Kinetics of the thermal degradation of Erica arborea by DSC: Hybrid kinetic method

The scope of this work was the determination of kinetic parameters of the thermal oxidative degradation of a Mediterranean scrub using a hybrid method developed at the laboratory. DSC and TGA were used in this study under air sweeping to record oxidative reactions. Two dominating and overlapped exothermic peaks were recorded in DSC and individualized using an experimental and numerical separation. This first stage allowed obtaining the enthalpy variation of each exothermic phenomenon. In a second time, a model free method was applied on each isolated curve to determine the apparent activation energies. A reactional kinetic scheme was proposed for the global exotherm composed of two independent and consecutive reactions. In fine mean values of enthalpy variation and apparent activation energy previously determined were injected in a model fitting method to obtain the reaction order and the preexponential factor of each oxidative reaction. We plan to use these data in a sub-model to be integrated in a wildland fire spread model

Structure and thermal behavior of nanocrystalline boehmite

First, the structural features of nanocrystalline boehmite synthesized by hydrolysis of aluminum sec-butoxide according to the Yoldas method are reported. The nanosized boehmite consists of rectangular platelets averaging 8 by 9 nm and 2–3 nm in thickness which contain a large excess of water. Dehydration by heating under vacuum induced an increase in the specific surface area, down to a minimum water content ( 0.2 H2O per Al2O3); values up to 470 m2/g can be reached. However this enlargement of specific surface area only results from water loss, the surface area remaining constant. The particle morphology, the excess of water, as well as the specific surface area, depend on the amount of acid used for the peptization during the synthesis. Second, a comprehensive investigation of the dehydration kinetics is presented. The simulations of the non-isothermal experiments at constant heating rates show that thermally stimulated transformation of nanocrystalline boehmite into alumina can be accurately modeled by a 4-reaction mechanism involving: (I) the loss of physisorbed water, (II) the loss of chemisorbed water, (III) the conversion of boehmite into transition alumina, (IV) the dehydration of transition alumina (loss of residual hydroxyl groups). The activation energy of each step is found to be very similar for experiments done in various conditions (heating rate, atmosphere, kind of sample,…)

Isoconversional kinetic analysis applied to five phosphoniumcation-based ionic liquids

Thermal degradation of five phosphonium cation-based ionic liquids ([P66614][BEHP], [P66614][(iC8)2PO2],[P66614][NTf2], [P44414][DBS] and [P4442][DEP]) was studied using dynamic methodology (25–600◦C at 5,10 and 20◦C/min) in both inert (nitrogen) and reactive (oxygen) atmospheres. In addition, isothermalexperiments (90 min at 200, 225 and 250◦C) were carried out with [P66614][(iC8)2PO2]. Results indicatethat thermal stability is clearly dominated by the coordination ability of the anion, with [P66614][NTf2] out-performing the other ones in both pyrolytic and oxidising conditions. Although the thermal degradationmechanism is affected by atmospheric conditions, the degradation trend remains practically constant.As the dynamic methodology usually overestimates the long-term thermal stability, an isoconversionalmethodology is better for predicting the long-term thermal stability of these ionic liquids in order to beused as base oil or additive in lubricants formulation. Finally, the model-free methodology can predict atlower costs the ILs performance in isothermal conditions

Vitrification during the Isothermal Cure of Thermosets: Comparison of Theoretical Simulations with Temperature-Modulated DSC and Dielectric Analysis

Vitrification during the isothermal cure of a thermoset, which is monitored by dynamic techniques such as temperature-modulated differential scanning calorimetry (TMDSC) or dielectric analysis (DEA), is analyzed in terms of its dependence on frequency. A simulation was used to obtain the vitrification time as a function of frequency, considering it as the time when the (frequency-dependent) glass transition temperature, Tg, of the curing system reaches the cure temperature. Simulations were carried out at different cure temperatures. Other parameters, such as the exponents (reaction orders) in the Kamal equation, l in the DiBenedetto equation (controlling the dependence of Tg on the degree of cure), and the activation energy for the frequency dependence of Tg, were also considered. The results are compared with those obtained experimentally by a TMDSC technique at low frequencies and by DEA at high frequencies. From the simulations it is found that the vitrification time decreases nonlinearly with log(frequency) in the low frequency range but approaches a linear dependence at high frequencies, in agreement with experimental data.Peer ReviewedPostprin

Finding the trigger to Iapetus' odd global albedo pattern: Dynamics of dust from Saturn's irregular satellites

The leading face of Saturn's moon Iapetus, Cassini Regio, has an albedo only one tenth that on its trailing side. The origin of this enigmatic dichotomy has been debated for over forty years, but with new data, a clearer picture is emerging. Motivated by Cassini radar and imaging observations, we investigate Soter's model of dark exogenous dust striking an originally brighter Iapetus by modeling the dynamics of the dark dust from the ring of the exterior retrograde satellite Phoebe under the relevant perturbations. In particular, we study the particles' probabilities of striking Iapetus, as well as their expected spatial distribution on the Iapetian surface. We find that, of the long-lived particles (greater than about 5 microns), most particle sizes (greater than about 10 microns) are virtually certain to strike Iapetus, and their calculated distribution on the surface matches up well with Cassini Regio's extent in its longitudinal span. The satellite's polar regions are observed to be bright, presumably because ice is deposited there. Thus, in the latitudinal direction we estimate polar dust deposition rates to help constrain models of thermal migration invoked to explain the bright poles (Spencer & Denk 2010). We also analyze dust originating from other irregular outer moons, determining that a significant fraction of that material will eventually coat Iapetus--perhaps explaining why the spectrum of Iapetus' dark material differs somewhat from that of Phoebe. Finally we track the dust particles that do not strike Iapetus, and find that most land on Titan, with a smaller fraction hitting Hyperion. As has been previously conjectured, such exogenous dust, coupled with Hyperion's chaotic rotation, could produce Hyperion's roughly isotropic, moderate-albedo surface.Comment: Accepted for publication in Icaru