Hydrolysis of N2O5 on submicron sulfuric acid aerosols

The kinetics of reactive uptake of gaseous N2O5 on submicron sulfuric acid aerosol particles has been investigated using a laminar flow reactor coupled with a differential mobility analyzer (DMA) to characterize the aerosol. The particles were generated by homogeneous nucleation of SO3/H2O mixtures. In the H2SO4 concentration range 26.3−64.5 wt % the uptake coefficient was γ = 0.033 ± 0.004, independent of acid strength. For an acid strength of 45 wt % γ was found to decrease with increasing temperature over the range 263−298 K. From this, temperature dependence values of −115 ± 30 kJ/mol and −25.5 ± 8.4 J/K mol were determined for the changes in enthalpy and entropy of the uptake process, respectively. The results are consistent with a previous model of N2O5 hydrolysis involving both a direct and an acid catalyzed mechanism, with uptake under the experimental conditions limited by mass accommodation.

Reactive uptake coefficients for heterogeneous reaction of N2O5 with submicron aerosols of NaCl and natural sea salt

The kinetics of uptake of gaseous N2O5 on submicron aerosols containing NaCl and natural sea salt have been investigated in a flow reactor as a function of relative humidity (RH) in the range 30-80% at 295±2K and a total pressure of 1bar. The measured uptake coefficients, γ, were larger on the aerosols containing sea salt compared to those of pure NaCl, and in both cases increased with increasing RH. These observations are explained in terms of the variation in the size of the salt droplets, which leads to a limitation in the uptake rate into small particles. After correction for this effect the uptake coefficients are independent of relative humidity, and agree with those measured previously on larger droplets. A value of γ=0.025 is recommended for the reactive uptake coefficient for N2O5 on deliquesced sea salt droplets at 298K and RH>40%.

Crystallization in poly(L-lactide)-b-poly(epsilon-caprolactone) double crystalline diblock copolymers: a study using X-ray scattering, differential scanning calorimetry, and polarized optical microscopy

The crystallization of well-defined poly(L-lactide)-b-poly(epsilon-caprolactone) diblock copolymers, PLLA-b-PCL, was investigated by time-resolved X-ray techniques, polarized optical microscopy (POM), and differential scanning calorimetry (DSC). Two compositions were studied that contained 44 and 60 wt % poly(L-lactide), PLLA (they are referred to as (L44C5614)-C-11 and (L60C409)-C-12, respectively, with the molecular weight of each block in kg/mol as superscript). The copolymers were found to be initially miscible in the melt according to small-angle X-ray scattering measurements (SAXS). Their thermal behavior was also indicative of samples whose crystallization proceeds from a mixed melt. Sequential isothermal crystallization from the melt at 100 degreesC (for 30 min) and then at 30 degreesC (for 15 min) was measured. At 100 degreesC only the PLLA block is capable of crystallization, and its crystallization kinetics was followed by both WAXS and DSC; comparable results were obtained that indicated an instantaneous nucleation with three-dimensional superstructures (Avrami index of approximately 3). The spherulitic nature of the superstructure was confirmed by POM. When the temperature was decreased to 30 degreesC, the PCL block was able to crystallize within the PLLA negative spherulites (with an Avrami index of 2, as opposed to 3 in homo-PCL), and its crystallization rate was much slower than an equivalent homo-PCL. Time-resolved SAXS experiments in (L60C409)-C-12 revealed an initial melt mixed morphology at 165 degreesC that upon cooling transformed into a transient microphase-separated lamellar structure prior to crystallization at 100 degreesC.

A thermoresponsive supramolecular polymer network comprising pyrene-functionalized gold nano-particles and a chain-folding polydiimide.

