Mass transfer limitation in thermogravimetry of biomass gasification

In order to determine the intrinsic reactivity behavior from thermogravimetry studies, the experimental conditions should be such that the reactions are not mass transfer limited. Biomass char usually has a higher reactivity than coal chars. Therefore, mass transfer limitations may be more problematic when studying biomass char reactivity. Chemical reaction kinetics and mass transfer processes present in thermogravimetry are used for modeling the overall reaction rate for spruce bark CO₂ gasification. Thermogravimetric experiments are carried out between 700 and 900 °C, and the CO₂ concentration is varied between 10 and 90 vol%. The intrinsic activation energy is found to be 120 kJ mol^?1. The transition temperature between regimes I and II is here defined when the fraction apparent to true activation energy equals 0.75. Higher external mass transfer (e.g., by decreasing the diffusion path through the crucible’s freeboard), decreasing the sample amounts, and higher CO₂ partial pressures for the Langmuir–Hinshelwood reaction type increase the transition temperature. The results show that the transition temperature between regimes I and II conditions is approx. 1,030 °C for 90 vol% CO₂.     

Wheel/rail noise generation due to nonlinear effects and parametric excitation

Two models are developed, one in the time domain and another in the frequency domain, to explain when a wheel/rail noise generation model requires the inclusion of discrete supports, parametric excitation, and the nonlinear contact spring. Numerical simulations indicate the inclusion of discrete supports to describe low frequency response, and also at higher frequencies, especially where the rail is very smooth or has a corrugation/wavelength corresponding to the pinned-pinned frequency. With a corrugation, it may become essential to include the nonlinear contact spring, as contact loss occurs at high corrugation amplitudes. As nonlinearity causes force generation over a broad frequency range, some contributions excite wheel resonances, resulting in high radiation levels, that require the inclusion of wheel/rail nonlinear effects and parametric excitation for accurate prediction.     

Photo-induced ligand substitution at a remote site via electron transfer in a porphyrin-appended rhenium carbonyl supermolecule

The photochemical and electrochemical properties of a Zn-porphyrin appended rhenium(I) tricarbonyl bipyridine 3-Me-pyridine complex have been investigated; visible-light sensitisation of electron transfer results in ligand substitution at a site remote from the chromophore.     

Bi-laplacian growth patterns in disordered media

Experiments in quasi-two-dimensional geometry (Hele-Shaw cells) in which a fluid is injected into a viscoelastic medium (foam, clay, or associating polymers) show patterns akin to fracture in brittle materials, very different from standard Laplacian growth patterns of viscous fingering. An analytic theory is lacking since a prerequisite to describing the fracture of elastic material is the solution of the bi-Laplace rather than the Laplace equation. In this Letter we close this gap, offering a theory of bi-Laplacian growth patterns based on the method of iterated conformal maps.     

Smectic membranes in motion: approaching the fast limits of x-ray photon correlation spectroscopy

The dynamics of the layer-displacement fluctuations in smectic membranes have been studied by x-ray photon correlation spectroscopy (XPCS). We report transitions from an oscillatory damping regime to simple exponential decay of the fluctuations, both as a function of membrane thickness and upon changing from specular to off-specular scattering. This behavior is in agreement with recent theories. Employing avalanche photodiode detectors and the uniform filling mode of the synchrotron storage ring, the fast limits of XPCS have been explored down to 50 ns.     

Effects of feedback from collimating, focusing, and spot-array generating outcoupler gratings in surface-emitting semiconductor lasers

We experimentally demonstrate that a grating outcoupler used for complex beam shaping (spot-array generation) can produce unintentional optical feedback that severely disturbs the integrated in-plane laser that illuminates the coupler. Simulations show that these outcouplers, in contrast to conventional collimating or focusing outcouplers, tend to produce high levels of feedback in spite of the detuning used to suppress feedback. Further, this feedback is focused to high intensity in the laser gain medium. This focused light acts as a seed for the nonlinear self-focusing that causes wave-front distortion and filamentation, which degrades the beam quality.     

Changes in orcine muscle water characteristics during growth--an in vitro low-field NMR relaxation study

This study investigates the effects of developmental stage and muscle type on the mobility and distribution of water within skeletal muscles, using low-field (1)H-NMR transverse relaxation measurements in vitro on four different porcine muscles (M. longissimus dorsi, M. semitendinosus, M. biceps femoris, M. vastus intermedius) from a total of 48 pigs slaughtered at various weight classes between 25 kg and 150 kg. Principal component analysis (PCA) revealed effects of both slaughter weight and muscle type on the transverse relaxation decay. Independent of developmental stage and muscle type, distributed exponential analysis of the NMR T(2) relaxation data imparted the existence of three distinct water populations, T(2b), T(21), and T(22), with relaxation times of approximately 1-10, 45-120, and 200-500 ms, respectively. The most profound change during muscle growth was a shift toward faster relaxation in the intermediate time constant, T(21). It decreased by approx. 24% in all four muscle types during the period from 25 to 150 kg live weight. Determination of dry matter, fat, and protein content in the muscles showed that the changes in relaxation time of the intermediate time constant, T(21), during growth should be ascribed mainly to a change in protein content, as the protein content explained 77% of the variation in the T(21) time constant. Partial least squares (PLS) regression revealed validated correlations in the region of 0.58 to 0.77 between NMR transverse relaxation data and muscle development for all the four muscle types, which indicates that NMR relaxation measurements may be used in the prediction of muscle developmental stage.     

Heterocyclization of compounds containing diazo and cyano groups. 6. Theoretical and experimental investigations of cyclization of 2-cyano-2-diazoacetamides to 5-hydroxy-1,2,3-triazole-4-carbonitriles

A series of N-alkyl- and N-aryl-2-cyano-2-diazoacetamides was synthesized by the reaction of 2-amino-2-cyanoacetamides with sodium nitrite in hydrochloric acid. The mechanism of their heteroclectrocyclization to 5-hydroxy-1,2,3-triazoles was investigated kinetically and theoretically by the B3LYP/6-31+G^* method. The conclusion was made on the basis of the determined activation energy of the cyclization process. reaction parameters , and kinetic isotope effects, that there is a difference between the mechanisms of cyclization of the N-alkyl and N-aryl derivatives of 2-cyano-2-diazoacetamide; cyclization of the N-alkyl derivatives takes place by a monorotatory mechanism, while cyclization of the N-aryl derivatives takes place by a mechanism where one of the stages is heteroelectrocyclization of 2-diazoacetimidates.For Communication 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 26–41, January, 2000.     

Trace distributions associated to the Schrödinger operator

Dedicated to Professor Shmuel Agmon