Comparison between Dcrit considering the abrupt variation and inflexion in the concrete mercury intrusion porosimetry curve

Experimental Techniques - Mercury intrusion porosimetry (MIP) has been widely used to evaluate the quality of concrete through the pore size distribution parameters. Two of these parameters are the...     

Synthesis of Dendronized Diblock Copolymers via Click Chemistry: The Effect of Dendronization on Phase Separation Behaviour

A novel route towards the synthesis of well‐defined linear–dendronized diblock copolymers is reported. Precursor alkyne containing diblock copolymers were modified in a highly efficient cycloaddition reaction with dendritic azides of different generation. The dendronization has been shown to be selective and could be driven to completion under ambient conditions. The phase separation of such dendronized diblock copolymers was investigated in dependence of the generation size being attached. Compared to a linear–linear diblock copolymer as starting material the dendronization yielded in a pronounced phase separation. The nanoscaled features observed in thin films strongly depended on the dendron size and a variety of morphologies could be identified. Hence, the unique combination of controlled radical polymerization and click chemistry allows for the triggering of structured surfaces in the nanometer‐regime.

     

White matter hyperintensities and dynamics of postural control

Background

White matter hyperintensities (WMHs) on MRI have been associated with age, cardiovascular risk factors and falls in the elderly. This study evaluated the relationship between WMHs and dynamics of postural control in older adults without history of falls.

Methods

We studied 76 community-living subjects without history of falls (age 64.5±7.3 years). Brain and WMH volume calculations and clinical rating were done on fluid-attenuation inversion recovery (FLAIR) and MP-RAGE MR images on 3 T. Balance was assessed from the center of pressure displacement using the force platform during 3 min of quiet standing using traditional and dynamic measures (using stabilogram-diffusion analysis). Gait speed was measured from 12-min walk.

Results

Age-adjusted periventricular and focal WMHs were associated with changes in certain dynamic balance measures, including reduced range of postural sway in anteroposterior direction (fronto-temporal WMHs, P=.045; parieto-occipital WMHs, P=.009) and more irregular long-term mediolateral fluctuations (P=.046). Normal walking speed was not affected by WMHs.

Conclusions

Periventricular and focal WMHs affect long-term dynamics of postural control, which requires engagement of feedback mechanisms, and may contribute to mobility decline in the elderly.     

Structural properties, electric response and electronic feature of perovskite

It has been observed that the semiconducting compound SnO₂ presents very good results as gas sensor. One important development has been performed to study perovskite oxides for this relevant application. One oxide material which constitutes an excellent candidate for this technological application is BaSnO₃. Polycrystalline samples with single phase of BaSnO₃ were synthesized by using the solid state reaction method. Samples were characterized structurally by means of X-ray diffraction (XRD) technique. Rietveld refinement, by using the GSAS code, reveals that this material synthesizes in a cubic perovskite, space group Pm3m (#221), with lattice parameter . Electric response was examined through the impedance spectroscopy technique. Results of Bode diagram, from an equivalent circuit, evidence the semiconductor character of material. We carried out a theoretical study by means of the calculation of the bands diagram and the density of states of the BaSnO₃. Calculation was performed by employing the density functional theory (DFT), with the generalized gradient approach (GGA). DFT theory permitted to establish that BaSnO₃ material has an indirect semiconducting behavior. The calculated gap for this perovskite-like stagnate is at least 0.4 eV. Bulk modulus for material was also determined to be 132 GPa.     

Structural studies of cyclic ureas: 3. Enthalpy of formation of barbital

A thermochemical and thermophysical study has been carried out for crystalline barbital [5,5′-diethylbarbituric acid]. The thermochemical study was made by static bomb combustion calorimetry, from which the standard () molar enthalpy of formation of the crystalline barbital, at T = 298.15 K, was derived as −(753.0 ± 1.8) kJ · mol⁻¹. The thermophysical study was made by differential scanning calorimetry over the temperature interval (265 to 470) K. A solid–solid phase transition was found at T = 413.3 K. The vapour pressures of the crystalline barbital were measured at several temperatures between T = (355 and 377) K, by the Knudsen mass-loss effusion technique, from which the standard molar enthalpy of sublimation, at T = 298.15 K was derived as (117.3 ± 0.6) kJ · mol⁻¹. The combination of the experimental results yielded the standard molar enthalpy of formation of barbital in the gaseous phase, at T = 298.15 K, as −(635.8 ± 1.9) kJ · mol⁻¹. This value is compared and discussed with our theoretical calculations by several methods (Gaussian-n theories G2 and G3, complete basis set CBS-QB3, density functional B3P86 and B3LYP) by means of atomization and isodesmic reaction schemes.     