A thermoresponsive, supramolecular nanocomposite has been prepared by the addition of pyrenyl functionalized gold nanoparticles (AuNPs) to a polydiimide that contains receptor residues designed to form defined complexes with pyrene. The novel pyrenyl-functionalized AuNPs (P-AuNPs) were characterized by transmission electron microscopy, with surface functionalization confirmed by infrared and UV–visible spectroscopic analyses. Mixing solutions of the P-AuNPs and a π-electron-deficient polydiimide resulted in the formation of electronically complementary, chain-folded and π–π-stacked complexes, so affording a new supramolecular nanocomposite network which precipitated from solution. The P-AuNPs bind to the polydiimide via π–π stacking interactions to create supramolecular cross-links. UV–visible spectroscopic analysis confirmed the thermally reversible nature of the complexation process, and transmission electron microscopy (TEM), infrared spectroscopy (IR), and differential scanning calorimetry (DSC) were used to characterize the supramolecular-nanocomposite material. The supramolecular polymer network is insoluble at room temperature, yet may be dissolved at temperatures above 60 °C. The thermal reversibility of this system is maintained over five heat/cool cycles without diminishment of the network characteristics. In contrast to the individual components, the nanocomposite formed self-supporting films, demonstrating the benefit of the supramolecular network in terms of mechanical properties. Control experiments probing the interactions between a model diimide compound that can also form a π-stacked complex with the π-electron rich pyrene units on P-AuNPs showed that, while complexation was readily apparent, precipitation did not occur because a supramolecular cross-linked network system could not be formed with this system.

A mathematical model of crystallization in an emulsion

A mathematical model incorporating many of the important processes at work in the crystallization of emulsions is presented. The model describes nucleation within the discontinuous domain of an emulsion, precipitation in the continuous domain, transport of monomers between the two domains, and formation and subsequent growth of crystals in both domains. The model is formulated as an autonomous system of nonlinear, coupled ordinary differential equations. The description of nucleation and precipitation is based upon the Becker–Döring equations of classical nucleation theory. A particular feature of the model is that the number of particles of all species present is explicitly conserved; this differs from work that employs Arrhenius descriptions of nucleation rate. Since the model includes many physical effects, it is analyzed in stages so that the role of each process may be understood. When precipitation occurs in the continuous domain, the concentration of monomers falls below the equilibrium concentration at the surface of the drops of the discontinuous domain. This leads to a transport of monomers from the drops into the continuous domain that are then incorporated into crystals and nuclei. Since the formation of crystals is irreversible and their subsequent growth inevitable, crystals forming in the continuous domain effectively act as a sink for monomers “sucking” monomers from the drops. In this case, numerical calculations are presented which are consistent with experimental observations. In the case in which critical crystal formation does not occur, the stationary solution is found and a linear stability analysis is performed. Bifurcation diagrams describing the loci of stationary solutions, which may be multiple, are numerically calculated.

The role of citrate precursors on the morphology of lanthanide oxides obtained by thermal decomposition

Two series of lanthanide oxides with different morphologies were synthesized through calcinations of two types of citrate polymeric precursors. These oxides were characterized by XRD patterns, SEM electronic microscopy, and N(2) adsorption isotherms. SEM microscopy analysis showed that the calcination of crystalline fibrous precursors [Ln(2)(LH)(3)center dot 2H(2)O] (L = citrate) originated fibrous shaped particles. On the other hand, the calcination of irregular shaped particles of precursors [LnL center dot xH(2)O] originated irregular shaped particles of oxide, pointing out a morphological template effect of precursors on the formation of the respective oxides.

Anisotropy of thermal stresses in confined dusty plasmas

Anisotropy of thermal stresses in confined dusty plasmas is considered. It is shown that in a multi-component low-temperature plasma containing electrons, ions and dust, the complicated dependence of the ion viscosity on ion temperature gradients leads to a plasma equilibrium state with anisotropic pressure. This pressure anisotropy can be of the order of the ion pressure in some limiting cases, in which the ion Larmor radius or the ion mean free path are of the order of the characteristic length of the plasma nonuniformity. For a sufficiently large dust number density, they contribute to the plasma pressure anisotropy and to its spatial dependence. Currently, it is not yet clear whether this equilibrium state is stable or not. Under these conditions, some convective plasma flows can arise in confinement devices. Therefore, this question needs special consideration.

