The dynamic water vapour sorption properties of natural fibres and viscoelastic behaviour of the cell wall: is there a link between sorption kinetics and hysteresis?

In a previous article, the sorption kinetics’ properties of a range of natural fibres were reported. Analysis of the sorption kinetics was made using the parallel exponential kinetics (PEK) model, and it was argued that the rate limiting step of the sorption process was determined by substrate swelling rather than being diffusion limited. The PEK model divides the sorption kinetics curve into two first-order kinetics processes (fast and slow) but there is as yet no generally accepted explanation of what these two processes represent. In this article, the PEK parameters for sorption have been further evaluated in terms of two Kelvin–Voigt elements arranged in series. The force constant in the spring of each Kelvin–Voigt elements determines the equilibrium moisture content for each of the processes, whereas the viscosity of the dashpot is represented by the time constant for each process. Determination of interfibrillar matrix modulus using the Kelvin–Voigt model gives values that are in line with what would be predicted, giving credence to this interpretation of the sorption kinetics. Possible interpretations of the fast and slow kinetics processes are discussed.     

光谱规则透射比标准装置的建立

本文介绍了中国计量科学研究院建立的光谱规则透射比标准装置，它是由日立340型分光光度计的基本部件和一台微型计算机组成的，用原子线谱灯检验了它的波长准确度，用截止波长滤光器法检验了它的杂散幅射比率，用双孔径法检验了它的光度非线性，经详细分析，该标准装置的决不确定度为2×10^-4透射比单位，与美国标准技术研究院结比对结果表明，在0．1－0．3透射比范围内的一致性优于6×10^-4.     

Pressure effects on water vapour lines: beyond the Voigt profile

A short overview of recent results on the effects of pressure (collisions) regarding the shape of isolated infrared lines of water vapour is presented. The first part of this study considers the basic collisional quantities, which are the pressure-broadening and -shifting coefficients, central parameters of the Lorentzian (and Voigt) profile and thus of any sophisticated line-shape model. Through comparisons of measured values with semi-classical calculations, the influences of the molecular states (both rotational and vibrational) involved and of the temperature are analysed. This shows the relatively unusual behaviour of H(2)O broadening, with evidence of a significant vibrational dependence and the fact that the broadening coefficient (in cm(-1) atm(-1)) of some lines increases with temperature. In the second part of this study, line shapes beyond the Voigt model are considered, thus now taking 'velocity effects' into account. These include both the influence of collisionally induced velocity changes that lead to the so-called Dicke narrowing and the influence of the dependence of collisional parameters on the speed of the radiating molecule. Experimental evidence of deviations from the Voigt shape is presented and analysed. The interest of classical molecular dynamics simulations, to model velocity changes, together with semi-classical calculations of the speed-dependent collisional parameters for line-shape predictions from 'first principles', are discussed.     

Fast transmittance model for satellite sounding

Through the use of new line-by-line spectral calculations in both the infrared and microwave regions, coefficients have been generated for the transmittance stage of the fast radiative transfer model used by the United Kingdom Meteorological Office. These permit the fast model to calculate the transmittance for the high-resolution infrared sounder and the microwave sounding unit instruments aboard the National Oceanic and Atmospheric Administration polar-orbiting satellite for a given atmospheric profile, simply by taking these coefficients in linear combination with a set of predictors. These are expressed in terms of the deviation of the profile from a reference. However, the method can be applied to any instrument within the range of the spectral calculations, thereby permitting new coefficients to be calculated as soon as the spectral response details for the instrument become available. It also permits effective consideration to be given in the longer term to new line data or improvements in line-shape theory. The process by which these coefficients have been obtained is described, along with a discussion of some of the tests carried out on their installation into the fast model; these tests show that they are suitable for operational use. The predictors employed by the fast model are discussed, and changes are proposed for those that relate to the water-vapor transmittance. In this respect it was found that the inclusion of predictors that depend primarily on the zenith angle of the radiation path leads to improvements in the transmittance calculation.     

Two-tone frequency-modulation spectroscopy for quantitative measurements of gaseous species: theoretical, numerical, and experimental investigation of line shapes

The capability of retrieving spectral information from line shapes recorded by two-tone frequency-modulation spectroscopy (TTFMS) is investigated. A TTFMS theory accounting for dispersion and nonlinear distortion of diode laser frequency modulation response is presented. The adequacy of the theory for a detailed modeling of line shapes recorded with high resolution is examined. An extensive error analysis of line parameters (i.e., width, intensity, and line center) retrieved by a nonlinear least-squares fitting procedure is made. Plots of residual errors with characteristic signatures that are due to incorrectly assigned modulation parameters and choice of line profile are presented. In least-squares fits to experimental oxygen data with a Voigt profile influence from collisional(Dicke) narrowing is clearly exhibited, and when we used a collisionally narrowed line profile deviations of the model were reduced to less than 0.2%. We demonstrate that accurate quantitative measurements by TTFMS over a wide range of concentrations, temperatures, and pressures are possible.     

