Modeling power law absorption and dispersion for acoustic propagation using the fractional Laplacian

The efficient simulation of wave propagation through lossy media in which the absorption follows a frequency power law has many important applications in biomedical ultrasonics. Previous wave equations which use time-domain fractional operators require the storage of the complete pressure field at previous time steps (such operators are convolution based). This makes them unsuitable for many three-dimensional problems of interest. Here, a wave equation that utilizes two lossy derivative operators based on the fractional Laplacian is derived. These operators account separately for the required power law absorption and dispersion and can be efficiently incorporated into Fourier based pseudospectral and k-space methods without the increase in memory required by their time-domain fractional counterparts. A framework for encoding the developed wave equation using three coupled first-order constitutive equations is discussed, and the model is demonstrated through several one-, two-, and three-dimensional simulations.     

Characterization of partially transesterified poly(beta-hydroxyalkanoate)s using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) was used for the characterization of a partially transesterified poly(beta-hydroxyalkanoate), PHA, polymer produced by the bacterial strain Alcaligenes eutrophus using saponified vegetable oils as the sole carbon sources. The transesterification was carried out separately under acidic and basic conditions to obtain PHA oligomers weighing less than 10 kDa. The intact oligomers were detected in their cationized [M + Na](+) and [M + K](+) forms by MALDI-TOFMS. A composition analysis, using the MALDI-TOF spectra, indicate that the oligomers obtained via acid catalysis were terminated with a methyl 3-hydroxybutyrate end group, and those obtained by base catalysis had a methyl crotonate (olefinic) termination. In addition to HB (hydroxy butyrate), the oligomers were found to contain a small percentage of HV (hydroxy valerate). This was independently confirmed using gas chromatography/mass spectrometry (GC/MS). In comparison, the analysis of a commercial PHA polymer, transesterified under identical conditions, only showed the presence of HB, i.e. a pure PHB homopolymer. Copyright 1999 John Wiley & Sons, Ltd.     

The Mechanism of the Decomposition of Peroxides and Hydroperoxides by Mineral Fillers

The interaction of fillers and pigments with free radical initiators has been studied. Clay minerals have a marked influence on both the rate and the mechanism of the decomposition of peroxides and hydroperoxides. Kaolinite is a particularly effective catalyst and causes rapid decomposition even at room temperature. The reaction of cumene hydroperoxide with kaolinite is first-order in peroxide and the rate constant is proportional to the ratio of clay to hydroperoxide. From a study of the products of the reaction and the influence of solvent on the decomposition, a mechanism involving an intramolecular rearrangement or closely associated ion pairs has been proposed. The application of these results to polymer filler composites is discussed.     

The effect of hair on auditory localization cues

Previous empirical and analytical investigations into human sound localization have illustrated that the head-related transfer function (HRTF) and interaural cues are affected by the acoustic material properties of the head. This study utilizes a recent analytical treatment of the sphere scattering problem (which accounts for a hemispherically divided surface boundary) to investigate the contribution of hair to the auditory cues below 5 kHz. The hair is modeled using a locally reactive equivalent impedance parameter, and cue changes are discussed for several cases of measured hair impedance. The hair is shown to produce asymmetric perturbations to the HRTF and the interaural time and level differences. The changes in the azimuth plane are explicated via analytical examination of the surface pressure variations with source angle. Experimental HRTFs obtained using a sphere with and without a hemispherical covering of synthetic hair show a good agreement with analytical results. Additional experimental and analytical investigations illustrate that the relative contribution of the hair remains robust, regardless of the placement of the pinnas, or inclusion of a cylindrical neck.     

Standardization for oxygen isotope ratio measurement - still an unsolved problem

Numerous organic and inorganic laboratory standards were gathered from nine European and North American laboratories and were analyzed for their delta(18)O values with a new on-line high temperature pyrolysis system that was calibrated using Vienna standard mean ocean water (VSMOW) and standard light Antartic precipitation (SLAP) internationally distributed reference water samples. Especially for organic materials, discrepancies between reported and measured values were high, ranging up to 2 per thousand. The reasons for these discrepancies are discussed and the need for an exact and reliable calibration of existing reference materials, as well as for the establishment of additional organic and inorganic reference materials is stressed. Copyright 1999 John Wiley & Sons, Ltd.     