The long wavelength limit of hard thermal loop effective actions

We derive a closed form expression for the long wavelength limit of the effective action for hard thermal loops in an external gravitational field. It is a function of the metric, independent of time derivatives. It is compared and contrasted with the static limit, and with the corresponding limits in an external Yang-Mills field. (C) 2009 Elsevier B.V. All rights reserved.

Energy-momentum tensor in thermal strong-field QED with unstable vacuum

Themean value of the one-loop energy-momentum tensor in thermal QED with an electric-like background that creates particles from vacuum is calculated. The problem is essentially different from calculations of effective actions ( similar to the action of Heisenberg-Euler) in backgrounds that respect the stability of vacuum. The role of a constant electric background in the violation of both the stability of vacuum and the thermal character of particle distribution is investigated. Restrictions on the electric field and the duration over which one can neglect the back-reaction of created particles are established.

Thermal and structural investigation of Er:YAl(3)(BO(3))(4) nanocrystalline powders

Pure Er:YAB (Er:YAl(3)(BO(3))(4)) nanometer-sized crystalline powder was produced from low cost chemical route, the polymeric precursor method. The initial homogeneous solutions were heat treated from 200 to 700A degrees C under oxygen atmosphere and the unique crystalline phase was synthesized at around 1150A degrees C. The thermal treatments and the initial stoichiometry play a very important role on the Er:YAB preparation. The thermal events of amorphous precursor resins and the crystallization process up to phase formation were investigated.

Surface modification and crystallization of the BaO-B2O3-SiO2 glassy system using CO2 laser irradiation

The surface modification and crystallization process of BaO-B2O3-SiO2 glass compositions when exposed to CO2 laser irradiation was evaluated as a function of the laser power, irradiation time and surface condition. The glass surface was modified by the application of laser power exceeding 0.40 W and an irradiation time of more than 300 s. Micro-Raman and X-ray diffraction measurements revealed at high laser power the formation of beta-BaB2O4 (beta-BBO) crystalline phase. The crystallization of the irradiated region was enhanced when beta-BBO micrometer sized particles were dispersed on the surface of the glass sample. The intensity of the second harmonic generation observed in the crystallized region was found to depend mainly on the condition of the glassy surface prior to glass irradiation. (C) 2007 Elsevier B.V. All rights reserved.

Zn(0.97)M(0.03)O (M = Co, Fe, and V) pigments: thermal, structural, and optical characterization

Zinc oxide is a widely used white inorganic pigment. Transition metal ions are used as chromophores and originate the ceramic pigments group. In this context, ZnO particles doped with Co, Fe, and V were synthesized by the polymeric precursors method, Pechini method. Differential scanning calorimetry (DSC) and thermogravimetry (TG) techniques were used to accurately characterize the distinct thermal events occurring during synthesis. The TG and DSC results revealed a series of decomposition temperatures due to different exothermal events, which were identified as H(2)O elimination, organic compounds degradation and phase formation. The samples were structurally characterized by X-Ray diffractometry revealing the formation of single phase, corresponding to the crystalline matrix of ZnO. The samples were optically characterized by diffuse reflectance measurements and colorimetric coordinates L*, a*, b* were calculated for the pigment powders. The pigment powders presented a variety of colors ranging from white (ZnO), green (Zn(0.97)Co(0.03)O), yellow (Zn(0.97)Fe(0.03)O), and beige (Zn(0.97)V(0.03)O).

Correlation between thermoluminescence sensitivity and crystallization temperatures of quartz: Potential application in geothermometry

