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28 records · Page 2

Tube method of sound-absorption measurement extended to frequencies far above cutoff

Equipment had been constructed for measuring sound absorption in the frequency range from 4 to 100 kHz in a large tube 25.4 cm in diameter and 4.8-m long. The technique employs a large moveable solid-dielectric capacitance transducer that completely fills the tube cross section and generates pulses of plane waves. An identical transducer terminates the other end of the tube and serves as a microphone to detect and reflect the sound pulses. Measurements in argon, nitrogen, and air indicate that the attenuation of the sound pulses differs by less than 1% from values calculated for the zero-order mode for frequencies up to 44 times the cutoff frequency for the first 'nonplane' mode. Above that frequency, the measured values are less than those predicted by theory by an amount that is approximately proportional to the wavelength to the -3.1 power. In a smaller tube of similar construction, the high-frequency deviation from theory is absent.

Shields, F. D.↗

A method for crystallographic mapping of an alpha-beta titanium alloy with nanometre resolution using scanning precession electron diffraction and open-source software libraries

An approach for the crystallographic mapping of two-phase alloys on the nanoscale using a combination of scanned precession electron diffraction and open-source python libraries is introduced in this paper. This method is demonstrated using the example of a two-phase α/β titanium alloy. The data were recorded using a direct electron detector to collect the patterns, and recently developed algorithms to perform automated indexing and analyse the crystallography from the results. Very high-quality mapping is achieved at a 3 nm step size. The results show the expected Burgers orientation relationships between the α laths and β matrix, as well as the expected misorientations between α laths. A minor issue was found that one area was affected by 180° ambiguities in indexing occur due to this area being aligned too close to a zone axis of the α with twofold projection symmetry (not present in 3D) in the zero-order Laue Zone, and this should be avoided in data acquisition in the future. Nevertheless, this study demonstrates a good workflow for the analysis of nanocrystalline two- or multi-phase materials, which will be of widespread use in analysing two-phase titanium and other systems and how they evolve as a function of thermomechanical treatments.

36 MATERIALS SCIENCE↗

Microcapsules and Methods for Making

Methods of forming multi-lamellar microcapsules having alternating layers of hydrophilic and hydrophobic immiscible liquid phases have been developed using different polymer/solvent systems. The methods use liquid-liquid diffusion and simultaneous lateral phase separation, controlled by proper timed-sequence exposures of immiscible phases and low shear mixing, to form narrow size distributions of spherical, multilamellar microcapsules. The use of special formulations of solubilized drugs, surfactants, and polymeric co-surfactants in aqueous vehicles which are dispersed in hydrocarbon solvents containing small quantities of oil, low molecular weight co-surfactants and glycerides that are aqueous insoluble enables the formation of unique microcapsules which can carry large amounts of pharmaceuticals in both aqueous and non-aqueous solvent compartments. The liquid microcapsules are quickly formed in a single step and can include a polymeric outer 'skin' which protects the microcapsules during physical manipulation or exposure to high shear forces. Water-in-oil and oil-in-water microcapsules have been formed both in 1 x g and in microgravity, which contain several types of drugs co-encapsulated within different fluid compartments inside the same microcapsule. Large, spherical multi-lamellar microcapsules have been formed including a cytotoxic drug co-encapsulated with a radiocontrast medium which has advantages for chemoembolization of vascular tumors. In certain cases, crystals of the drug form inside the microcapsules providing zero-order and first order, sustained drug release kinetics.

Morrison, Dennis R.↗

Identification and quantification of distinct active sites in Hf-Beta zeolites for transfer hydrogenation catalysis