Experimental method for determining the damping parameter of spectral lines emitted by a microwave plasma at atmospheric pressure

In this work, a simple method for experimentally obtaining the value of the damping parameter or a-parameter of the spectral lines emitted by an argon plasma generated at atmospheric pressure is presented. The value of this coefficient indicates the proportion existing between the Lorentzian and Doppler components of the total line profile, which can be approximated to a Voigt function for our experimental conditions. The a-parameter values found were within the value interval recorded in the literature. The results obtained showed that the damping coefficient of the lines next to the fundamental level remains practically constant along the plasma column, whereas for the spectral lines involving high-lying levels, the a-parameter is sensitive to the changes in the electron density in the plasma. In this work it is also proved that the self-absorption phenomenon induces errors in the calculation of a, due to an increase in the broadening of the line profile produced by this phenomenon.     

A simple viscoelastic model for soft tissues the frequency range 6-20 MHz

In this paper, we present measurements of the shear properties of porcine skeletal muscle, liver, and kidney and a novel model describing them. Following a previously used method, shear mechanical impedances are measured, and complex shear moduli are obtained in the frequency range 6-20 MHz. As indicated in previous results, negative storage moduli are obtained in some measurements, which yield negative shear moduli in traditional linear viscoelastic models such as the Maxwell model, the Voigt model, and the Kelvin model. To resolve this problem, we propose a simple extension of the Voigt model. A mass is introduced into the model to account for the extra phase shift that apparently produces the negative moduli, and the shear stress thereby is related to the inertia of the material. The observed negative storage moduli are predicted by the new model when the relaxation time of the material is large and the working frequency is high. The model is fitted to experimental data to obtain values for material constants.     

A simple viscoelastic model for soft tissues in the frequency range 6-20 MHz.

In this paper, we present measurements of the shear properties of porcine skeletal muscle, liver, and kidney and a novel model describing them. Following a previously used method, shear mechanical impedances are measured, and complex shear moduli are obtained in the frequency range 6-20 MHz. As indicated in previous results, negative storage moduli are obtained in some measurements, which yield negative shear moduli in traditional linear viscoelastic models such as the Maxwell model, the Voigt model, and the Kelvin model. To resolve this problem, we propose a simple extension of the Voigt model. A mass is introduced into the model to account for the extra phase shift that apparently produces the negative moduli, and the shear stress thereby is related to the inertia of the material. The observed negative storage moduli are predicted by the new model when the relaxation time of the material is large and the working frequency is high. The model is fitted to experimental data to obtain values for material constants.     

Evaluating the mechanical properties of grain-boundary phases in nano- and submicrocrystalline materials using a model of an elastic multilayer periodic medium

It is shown that determination of the mechanical characteristics of grain-boundary phases in nanoand submicrocrystalline materials using the results of sound velocity measurements interpreted within the framework of the Reuss and Voigt models is incorrect. A more general method is proposed for this purpose, which is based on the model of elastic wave propagation in a multilayer periodic medium.     

Single-layer model for surface roughness

Random roughness of an optical surface reduces its specular reflectance and transmittance by the scattering of light. The reduction in reflectance can be modeled by a homogeneous layer on the surface if the refractive index of the layer is intermediate to the indices of the media on either side of the surface. Such a layer predicts an increase in the transmittance of the surface and therefore does not provide a valid model for the effects of scatter on the transmittance. Adding a small amount of absorption to the layer provides a model that predicts a reduction in both reflectance and transmittance. The absorbing layer model agrees with the predictions of a scalar scattering theory for a layer with a thickness that is twice the rms roughness of the surface. The extinction coefficient k for the layer is proportional to the thickness of the layer.     