The thermoluminescence (TL) characteristics of quartz are highly dependent of its thermal history. Based on the enhancement of quartz luminescence occurred after heating, some authors proposed to use quartz TL to recover thermal events that affected quartz crystals. However, little is know about the influence of the temperature of quartz crystallization on its TL characteristics. In the present study, we evaluate the TL sensitivity and dose response curves of hydrothermal and metamorphic quartz with crystallization temperatures from 209 +/- 15 to 633 +/- 27 degrees C determined through fluid inclusion and mineral chemistry analysis. The studied crystals present a cooling thermal history, which allow the acquiring of their natural TL without influence of heating after crystallization. The TL curves of the studied samples present two main components formed by different peaks overlapped around 110 C and 200-400 degrees C. The TL sensitivity in the 200-400 degrees C region increases linearly with the temperature of quartz crystallization. No relationship was observed between temperatures of quartz crystallization and saturation doses (<100 Gy). The elevated TL sensitivity of the high temperature quartz is attributed to the control exerted by the temperature of crystallization on the substitution of Si(4+) by ions such as Al(3+) and Ti(4+), which produce defects responsible for luminescence phenomena. The linear relationship observed between TL in the 200-400 degrees C region and crystallization temperature has potential use as a quartz geothermometer. The relative abundance of quartz in the earth crust and the easiness to measure TL are advantageous in relation to geothermometry methods based on chemistry of other minerals. (C) 2010 Elsevier Ltd. All rights reserved.

Thermal history versus sedimentary history: OSL sensitivity of quartz grains extracted from rocks and sediments

The optically stimulated luminescence (OSL) sensitivity of quartz has a significant influence on luminescence dating procedures. Furthermore, identifying the natural controls of quartz OSL sensitivity is an important step towards new applications of OSL in geology such as provenance tracing. We evaluate the OSL sensitivity (total and the proportion of the informally assigned fast, medium and slow components) of single grains of quartz extracted from 10 different igneous and metamorphic rocks with known formation conditions; and from fluvial and coastal sediments with different sedimentary histories and known source rocks. This sample suite allows assessment of the variability of the OSL sensitivity of single quartz grains with respect to their primary origin and sedimentary history. We observed significant variability in the OSL sensitivity of grains within all studied rock and sediment samples, with the brightest grains of each sample being those dominated by the fast component. Quartz from rocks formed under high temperature (> 500 degrees C) conditions, such as rhyolites and metamorphic rocks from the amphibolite facies, display higher OSL sensitivity. The OSL sensitivity of fluvial sediments which have experienced only a short transport distance is relatively low. These sediments show a small increase in OSL sensitivity downstream, mainly due to a decreasing fraction of ""dim"" grains. The quartz grains from coastal sands present very high sensitivity and variability, which is consistent with their long sedimentary history. The high variability of the OSL sensitivity of quartz from coastal sands is attributed more to the mixture of grains with distinct sedimentary histories than to the provenance from many types of source rocks. The temperature of crystallization and the number of cycles of burial and solar exposure are suggested as the main natural factors controlling the OSL sensitivity of quartz grains. The increase in OSL sensitivity due to cycles of erosion and deposition surpasses the sensitivity inherited from the source rock, with this increase being mainly related to the sensitization of fast OSL components. The discrimination of grains with different sedimentary histories through their OSL sensitivities can allow the development of quantitative provenance methods based on quartz. (C) 2010 Elsevier B.V. All rights reserved.

Processamento e caracterização de compósitos Poli(METACRILATO DE METILA)/Sílica (PMMA/SiO2)

Currently the search for new materials with properties suitable for specific applications has increased the number of researches that aim to address market needs. The poly (methyl methacrylate) (PMMA) is one of the most important polymers of the family of polyacrylates and polymethacrylates, especially for its unique optical properties and weathering resistance, and exceptional hardness and gloss. The development of polymer composites by the addition of inorganic fillers to the PMMA matrix increases the potential use of this polymer in various fields of application. The most commonly used inorganic fillers are particles of silica (SiO2), modified clays, graphite and carbon nanotubes. The main objective of this work is the development of PMMA/SiO2 composites at different concentrations of SiO2, for new applications as engineering plastics. The composites were produced by extrusion of tubular film, and obtained via solution for application to commercial PMMA plates, and also by injection molding, for improved the abrasion and scratch resistance of PMMA without compromising transparency. The effects of the addition of silica particles in the polymer matrix properties were evaluated by the maximum tensile strength, hardness, abrasion and scratch resistance, in addition to preliminary characterization by torque rheometry and melt flow rate. The results indicated that it is possible to use silica particles in a PMMA matrix, and a higher silica concentration produced an increase of the abrasion and scratch resistance, hardness, and reduced tensile strength