Molecular distribution of some commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Nonylphenol ethoxylates (NPEs) belong to a group of nonionic surfactants that are collectively referred to as alkylphenol ethoxylates (APEs). APEs find widespread use in heavy-duty commercial and household cleaning formulations, shampoos, and industrial processing, i.e. textile manufacture. Their environmental impact depends on the molecular distribution and the extent of their biodegradation in municipal sewage systems, waterways and rivers. We have established two sample preparation methods that have enabled the determination of the molecular distributions of six commercial nonylphenol ethoxylates using matrix-assisted laser desorption/ionization (MALDI) time-of-flight (TOF) mass spectrometry (MS). In both methods, alpha-cyano-4-hydroxycinnamic acid, dissolved in acetonitrile/tetrahydrofuran, was used as the matrix. In one set of experiments, the NPEs were dissolved in an acetonitrile/tetrahydrofuran solvent system prior to mixing with the matrix solution, and the resulting MALDI-TOF mass spectra produced mostly sodiated molecules [M + Na](+). The NPEs, all having the formula 4-(C(9)H(19))-C(6)H(4)-(OCH(2)CH(2))(n)-OH, are Surfonic (R)N-95, N-100, N-102, N-120, N-150 and N-300. Surfonic N-95 and N-100 gave n values of 5-20; Surfonic N-102, N-120, N-150, and N-300 gave n values of 5-21, 5-22, 8-25 and 15-40, respectively. In order to develop a sample preparation method that could be used with less polar NPEs, we dissolved the NPEs (except N-300) in pentane prior to mixing with the matrix solution, and found that the MALDI spectral quality was unaffected by the solvent systems. Copyright 1999 John Wiley & Sons, Ltd.     

The effect of impedance on interaural azimuth cues derived from a spherical head model

Recent implementations of binaural synthesis have combined high-frequency pinna diffraction data with low-frequency acoustic models of the head and torso. This combination ensures that the salient cues required for directional localization in the horizontal plane are consistent with psychophysical expectations, regardless of the accuracy or match of the high-frequency cues, or the fidelity of experimental low-frequency information. This paper investigates the effect of a nonrigid boundary condition on the surface pressure and the resulting interaural cues used for horizontal localization. These are derived from an analytical single sphere diffraction model assuming a locally reacting and uniformly distributed impedance boundary condition. Decreasing the magnitude of a purely resistive surface impedance results in an overall decrease in the sphere surface pressure level, particularly in the posterior region. This produces nontrivial increases in both the interaural level and time difference, especially for sound source directions near the interaural axis. When the surface impedance contains a reactive component the interaural cues exhibit further changes. The basic impedance characteristics of human hair and their incorporation into the sphere diffraction model are also discussed.     

An experimental study of the acoustic impedance characteristics of human hair

Previous analytical and empirical studies of the human auditory system have shown that the cues used for localization are modified by the inclusion of nonrigid scattering surfaces (clothing, hair etc). This paper presents an investigation into the acoustic impedance properties of human hair. The legitimacy of a locally reactive surface assumption is investigated, and an appropriate boundary condition is formulated to account for the physiological composition of a human head with hair. This utilizes an equivalent impedance parameter to allow the scattering boundary to be defined at a reference plane coincident with the inner rigid surface of the head. Experimental examination of a representative synthetic hair material at oblique incidence is used to show that a locally reactive surface assumption is legitimate. Additional experimental analysis of a simple scattering problem illustrates that the equivalent impedance must be used in favor of the traditional surface impedance to yield physically correct pressure magnitudes. The equivalent acoustic impedance properties of a representative range of human hair samples are discussed, including trends with sample thickness, fiber diameter, bulk density, and mass.     

Acoustic scattering by a sphere with a hemispherically split boundary condition

A general analytical model is developed for the scattering of sound by a sphere with a nonuniform impedance boundary condition that is divided into two uniformly distributed hemispheres. In addition to the overall solution for the time harmonic pressure, the analytical result gives insight into the modal contributions and coupling for different cases of source incidence and boundary impedance. Modal cross coupling is shown to exist between incoming and scattered wave modes of equi-order and nonequal degree when the degrees are opposite in parity (odd-even or even-odd coupling). This cross coupling is strongest between modes of adjacent degree, and decreases as the degrees become dissimilar. The overall magnitude of the cross coupling is dependent on the extent of the impedance mismatch between the two surface hemispheres. Simulation and discussion are given for several specific cases of source incidence and impedance (each hemisphere is given a different constant impedance value). These results are consistent with expectations from the scattering of sound by a sphere with a uniformly distributed surface boundary. The broad scattering characteristics of the hemispherically divided sphere are shown to be analogous to connecting the appropriate sectors from the corresponding uniformly distributed spheres.