A critical analysis of polymer cure modeling for microelectronics applications

A review of polymer cure models used in microelectronics packaging applications reveals no clear consensus of the chemical rate constants for the cure reactions, or even of an effective model. The problem lies in the contrast between the actual cure process, which involves a sequence of distinct chemical reactions, and the models, which typically assume only one, (or two with some restrictions on the independence of their characteristic constants.) The standard techniques to determine the model parameters are based on differential scanning calorimetry (DSC), which cannot distinguish between the reactions, and hence yields results useful only under the same conditions, which completely misses the point of modeling. The obvious solution is for manufacturers to provide the modeling parameters, but failing that, an alternative experimental technique is required to determine individual reaction parameters, e.g. Fourier transform infra-red spectroscopy (FTIR).

Implications of streamlining theory for microbial ecology

Whether a small cell, a small genome or a minimal set of chemical reactions with self-replicating properties, simplicity is beguiling. As Leonardo da Vinci reportedly said, 'simplicity is the ultimate sophistication'. Two diverging views of simplicity have emerged in accounts of symbiotic and commensal bacteria and cosmopolitan free-living bacteria with small genomes. The small genomes of obligate insect endosymbionts have been attributed to genetic drift caused by small effective population sizes (Ne). In contrast, streamlining theory attributes small cells and genomes to selection for efficient use of nutrients in populations where Ne is large and nutrients limit growth. Regardless of the cause of genome reduction, lost coding potential eventually dictates loss of function. Consequences of reductive evolution in streamlined organisms include atypical patterns of prototrophy and the absence of common regulatory systems, which have been linked to difficulty in culturing these cells. Recent evidence from metagenomics suggests that streamlining is commonplace, may broadly explain the phenomenon of the uncultured microbial majority, and might also explain the highly interdependent (connected) behavior of many microbial ecosystems. Streamlining theory is belied by the observation that many successful bacteria are large cells with complex genomes. To fully appreciate streamlining, we must look to the life histories and adaptive strategies of cells, which impose minimum requirements for complexity that vary with niche.

Chemistry and Release of Gases from the Surface Ocean

The sea-surface layer is the very upper part of the sea surface where reduced mixing leads to strong gradients in physical, chemical and biological properties1. This surface layer is naturally reactive, containing a complex chemistry of inorganic components and dissolved organic matter (DOM), the latter including amino acids, proteins, fatty acids, carbohydrates, and humic-type components,2 with a high proportion of functional groups such as carbonyls, carboxylic acids and aromatic moieties.3 The different physical and chemical properties of the surface of the ocean compared with bulk seawater, and its function as a gateway for molecules to enter the atmosphere or ocean phase, make this an interesting and important region for study. A number of chemical reactions are believed to occur on and in the surface ocean; these may be important or even dominant sources or sinks of climatically-active marine trace gases. However the sea surface, especially the top 1um to 1mm known as the sea surface microlayer (ssm), is critically under-sampled, so to date much of the evidence for such chemistry comes from laboratory and/or modeling studies. This review discusses the chemical and physical structure of the sea surface, mechanisms for gas transfer across it, and explains the current understanding of trace gas formation at this critical interface between the ocean and atmosphere.

The Validation of a Two-Dimensional Transient Catalyst Model for Direct Injection Two-Stroke Applications

This paper describes the detailed validation of a computer model designed to simulate the transient light-off in a two-stroke oxidation catalyst. A plug flow reactor is employed to provide measurements of temperature and gas concentration at various radial and axial locations inside the catalyst. These measurements are recorded at discrete intervals during a transient light-off in which the inlet temperature is increased from ambient to 300oC at rates of up to 6oC/sec. The catalyst formulation used in the flow reactor, and its associated test procedures, are then simulated by the computer and a comparison made between experimental readings and model predictions. The design of the computer model to which this validation exercise relates is described in detail in a separate technical paper. The first section of the paper investigates the warm-up characteristics of the substrate and examines the validity of the heat transfer predictions between the wall and the gas in the absence of chemical reactions. The predictions from a typical single-component CO transient light-off test are discussed in the second section and are compared with experimental data. In particular the effect of the temperature ramp on the light-off curve and reaction zone development is examined. An analysis of the C3H6 conversion is given in the third section while the final section examines the accuracy of the light-off curves which are produced when both CO and C3H6 are present in the feed gas. The analysis shows that the heat and mass transfer calculations provided reliable predictions of the warm-up behaviour and post light-off gas concentration profiles. The self-inhibition and cross-inhibition terms in the global rate expressions were also found to be reasonably reliable although the surface reaction rates required calibration with experimental data.

