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At least 433 records · Page 24

Reaction rate constant of HO2+O3 measured by detecting HO2 from photofragment fluorescence

A room-temperature discharge-flow system investigation of the rate constant for the reaction 'HO2 + O3 yields OH + 2O2' has detected HO2 through the OH(A-X) fluorescence produced by photodissociative excitation of HO2 at 147 nm. A reaction rate constant of 1.9 + or - 0.3 x 10 to the -15th cu cm/molecule per sec is obtained from first-order decay of HO2 in excess O3; this agrees well with published data.

Manzanares, E. R.↗

Short time Fourier analysis of the electromyogram - Fast movements and constant contraction

Short-time Fourier analysis was applied to surface electromyograms (EMG) recorded during rapid movements, and during isometric contractions at constant forces. A portion of the data to be transformed by multiplying the signal by a Hamming window was selected, and then the discrete Fourier transform was computed. Shifting the window along the data record, a new spectrum was computed each 10 ms. The transformed data were displayed in spectograms or 'voiceprints'. This short-time technique made it possible to see time-dependencies in the EMG that are normally averaged in the Fourier analysis of these signals. Spectra of EMGs during isometric contractions at constant force vary in the short (10-20 ms) term. Short-time spectra from EMGs recorded during rapid movements were much less variable. The windowing technique picked out the typical 'three-burst pattern' in EMG's from both wrist and head movements. Spectra during the bursts were more consistent than those during isometric contractions. Furthermore, there was a consistent shift in spectral statistics in the course of the three bursts. Both the center frequency and the variance of the spectral energy distribution grew from the first burst to the second burst in the same muscle. The analogy between EMGs and speech signals is extended to argue for future applicability of short-time spectral analysis of EMG.

Hannaford, Blake↗

Quaternions as astrometric plate constants

A new method for solving problems in relative astrometry is proposed. In it, the relationship between the measured quantities and the components of the position vector of a star is modeled using quaternions, in effect replacing the plate constants of a standard four-plate-constant solution with the four components of a quaternion. The method allows a direct solution for the position vectors of the stars, and hence for the equatorial coordinates. Distortions, magnitude, and color effects are readily incorporated into the formalism, and the method is directly applicable to overlapping-plate problems. The advantages of the method include the simplicity of the resulting equations, their freedom from singularities, and the fact that trigonometric functions and tangential point transformations are not needed to model the plate material. A global solution over the entire sky is possible.

Jefferys, William H.↗

A priori predictions of the rotational constants for protonated formaldehyde and protonated methanol

Protonated formaldehyde and protonated methanol are candidate interstellar molecules and models for classes of protonated oxygen compounds. Ab initio molecular orbital theory has been used to compute rotational constants to guide spectroscopic searches both in the laboratory and in space. The ab initio results are empirically correct to account for systematic deficiencies in the theory and zero-point vibrational effects; they are expected to be accurate to about + or - 2 percent. For H2COH(+) the resultant constants are (in GHz) A = 194.3, B = 34.28, and C = 29.14; for H3COH2(+) A = 103.7, B = 21.18, and C = 20.30.

Defrees, D. J.↗

Determination of calibration constants for the hole-drilling residual stress measurement technique applied to orthotropic composites. I - Theoretical considerations

The hole-drilling technique for the measurement of residual stresses using electrical resistance strain gages has been widely used for isotropic materials and has been adopted by the ASTM as a standard method. For thin isotropic plates, with a hole drilled through the thickness, the idealized hole-drilling calibration constants are obtained by making use of the well-known Kirsch's solution. In this paper, an analogous attempt is made to theoretically determine the three idealized hole-drilling calibration constants for thin orthotropic materials by employing Savin's (1961) complex stress function approach.

Prasad, C. B.↗

A loading system for creep testing under constant compressive stress

A critical analysis is made of layouts assuring constant stress under creep, pointing out the difficulties of using these layouts for compressive testing. A new mechanical system to maintain stress during creep testing is proposed. Constant stress is achieved by a definite motion of the load. The proposed system can be used in tensile or compressive testing. Practical measurements reveal that the stress constancy error is not greater than plus or minus 1.5 percent up to relative deformation of 30 percent.

