NFE properties of materials derived from graphene, such as graphite, fullerenes, and nanotubes. Through low-temperature scanning tunneling microscopy (LT-STM), time-resolved two-photon photoemission spectroscopy (TR-2PP), and density functional theory (DFT), we describe the real and reciprocal space electronic properties of SAMOs for single C(60) molecules and their self-assembled 1D and 2D quantum structures on single-crystal metal surfaces.