Experimental test of a perturbation model for time-resolved imaging in diffusive media

We report what to our knowledge is a novel perturbation approach for time-resolved transmittance imaging in diffusive media, based on the diffusion approximation with extrapolated boundary conditions. The model relies on the method of Padé approximants and consists of a nonlinear approximation of time-resolved transmittance curves in the presence of an inclusion. The proposed model is intended to extend the range of applicability of perturbation models when applied to inclusions that are non-point-like. We test the model on different tissue phantoms with scattering only, absorbing only, and both scattering and absorbing inclusions. Maps of the optical properties are displayed, and the results are compared with those obtained by means of the usual linear approximation of time-resolved transmittance curves. We found that the nonlinear approach gives a better prediction for absolute values of the scattering and absorption coefficients of inclusions, when the inclusion optical properties are higher than the surrounding background. Furthermore, better-resolved spots and a reduced cross talk between the two parameters are found in the reconstructed maps. Because the range of the optical properties spanned by the considered phantoms covers the values expected for optical mammography, the application of the reported reconstruction method to in vivo images of a breast appears promising from a diagnostic viewpoint.     

An alternative analytical formulation for the Voigt function applied to resonant effects in nuclear processes

The Voigt function H(a,v) is defined as the convolution of the Gaussian and Lorentzian functions. Recent papers puplished in different areas of physics emphasize the importance of the fast and accurate calculation of the Voigt function for different orders of magnitude of variables a and v. An alternative analytical formulation for the Voigt function is proposed in this paper. This formulation is based on the solution of the non-homogeneous ordinary differential equation, satisfied by the Voigt function, using the Frobenius and parameter variation methods. The functional form of the Voigt function, as proposed, proved simple and precise. Systematic tests are accomplished demonstrating some advantages with other existent methods in the literature and with the numeric method of reference.     

First experiments to determine snow density from diffuse near-infrared transmittance

Snow density is one of the key properties to characterize a snow cover. We present diffuse near-infrared transmittance measurements with an integrating sphere setup in the laboratory. We analyze 8 snow samples taken from melt forms, decomposed, rounded, faceted and machine made snow. Reference measurements of specific surface area (optically equivalent grain size) and density are done by micro-computed tomography and used as input for transmittance calculations. A diffuse flux extinction model cannot be applied to simulate transmittance as our setup cannot be approximated by an infinite snow block thickness. Calculations with a more intricate radiative transfer model (DISORT) agree with our measurements within the estimated grain size and density variability for all probed natural snow types. Only our machine made snow shows a morphology which cannot be modeled by DISORT. Thus, our results show for the first time a direct experimental correlation between transmittance and snow specific surface area and density without the need for an empirical fitting parameter. We feel this to be an important step towards a possible high-resolution, quantitative optical measurement method to determine snow density in combination with an independent specific surface area measurement.     

Extraction of chemical information of suspensions using radiative transfer theory to remove multiple scattering effects: application to a model multicomponent system

The effectiveness of a scatter correction approach based on decoupling absorption and scattering effects through the use of the radiative transfer theory to invert a suitable set of measurements is studied by considering a model multicomponent suspension. The method was used in conjunction with partial least-squares regression to build calibration models for estimating the concentration of two types of analytes: an absorbing (nonscattering) species and a particulate (absorbing and scattering) species. The performances of the models built by this approach were compared with those obtained by applying empirical scatter correction approaches to diffuse reflectance, diffuse transmittance, and collimated transmittance measurements. It was found that the method provided appreciable improvement in model performance for the prediction of both types of analytes. The study indicates that, as long as the bulk absorption spectra are accurately extracted, no further empirical preprocessing to remove light scattering effects is required.     

Strip gratings on dielectric substrates as output couplers for submillimeter lasers

This paper describes the use and advantages of metallic strip gratings on dielectric substrates as output couplers for both optically pumped and discharge-excited submillimeter lasers. Formulas are presented for the calculation of transmittance and loss of such couplers, taking account of loss in the strip grating as well as loss and multiple reflections in the substrate. Included are expressions for the phase shifts on reflection and transmission by an arbitrary lossy grid on a plane boundary between two dielectrics according to a transmission-line model that is applicable for wavelengths in both dielectrics longer than the grid period. In relation to these phase shifts attention is drawn to an important sign convention. The theory is shown to agree well with measured transmittance of a typical device between 500 and 1600 GHz as well as spot measurements at 891 (337-microm HCN laser), 1540, and 1578 GHz (195- and 190-microm DCN laser). Finally, the theory is used to design a low-loss coupler for the low-gain 119-microm line of discharge excited H2O.     

Fast radiative-transfer model based on the correlated k-distribution method for a high-resolution satellite sounder

A fast radiative-transfer model for the Atmospheric Infrared Sounder (AIRS) was developed by use of a correlated k-distribution method. Transmittances produced by the correlated k-distribution method are systematically displaced from those produced by a line-by-line method, and empirical correction is possible. A fast radiative model that includes this empirical correction has exhibited practical performance in tests of transmittance and brightness temperature that used an independent set of atmospheric profiles.     