Effect of heat treatment on the antioxidant activity, color, and free phenolic acid profile of malt

Green malt was kilned at 95 degrees C following two regimens: a standard regimen (SKR) and a rapid regimen (RKR). Both resulting malts were treated further in a tray dryer heated to 120 degrees C, as was green malt previously dried to 65 degrees C (TDR). Each regimen was monitored by determining the color, antioxidant activity (by both ABTS(center dot+) and FRAP methods), and polyphenolic profile. SKR and RKR malts exhibited decreased L* and increased b* values above approximately 80 degrees C. TDR malts changed significantly less, and color did not develop until 110 degrees C, implying that different chemical reactions lead to color in those malts. Antioxidant activity increased progressively with each regimen, although with TDR malts this became significant only at 110-120 degrees C. The RKR malt ABTS(center dot+) values were higher than those of the SKR malt. The main phenolics, that is, ferulic, p-coumaric, and vanillic acids, were monitored throughout heating. Ferulic acid levels increased upon heating to 80 degrees C for SKR and to 70 degrees C for RKR, with subsequent decreases. However, the levels for TDR malts did not increase significantly. The increase in free phenolics early in kilning could be due to enzymatic release of bound phenolics and/or easier extractability due to changes in the matrix. The differences between the kilning regimens used suggest that further modification of the regimens could lead to greater release of bound phenolics with consequent beneficial effects on flavor stability in beer and, more generally, on human health.

CO oxidation and NO reduction on metal surfaces: density functional theory investigations

This article reviews the accumulated theoretical results, in particular density functional theory calculations, on two catalytic processes, CO oxidation and NO reduction on metal surfaces. Owing to their importance in automotive emission control, these two reactions have generated a lot of interest in the last 20 years. Here the pathways and energetics of the involved elementary reactions under different catalytic conditions are described in detail and the understanding of the reactions is generalized. It is concluded that density functional theory calculations can be applied to catalysis to elucidate mechanisms of complex surface reactions and to understand the electronic structure of chemical processes in general. The achieved molecular knowledge of chemical reactions is certainly beneficial to new catalyst design.

Plasma chloriding of thin-film silver - A novel process in silver-silver chloride reference electrode fabrication

Silver thin films were modified using a novel plasma modification process for the development of thin-film silver-silver chloride reference electrodes. The surface, physical, and electrochemical properties of these electrodes were investigated by atomic force microscopy, thickness and resistivity measurement techniques, as well as impedance spectroscopy and potentiometry. After plasma treatment, thin-film growth was observed and the electrodes, in general, exhibited low interface impedance and a roughened surface. Evidence of a complex surface reorganization was found. Correlating plasma conditions with film properties suggested that increasing pressure and exposure duration increased species availability, therefore governing the reaction rates, while input power appeared to influence the type of surface chemical reactions. Results also indicated that Ar/Cl-2 mixtures should be employed rather than pure chlorine plasmas. (C) 2002 The Electrochemical Society.

Cyanopolyynes in hot cores: modelling G305.2+0.2

We present results from a time-dependent gas-phase chemical model of a hot core based on the physical conditions of G305.2+0.2. While the cyanopolyyne HC3N has been observed in hot cores, the longer chained species, HC5N, HC7N and HC9N, have not been considered as the typical hot-core species. We present results which show that these species can be formed under hot core conditions. We discuss the important chemical reactions in this process and, in particular, show that their abundances are linked to the parent species acetylene which is evaporated from icy grain mantles. The cyanopolyynes show promise as ‘chemical clocks’ which may aid future observations in determining the age of hot core sources. The abundance of the larger cyanopolyynes increases and decreases over relatively short time-scales, ~10^2.5 yr. We present results from a non-local thermodynamic equilibrium statistical equilibrium excitation model as a series of density, temperature and column density dependent contour plots which show both the line intensities and several line ratios. These aid in the interpretation of spectral-line data, even when there is limited line information available. In particular, non-detections of HC5N and HC7N in Walsh et al. are analysed and discussed.

Carbon chemistry in Galactic bulge planetary nebulae

Galactic bulge planetary nebulae show evidence of mixed chemistry with emission from both silicate dust and polycyclic aromatic hydrocarbons (PAHs). This mixed chemistry is unlikely to be related to carbon dredge-up, as third dredge-up is not expected to occur in the low-mass bulge stars. We show that the phenomenon is widespread and is seen in 30 nebulae out of 40 of our sample, selected on the basis of their infrared flux. Hubble Space Telescope (HST) images and Ultraviolet and Visual Echelle Spectrograph (UVES) spectra show that the mixed chemistry is not related to the presence of emission-line stars, as it is in the Galactic disc population. We also rule out interaction with the interstellar medium (ISM) as origin of the PAHs. Instead, a strong correlation is found with morphology and the presence of a dense torus. A chemical model is presented which shows that hydrocarbon chains can form within oxygen-rich gas through gas-phase chemical reactions. The model predicts two layers, one at A_V~ 1.5, where small hydrocarbons form from reactions with C+, and one at A_V~ 4, where larger chains (and by implication, PAHs) form from reactions with neutral, atomic carbon. These reactions take place in a mini-photon-dominated region (PDR). We conclude that the mixed-chemistry phenomenon occurring in the Galactic bulge planetary nebulae is best explained through hydrocarbon chemistry in an ultraviolet (UV)-irradiated, dense torus.