Dobes, F.↗

The calibration and operation of a constant-temperature crossed-wire probe in supersonic flow

The calibration and operation of a constant-temperature crossed-wire probe in supersonic flow is considered. Crossed-wire probes offer considerable advantages over single, inclined wires: the kinematic shear stress can be derived from a single point measurement; the rms quantities can be derived from the same measurement, and the instantaneous quantities can be obtained as a continuous function of time. However, using a crossed-wire probe in supersonic flow is subject to the following practical difficulties: the problem of flow interference, where the shock waves from one wire and its supports interfere with the flow over the other wire; the necessity for high frequency response to resolve the spectral content, and the sensitivity of the results to small changes in the calibration constants. In the present contribution, each of these problems is addressed. Practical solutions are suggested, and some encouraging results are presented.

Fernando, E. M.↗

Determination of calibration constants for the hole-drilling residual stress measurement technique applied to orthotropic composites. II - Experimental evaluations

The first step in the extension of the semidestructive hole-drilling technique for residual stress measurement to orthotropic composite materials is the determination of the three calibration constants. Attention is presently given to an experimental determination of these calibration constants for a highly orthotropic, unidirectionally-reinforced graphite fiber-reinforced polyimide composite. A comparison of the measured values with theoretically obtained ones shows agreement to be good, in view of the many possible sources of experimental variation.

Prasad, C. B.↗

Dependence of rate constants on vibrational temperatures - An Arrhenius description

An interpretation of the variation of rate constants with vibrational temperature is proposed which introduces parameters analogous to those of the classical Arrhenius expression. The constancy of vibrational activation energy is studied for the dissociaton of NO, the ion-molecular reaction of O(+) with N2, and the atom exchange reaction of I with H2. It is found that when a Boltzmann distribution for vibrational states is applicable, the variation of the rate constant with the vibrational temperature can be used to define a vibrational activation energy. The method has application to exchange reactions where a vibrational energy threshold exists.

Ford, D. I.↗

A model for solar constant secular changes

In this paper, contrast models for solar active region and global photospheric features are used to reproduce the observed Active Cavity Radiometer and Earth Radiation Budget secular trends in reasonably good fashion. A prediction for the next decade of solar constant variations is made using the model. Secular trends in the solar constant obtained from the present model support the view that the Maunder Minimum may be related to the Little Ice Age of the 17th century.

Schatten, Kenneth H.↗

The equilibrium constant for N2O5 = NO2 + NO3 - Absolute determination by direct measurement from 243 to 397 K

Direct determinations of the equilibrium constant for the reaction N2O5 = NO2 + NO3 were carried out by measuring NO2, NO3, and N2O5 using long-path visible and infrared absorption spectroscopy as a function of temperature from 243 to 397 K. The first-order decay rate constant of N2O5 was experimentally measured as a function of temperature. These results are in turn used to derive a value for the rate coefficient for the NO-forming channel in the reaction of NO3 with NO2. The implications of the results for atmospheric chemistry, the thermodynamics of NO3, and for laboratory kinetics studies are discussed.

Cantrell, C. A.↗

Theoretical study of the nitrogen atom hyperfine coupling constant

The nitrogen-atom isotropic hyperfine coupling constant A(iso) is studied as a function of improvements in both the one-particle and n-particle basis sets. The study underscores the importance of diffuse basis functions. For example, the (9s 5p) primitive set of Huzinaga (1965) augmented with an even-tempered diffuse s function yields values for A(iso) that are virtually identical to an energy-optimized (23s 12p) even-tempered set. The A(iso) constant is found to converge relatively quickly with increasing l quantum numbers: d, f, and g functions are estimated to contribute 2.5 + or - 0.2, 0.4 + or - 0.1, and 0.05 + or - 0.05 MHz, respectively. Full CI calibration calculations indicate that very high levels of correlation treatment are required for quantitative results. In addition, a strong coupling is observed between the one-particle and n-particle requirements. The best result, 10.4 MHz, is in excellent agreement with the accurate experimental value of 10.4509 MHz.