Despite the significant progress made in characterizing different framework heteroatom sites that exist in Lewis acidic zeolites with probe molecule adsorption and spectroscopy, methods to reliably quantify site counts remain indefinite and have been primarily limited to Sn and Ti Lewis acid sites. Here, methods to quantify framework Lewis acidic Hf 4+ sites in zeolite Beta (Hf-Beta) with two Lewis base titrants (pyridine, deuterated acetonitrile) were developed using infrared (IR) spectroscopy. Lewis acid site counts for Hf-Beta zeolites were validated by measuring integrated molar extinction coefficients (IMECs; ε, cm μmol –1 ) on Sn-Beta zeolites using identical Lewis base titrants to benchmark site counts with established literature procedures to quantify Lewis acid sites in Beta zeolites from IR spectra. Highlighting the importance of benchmarking active site counts against well-established experimental protocols, IMECs of CD 3 CN bound to open (ε(Sn; 2316 cm –1 ): 1.80 ± 0.25) and closed (ε(Sn; 2308 cm –1 ): 3.76 ± 0.33) Sn sites were ~1.8x larger than those previously reported while total Lewis acid site counts agreed with those measured by pyridine (ε(Sn; 1451 cm –1 ): 1.58 ± 0.16) on six different Sn-Beta zeolites. IMECs measured for IR peaks reflecting pyridine bound to Lewis acidic Hf sites (ε(Hf; 1448 cm –1 ): 1.54 ± 0.21) and CD 3 CN bound to open (ε(Hf; 2313 cm –1 ): 2.40 ± 0.22) and closed (ε(Hf; 2307 cm –1 ): 3.55 ± 0.41) Hf sites, gave similar counts for the total number of Lewis acidic sites across six Hf-Beta zeolites (Si/Hf = 100–413). Consistent with previous reports with Sn-Beta catalysts where open Sn sites are responsible for catalytic turnover, apparent first and zero-order MPVO rate constants (0.01–1 M cyclohexanone in 2-butanol; per total Hf, 373 K) correlated with the total number of open Hf sites, per total Hf, but not with the total number of closed Hf sites or total Lewis acid site counts. Measured initial MPVO rates (0.1 M cyclohexanone in 2-butanol, per open Hf, 373 K) were ~25x higher on hydrophobic Hf-Beta-F than on hydrophilic Hf-Beta-OH zeolites. Overall, the apparent first-order MPVO rate constants (2-butanol solvent, per open Hf, 373 K) were ~6x higher on Hf-Beta-F than on Hf-Beta-OH zeolites. The characterization methods reported here enable normalization of MPVO turnover rates on Sn- and Hf-Beta zeolites by their number of open sites. Finally, this enables performing quantitative rate comparisons across Lewis acid zeolites of varying active site identity, solvation, and pore topology used in liquid-phase catalysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Zero-Order Reaction Kinetics v3.0

Zero-RK is a software package that simulates chemically reacting systems using sparse, preconditioned, adaptive matrix methods to achieve orders-of-magnitude reduction in simulation time while maintaining accurate results.

Mcnenly, MatthewJ.↗

Zero-Order Reaction Kinetics v. 3.4.hip

Zero-RK is a software package that simulates chemically reacting systems using sparse, preconditioned, adaptive matrix methods to achieve orders-of-magnitude reduction in simulation time while maintaining accurate results.

Mcnenly, MatthewJ↗

Zero-Order Reaction Kinetics v. 3.6

Zero-RK is a software package that simulates chemically reacting systems using sparse, preconditioned, adaptive matrix methods to achieve orders-of-magnitude reduction in simulation time while maintaining accurate results.

McNenly, MatthewJ [Lawrence Livermore National Lab↗

Validation of zero-order feedback strategies for medium range air-to-air interception in a horizontal plane

A zero order feedback solution of a variable speed interception game between two aircraft in the horizontal plane, obtained by using the method of forced singular perturbation (FSP), is compared with the exact open loop solution. The comparison indicates that for initial distances of separation larger than eight turning radii of the evader, the accuracy of the feedback approximation is better than one percent. The result validates the zero order FSP approximation for medium range air combat analysis.

