Multiple small-angle scattering—A review

Small-angle scattering (SAS) is a powerful experimental technique in condensed matter physics for studying structural features of inhomogeneities of colloidal dimensions. So far the technique has been largely exploited to study thin samples for which the single scattering approximation, for the radiation-matrix interaction, holds good. The single scattering approximation is invalid when the thickness of the sample exceeds the scattering mean free path. This situation calls for a guideline to analyse the scattering data having significant contribution from multiple scattering. Since multiple scattering broadens the scattering profile, the beam broadening nature of multiple scattering can also be exploited, by making the sample suitably thick, to study large size inhomogeneities which are otherwise inaccessible to a small-angle scattering set up because of its resolution constraints. The present article presents a review and extension of the theoretical basis for analysing multiple scattering data from the point of view of a recent formalism on multiple small-angle scattering. The formalism is valid for both monodisperse and polydisperse scattering media characterized by the presence of large size inhomogeneities in the matrix. It is shown that multiple scattering from a polydisperse sample can be described by a system of coupled integrodifferential equation. However, multiple scattering from a monodisperse sample can be described by a Fokker-Planck type of equation. These equations have been analysed with an emphasis laid on the nature of the structural information pertaining to the inhomogeneities which is extractable from the multiple scattering profile. When the linear dimension of inhomogeneities becomes comparable to the scattering mean free path of the radiation in the sample, the statistical nature of the medium becomes pronounced. The statistical nature of the medium modulates the scattering profile. The modulation effect could be broadening or narrowing of the profile depending upon the nature of the inhomogeneities and their population distribution. The limiting regimes of validity and the implications of various approximations, frequently used to analyse the scattering data, have been indicated.     

Diffraction limit of the theory of multiple small-angle neutron scattering by a dense system of scatterers

Multiple small-angle neutron scattering by a high-density system of inhomogeneities has been considered. A combined approach to the analysis of multiple small-angle neutron scattering has been proposed on the basis of the synthesis of the Zernike–Prince and Moliére formulas. This approach has been compared to the existing multiple small-angle neutron scattering theory based on the eikonal approximation. This comparison has shown that the results in the diffraction limit coincide, whereas differences exist in the refraction limit because the latter theory includes correlations between successive scattering events. It has been shown analytically that the existence of correlations in the spatial position of scatterers results in an increase in the number of unscattered neutrons. Thus, the narrowing of spectra of multiple small-angle neutron scattering observed experimentally and in numerical simulation has been explained.     

Long-range intensity correlations for the multiple scattering of waves in unordered media

The long-range correlations in the reflected and transmitted fluxes in the case of the coherent transport of waves in an unordered medium with discrete inhomogeneities are considered. The correlator and spectrum of the intensity fluctuations are expressed in a general form in terms of the one-center scattering amplitude and the propagators of the mean radiated intensity. The random interference of the waves and the fluctuations of the number of scattering centers in a microvolume of the medium are taken into account simultaneously. Detailed calculations are performed for two limiting radiation propagation regimes, viz., spatial diffusion and small-angle multiple scattering. It is shown that the conservation of the total flux upon elastic scattering leads to the formation of a dip in the spectrum and, accordingly, a negative correlation between the intensities at large distances. In the case of spatial diffusion this feature is displayed upon reflection, and in the case of small-angle multiple scattering it is displayed upon transmission through a slab. The relative roles of the various sources of intensity fluctuations, as well as the sensitivity of the correlations to factors that influence the wave propagation regime, viz., the finite size of the scattering sample, absorption in the medium, and the presence of a frequency shift in the incident waves, are analyzed. We find that fluctuations in the distribution of the scatterers show up most strongly in a medium with strong, i.e., “non-Born,” centers, especially if they exhibit absorption. Zh. éksp. Teor. Fiz. 111, 1674–1716 (May 1997)     

Micro x-ray small-angle scattering with synchrotron radiation

Abstract

Three small-angle scattering cameras based on mirror/monochromator optics, a circular Bragg-Fresnel (BF) lens, and a microcollimation system combined with a double-focusing mirror have been tested for microfocusing applications. In order to reach a focal spot less than or equal to 10 μm. a microcollimation system provides a flexible solution for medium-resolution applications. When using a glass capillary as a collimation system, a minimum s-value of 5·10^?2 nm^?1 was attained. Scanning small-angle x-ray scattering (SAXS) patterns from a poly(tetramethyl-p-silphenylene)-siloxane spherulite and a 40-μm polyethyl-eneterephthalate fiber were obtained in a few seconds per pattern with a 4 μm diameter beam at a wavelength of λ = 0.095 nm.     