Bauschlicher, Charles W., Jr.↗

Temperature Dependence Of Elastic Constants Of Polymers

Two papers extend theory of elastic constants of disordered solids to finite temperatures below glass-transition temperatures. First paper, entitled "Elastic Constants of Disordered Solids II: Temperature Dependence," applies to cryogenic temperatures. Second paper, entitled "Theory of Thermoelastic Properties for Polymer Glasses," develops unified treatment for static compressional and elongational properties at temperatures up to glass-transition temperatures.

Simha, Robert↗

Determination of surfaces of constant inelastic strain rate at elevated temperature

An experimental effort to perform special exploratory multiaxial deformation tests on tubular specimens of type 316 stainless steel at 650 C (1200 F) is described. One test specimen was subjected to a time-independent torsional shear strain test history, and surfaces of constant inelastic strain rate (SCISRs) in an axial/torsional stress space were measured at various predetermined points during the test. A second specimen was subjected to a 14-week time-dependent (creep-recovery-creep periods) torsional shear stress histogram SCISRs determinations made at 17 points during the test. The tests were conducted in a high temperature, computer controlled axial/torsional test facility using high-temperature multiaxial extensometer. The effort was successful, and for the first time the existence of surfaces of constant inelastic strain rate was experimentally demonstrated.

Battiste, R. L.↗

Electron attachment lineshapes, cross sections and rate constants at ultra-low energies in several halomethyl and haloethyl molecules

Electron attachment lineshapes, cross sections and rate constants are reported for the molecules CH2Br2, CF2Br2, CF3Br, CBrCl3, BrCN, C2H2Br4, CH3l, C2H5l and 1,1,1,-C2Cl3F3. Use is made of the krypton photoionization method. In addition, the signal intercomparison technique is used to obtain individual channel cross sections and rate constants for Br(-) and CN(-) formation from BrCN, and for Br(-) and Br2(-) formation from CF2Br2. Present results in 1,1,1,-C2Cl3F3 using a new ion extraction grid geometry are compared with earlier results, and differences discussed in terms of the electric field equipotentials of two extraction systems used in the present work. Approximate potential energy curves for BrCN are presented, and the temperature dependence of the Br(-) channel cross section discussed.

Alajajian, S. H.↗

Additives Lower Dielectric Constants Of Polyimides

Dielectric constants as low as 2.43 make polyimides more attractive for electronic applications. Process makes aromatic condensation polyimide films and coatings with dielectric constants lowered by incorporation of diamic acid additives. Materials provide better electrical insulation without sacrificing temperature stability of polyimide binders. Applicable whenever high temperature, low absorption of moisture, and high electrical-insulation properties needed. Applications include semiconductors and printed-circuit boards for computer industry and possibly automotive industry.

Stoakely, Diane M.↗

Rate constant for reaction of atomic hydrogen with germane

Due to the interest in the chemistry of germane in the atmospheres of Jupiter and Saturn, and because previously reported kinetic reaction rate studies at 298 K gave results differing by a factor of 200, laboratory measurements were performed to determine the reaction rate constant for H + GeH4. Results of the study at 298 K, obtained via the direct technique of flash photolysis-resonance fluorescence, yield the reaction rate constant, k = (4.08 + or - 0.22) x 10(exp -12) cu cm/s.

Nava, David F.↗

Theoretical study of the nitrogen-atom hyperfine coupling constant. II

The N hyperfine coupling constant has been computed using multireference configuration interaction (MRCI) and averaged coupled pair functional (ACPF) treatments in very large one-particle basis sets. Unlike previous calculations, no selection of configurations has been performed. The calculations again illustrate the difficulty of computing the N hyperfine coupling constant accurately. The best MRCI result of 10.7 MHz is larger than the accurate experimental value of 10.4509 MHz, while the best ACPF result (10.3 MHz) is smaller than experiment. The difference between this work and previous calculations is discussed.

Bauschlicher, Charles W., Jr.↗