Shinar, J.↗

Nonlinear zero-sum differential game analysis by singular perturbation methods

A class of nonlinear, zero-sum differential games, exhibiting time-scale separation properties, can be analyzed by singular-perturbation techniques. The merits of such an analysis, leading to an approximate game solution, as well as the 'well-posedness' of the formulation, are discussed. This approach is shown to be attractive for investigating pursuit-evasion problems; the original multidimensional differential game is decomposed to a 'simple pursuit' (free-stream) game and two independent (boundary-layer) optimal-control problems. Using multiple time-scale boundary-layer models results in a pair of uniformly valid zero-order composite feedback strategies. The dependence of suboptimal strategies on relative geometry and own-state measurements is demonstrated by a three dimensional, constant-speed example. For game analysis with realistic vehicle dynamics, the technique of forced singular perturbations and a variable modeling approach is proposed. Accuracy of the analysis is evaluated by comparison with the numerical solution of a time-optimal, variable-speed 'game of two cars' in the horizontal plane.

Sinar, J.↗

Improved Phase-Mask Fabrication of Fiber Bragg Gratings

An improved method of fabrication of Bragg gratings in optical fibers combines the best features of two prior methods: one that involves the use of a phase mask and one that involves interference between the two coherent laser beams. The improved method affords flexibility for tailoring Bragg wavelengths and bandwidths over wide ranges. A Bragg grating in an optical fiber is a periodic longitudinal variation in the index of refraction of the fiber core. The spatial period (Bragg wavelength) is chosen to obtain enhanced reflection of light of a given wavelength that would otherwise propagate relatively unimpeded along the core. Optionally, the spatial period of the index modulation can be made to vary gradually along the grating (such a grating is said to be chirped ) in order to obtain enhanced reflection across a wavelength band, the width of which is determined by the difference between the maximum and minimum Bragg wavelengths. In the present method as in both prior methods, a Bragg grating is formed by exposing an optical fiber to an ultraviolet-light interference field. The Bragg grating coincides with the pattern of exposure of the fiber core to ultraviolet light; in other words, the Bragg grating coincides with the interference fringes. Hence, the problem of tailoring the Bragg wavelength and bandwidth is largely one of tailoring the interference pattern and the placement of the fiber in the interference pattern. In the prior two-beam interferometric method, a single laser beam is split into two beams, which are subsequently recombined to produce an interference pattern at the location of an optical fiber. In the prior phase-mask method, a phase mask is used to diffract a laser beam mainly into two first orders, the interference between which creates the pattern to which an optical fiber is exposed. The prior two-beam interferometric method offers the advantage that the period of the interference pattern can be adjusted to produce gratings over a wide range of Bragg wavelengths, but offers the disadvantage that success depends on precise alignment and high mechanical stability. The prior phase-mask method affords the advantages of compactness of equipment and relative insensitivity to both misalignment and vibration, but does not afford adjustability of the Bragg wavelength. The present method affords both the flexibility of the prior two-beam interferometric method and the compactness and stability of the prior phase-mask method. In this method (see figure), a laser beam propagating along the x axis is normally incident on a phase mask that lies in the (y,z) plane. The phase of light propagating through the mask is modulated with a spatial periodicity, p, along the y axis chosen to diffract the laser light primarily to first order at the angle . (The zero-order laser light propagating along the x axis can be used for alignment and thereafter suppressed during exposure of the fiber.) The diffracted light passes through a concave cylindrical lens, which converts the flat diffracted wave fronts to cylindrical ones, as though the light emanated from a line source. Then two parallel flat mirrors recombine the diffracted beams to form an interference field equivalent to that of two coherent line sources at positions A and B (virtual sources). The interference pattern is a known function of the parameters of the apparatus and of position (x,y) in the interference field. Hence, the tilt, wavelength, and chirp of the Bragg grating can be chosen through suitable adjustments of the apparatus and/or of the position and orientation of the optical fiber. In particular, the Bragg wavelength can be adjusted by moving the fiber along the x axis, and the bandwidth can be modified over a wide range by changing the fiber tilt angle or by moving the phase mask and/or the fiber. Alignment is easy because the zero-order beam defines the x axis. The interference is relatively stable and insensitive to the mechanical vibration because of the gh symmetry and compactness of the apparatus, the fixed positions of the mirrors and lens, and the consequent fixed positions of the two virtual line sources, which are independent of the translations of the phase mask and the laser relative to the lens.

Grant, Joseph↗