Gas and grain chemistry in a protoplanetary disk

The chemistry in a protoplanetary accretion disk is modelled between a radius of 100 and 0.1 AU of the central object. We find that interaction of the gas with the dust grains is very important, both by removing a large fraction of the material from the gas in the outer regions and through the chemical reactions which can occur on the dust grain surfaces. In addition, collision with grains neutralises gaseous ions effectively and keeps the ionization fraction low. This results in a chemistry which is dominated by neutral-neutral reactions, even if ionization is provided by cosmic rays or by the decay of radioactive isotopes. We model the effects of two desorption processes with very different efficiencies and find that while these produce similar results over much of the disk for many species, some molecules are extremely sensitive to the nature of the desorption and may one day be used as an observational test for the desorption process.

Galactic Bulge PNe:Carbon molecules in oxygen-rich environments

Galactic bulge planetary nebulae show evidence of mixed chemistry with emission from both silicate dust and PAHs. This mixed chemistry is unlikely to be related to carbon dredge up, as third dredge-up is not expected to occur in the low mass bulge stars. We show that the phenomenon is widespread, and is seen in 30 nebulae out of our sample of 40. A strong correlation is found between strength of the PAH bands and morphology, in particular, the presence of a dense torus. A chemical model is presented which shows that hydrocarbon chains can form within oxygen-rich gas through gas-phase chemical reactions. We conclude that the mixed chemistry phenomenon occurring in the galactic bulge planetary nebulae is best explained through hydrocarbon chemistry in an UV-irradiated, dense torus. © 2012 International Astronomical Union.

Complex organic molecules in protoplanetary disks

Context. Protoplanetary disks are vital objects in star and planet formation, possessing all the material, gas and dust, which may form a planetary system orbiting the new star. Small, simple molecules have traditionally been detected in protoplanetary disks; however, in the ALMA era, we expect the molecular inventory of protoplanetary disks to significantly increase.

Aims. We investigate the synthesis of complex organic molecules (COMs) in protoplanetary disks to put constraints on the achievable chemical complexity and to predict species and transitions which may be observable with ALMA.

Methods. We have coupled a 2D steady-state physical model of a protoplanetary disk around a typical T Tauri star with a large gas-grain chemical network including COMs. We compare the resulting column densities with those derived from observations and perform ray-tracing calculations to predict line spectra. We compare the synthesised line intensities with current observations and determine those COMs which may be observable in nearby objects. We also compare the predicted grain-surface abundances with those derived from cometary comae observations.

Results. We find COMs are efficiently formed in the disk midplane via grain-surface chemical reactions, reaching peak grain-surface fractional abundances similar to 10(-6)-10(-4) that of the H nuclei number density. COMs formed on grain surfaces are returned to the gas phase via non-thermal desorption; however, gas-phase species reach lower fractional abundances than their grain-surface equivalents, similar to 10(-12)-10(-7). Including the irradiation of grain mantle material helps build further complexity in the ice through the replenishment of grain-surface radicals which take part in further grain-surface reactions. There is reasonable agreement with several line transitions of H2CO observed towards T Tauri star-disk systems. There is poor agreement with HC3(N) lines observed towards LkCa 15 and GO Tau and we discuss possible explanations for these discrepancies. The synthesised line intensities for CH3OH are consistent with upper limits determined towards all sources. Our models suggest CH3OH should be readily observable in nearby protoplanetary disks with ALMA; however, detection of more complex species may prove challenging, even with ALMA "Full Science" capabilities. Our grain-surface abundances are consistent with those derived from cometary comae observations providing additional evidence for the hypothesis that comets (and other planetesimals) formed via the coagulation of icy grains in the Sun's natal disk.

Polymerisable squaramide receptors for anion binding and sensing

A novel series of polymerisable squaramides has been synthesised in high yields using simple chemical reactions, and evaluated in the binding of anionic species. These vinyl monomers can be used as functional building blocks in co-polymerisations with a plethora of co-monomers or cross-linkers, grace to their compatibility with free-radical polymerisation reactions. Aromatic substituted squaramides were found to be the strongest receptors, while binding of certain anions was accompanied by a strong colour change, attributed to the de-protonation of the squaramide. The best performing squaramide monomers were incorporated in molecularly imprinted polymers (MIPs) targeting a model anion and their capacities and selectivity were evaluated by rebinding experiments. Polymers prepared using the new squaramide monomers were compared to urea based co-polymers, and were found to contain up to 80% of the theoretical maximum number of binding sites, an exceptionally high value compared to previous reports. Strong polymer colour changes were observed upon rebinding of certain anions, equivalent to those witnessed in solution, paving the way for application of such materials in anion sensing devices.



Graphical abstract: Polymerisable squaramide receptors for anion binding and sensing

The optimized geometric structure of the (0001) surface of α-Fe 2O3

A tridimensional model of α-Fe₂O₃ and models of (0001) and (1102) surfaces on it were built. Then the structural optimization of the (0001) surface was presented which explored the influence of the system scale and the terminal surface configuration. Four different models including two different system scale structures (MODEL□ and MODEL□) and two different terminal structures (MODEL□ and MODEL□) were analyzed in this paper. It was concluded that the boundary effect was more important in a smaller system in the structure optimization. And the Fe-terminated was more stable than the O-terminated structure which was agreed with the experiences, this structural model can be used in further work including the monatomic adsorption/desorption and the chemical reactions on this surface.