Determination of optical constants and thicknesses of In2O3:Sn films from transmittance data

Indium tin oxide (ITO) thin films were deposited on quartz substrates by direct current magnetron sputtering and annealed in N₂ and air. The normal incidence transmittance of the films was measured by a spectrophotometer. The electrical parameters such as carrier concentration, mobility and resistivity were investigated by van der Pauw method. An optical model has been proposed to simulate the optical constants and thicknesses of the films from transmittance data, which combines the Forouhi-Bloomer model and modified Drude model. The relaxation energy in the Drude term is taken as energy-dependent for a better fitting in the visible spectral range. The simulated transmittance is in good agreement with the measured spectrum in the whole measurement wavelength range. The electrical parameters obtained from the optical simulation are well consistent with those measured electrically by van der Pauw method. The experimental results also indicate that the different post-deposition annealing treatments yield the distinct optical and electrical properties of ITO films.     

Reflectance and transmittance model for recto-verso halftone prints

We propose a spectral prediction model for predicting the reflectance and transmittance of recto-verso halftone prints. A recto-verso halftone print is modeled as a diffusing substrate surrounded by two inked interfaces in contact with air (or with another medium). The interaction of light with the print comprises three components: (a) the attenuation of the incident light penetrating the print across the inked interface, (b) the internal reflectance and internal transmittance that accounts for the substrate's intrinsic reflectance and transmittance and for the multiple Fresnel internal reflections at the inked interfaces, and (c) the attenuation of light exiting the print across the inked interfaces. Both the classical Williams-Clapper and Clapper-Yule spectral prediction models are special cases of the proposed recto-verso reflectance and transmittance model. We also extend the Kubelka-Munk model to predict the reflectance and transmittance of recto-verso halftone prints. The extended Kubelka-Munk model is compatible with the proposed recto-verso reflectance and transmittance model. In the case of a homogeneous substrate, the recto-verso model's internal reflectance and transmittance can be expressed as a function Kubelka-Munk's scattering and absorption parameters, or the Kubelka-Munk's scattering and absorption parameters can be inferred from the recto-verso model's internal reflectance and transmittance, deduced from spectral measurements. The proposed model offers new perspectives both for spectral transmission and reflection predictions and for characterizing the properties of printed diffuse substrates.     

Perturbation approach to the time-resolved transmittance for a spatially varying scattering inclusion in a diffusive slab

In the framework of the perturbation approach to the diffusion equation, an analytical expression is derived to describe the effects on the time-resolved transmittance due to the presence of a spatially varying scattering inclusion hidden inside a diffusive slab. This formula assumes that the reduced scattering coefficient of the inclusion is spatially Gaussian distributed and complements that obtained for the absorptive case. The accuracy and the application range of the perturbed transmittance are investigated through comparisons with the numerical solutions of the time-dependent diffusion equation given by using the finite-element method. The proposed perturbation model is validated through a fitting procedure that determines the relative error in retrieving the scattering perturbation parameter of the inclusion located at the midplane of the slab.     

Systematic errors inherent in the current modeling of the reflected downward flux term used by remote sensing models

An underlying assumption of satellite data assimilation systems is that the radiative transfer model used to simulate observed satellite radiances has no errors. For practical reasons a fast-forward radiative transfer model is used instead of a highly accurate line-by-line model. The fast model usually replaces the spectral integration of spectral quantities with their monochromatic equivalents, and the errors due to these approximations are assumed to be negligible. The reflected downward flux term contains many approximations of this nature, which are shown to introduce systematic errors. In addition, many fast-forward radiative transfer models simulate the downward flux as the downward radiance along a path defined by the secant of the mean emergent angle, the diffusivity factor. The diffusivity factor is commonly set to 1.66 or to the secant of the satellite zenith angle. Neither case takes into account that the diffusivity factor varies with optical depth, which introduces further errors. I review the two most commonly used methods for simulating reflected downward flux by fast-forward radiative transfer models and point out their inadequacies and limitations. An alternate method of simulating the reflected downward flux is proposed. This method transforms the surface-to-satellite transmittance profile to a transmittance profile suitable for simulating the reflected downward flux by raising the former transmittance to the power of kappa, where kappa itself is a function of channel, surface pressure, and satellite zenith angle. It is demonstrated that this method reduces the fast-forward model error for low to moderate reflectivities.