Ester-additives as inhibitors of the gelification of soybean oil methyl esters in biodiesel

Biodiesel from soybean oil transesterified with methanol (TSO) becomes viscous and gelifies at low storage temperatures which makes it difficult to pump. To inhibit this behaviour bulky esters were added to reduce the crystallization temperature of TSO and to modify the rate of conversion of crystallized mass. This rate was found to follow a JMAK kinetic model. The Avrami’s parameter n was constant for TSO, while two n values were found for TSO-additive solutions, meaning that the additives first slowed down the rate of nucleation and, later on as enough nuclei had been formed, crystal growth rate dominated and the previous crystallization rate was recovered.     

Weak maximum principle and accessory problem for control problems on time scales

In this paper we derive the first and second variations for a nonlinear time scale optimal control problem with control and state-endpoints equality constraints. Using the first variation, a first order necessary condition for weak local optimality is obtained under the form of a weak maximum principle generalizing the Dubois–Reymond Lemma to the optimal control setting and time scales. A second order necessary condition in terms of the accessory problem is derived by using the nonnegativity of the second variation at all admissible directions. The control problem is studied under a controllability assumption, and with or without the shift in the state variable. These two forms of the problem are shown to be equivalent.     

The development of a method for the determination of trace elements in fuel alcohol by ETV-ICP-MS using isotope dilution calibration

A method for the determination of Ag, Cd, Cu, Pb and Tl in fuel alcohol by isotope dilution electrothermal vaporization inductively coupled plasma mass spectrometry (ID ETV-ICP-MS) is proposed. The analytes were separated in two groups: Ag and Cu were determined without modifier and Cd, Pb and Tl with the use of Pd as chemical modifier. The employed ETV operational conditions were pyrolysis temperature of 800 °C for Cd, Pb and Tl and of 900 °C for Ag and Cu and vaporization temperature of 2400 °C for both groups. Seven common, one with additive and one anhydrous fuel ethanol samples were analyzed. The spiked and reference isotopes were, respectively, ¹⁰⁹Ag and ¹⁰⁷Ag, ¹¹²Cd and ¹¹¹Cd, ⁶³Cu and ⁶⁵Cu, ²⁰⁶Pb and ²⁰⁸Pb and ²⁰³Tl and ²⁰⁵Tl. The added amounts of the enriched isotope material were the same for all samples: 4.6 ng of ¹⁰⁹Ag, 5 ng of ¹¹²Cd, 21.1 ng of ⁶³Cu, 9 ng of ²⁰⁶Pb and 0.21 ng of ²⁰³Tl. The blank was bi-distilled ethanol, acidified with 0.3% (v/v) nitric acid, as the samples. The limits of detection (LODs) were calculated as three times the standard deviation of the concentrations in the blank (n = 10) and were, in μg L⁻¹, for Ag: 0.02, for Cd: 0.08, for Cu: 0.1, for Pb: 0.05 and for Tl: 0.001. The obtained concentrations in the samples were in agreement with those obtained by external calibration (EC), according to the paired t-test. The isotope dilution (ID) showed to be a robust, fast and simple calibration technique for the analysis of fuel ethanol.     

Nonlinear propagation of spark-generated N-waves in air: modeling and measurements using acoustical and optical methods

The propagation of nonlinear spherically diverging N-waves in homogeneous air is studied experimentally and theoretically. A spark source is used to generate high amplitude (1.4 kPa) short duration (40 μs) N-waves; acoustic measurements are performed using microphones (3 mm diameter, 150 kHz bandwidth). Numerical modeling with the generalized Burgers equation is used to reveal the relative effects of acoustic nonlinearity, thermoviscous absorption, and oxygen and nitrogen relaxation on the wave propagation. The results of modeling are in a good agreement with the measurements in respect to the wave amplitude and duration. However, the measured rise time of the front shock is ten times longer than the calculated one, which is attributed to the limited bandwidth of the microphone. To better resolve the shock thickness, a focused shadowgraphy technique is used. The recorded optical shadowgrams are compared with shadow patterns predicted by geometrical optics and scalar diffraction model of light propagation. It is shown that the geometrical optics approximation results in overestimation of the shock rise time, while the diffraction model allows to correctly resolve the shock width. A combination of microphone measurements and focused optical shadowgraphy is therefore a reliable way of studying evolution of spark-generated shock waves in air.