Elastic scattering of electrons from tetrahydrofurfuryl alcohol

Differential cross-sections (DCSs) for elastic scattering of electrons from tetrahydrofurfuryl alcohol (THFA), which can be considered as an analogue molecule to DNA sugar deoxyribose, were determined using crossed beam measurements for incident energies from 40 eV to 300 eV and scattering angles from 30° to 110°. The relative DCSs were measured both as a function of incident electron energy and scattering angle, allowing absolute calibration of the whole data set via normalization to a single point. The absolute calibration has been performed according to calculated absolute DCSs obtained by the corrected independent atom method using an improved quasifree absorption model. The calculated data-set includes DCSs and integral elastic and inelastic cross-sections in the incident energy range from 5 eV to 5000 eV. The theoretical results agree very well with the experimental ones, regarding the shape of DCSs. Moreover, the same theoretical procedure has been used to obtain DCSs for elastic electron scattering from a simpler deoxyribose analogue tetrahydrofuran (THF), which agree very well, both in shape and on the absolute scale, with the recent experimentally obtained absolute DCSs [A.R. Milosavljević et al., Eur. Phys. J. D 35, 411 (2005)]. The present results are also compared with the recent theoretical data for THF and THFA. Finally, according to both experimental and theoretical data, the DCSs for elastic electron scattering from THFA and THF molecules appear to be very similar both in shape and absolute scale.     

Effect of scattering media on decays of high-energy particles

The effect of multiple scattering on the decay of high-energy particles has been studied. The self-consistent method for the calculation of decay rates of particles undergoing multiple elastic collisions in an equilibrium medium has been developed. Influence of multiple scattering on the decay rate of a neutral pion in a hadron gas has been studied. Zh. éksp. Teor. Fiz. 116, 3–10 (July 1999)     

Characterization of porous materials by small-angle scattering

Characterization of porous materials by small-angle scattering has been extensively pursued for several years now as the pores are often of mesoscopic size and compatible with the length scale accessible by the technique using both neutrons and X-rays as probing radiation. With the availability of ultra small-angle scattering instruments, one can investigate porous materials in the sub-micron length scale. Because of the increased accessible length scale vis-a-vis the multiple scattering effect, conventional data analysis procedures based on single scattering approximation quite often fail. The limitation of conventional data analysis procedures is also pronounced in the case of thick samples and long wavelength of the probing radiation. Effect of multiple scattering is manifested by broadening the scattering profile. Sample thickness for some technologically important materials is often significantly high, as the experimental samples have to replicate all its essential properties in the bulk material. Larger wavelength of the probing radiation is used in some cases to access large length scale and also to minimize the effect of double Bragg reflections.     

Multiple small-angle neutron scattering for an arbitrary value of the born parameter

Computer calculations are made of the intensity of multiple small-angle neutron scattering using the general Moliére formula [8] over a wide range of variation of the Born parameter, embracing the diffraction and refraction regimes, and a transition region between diffraction and reflection. A comparison is made with approximate formulas obtained earlier by Maleev et al. [9, 10] in the limiting cases of the Born parameter α ? 1 and α ? 1 for the diffraction and refraction regimes, respectively. It is shown that over a wide range of values of α the results of the calculations using the approximate and general formulas are the same. The theoretical conclusions were checked experimentally using data from measurements of small-angle neutron scattering for the domain structure of ferromagnets. Measurements were made of the neutron beam broadening for samples of different thickness and these were used to determine the effective domain sizes in pure iron and nickel exposed to thermal treatment and plastic deformation, and also in the Invar alloys Fe⁶⁵Ni³⁵and Fe³Pt. An analysis is made of the angular dependence of magnetic small-angle neutron scattering at the asymptote.     

Carbide precipitates in solution-quenched PH13-8 Mo stainless steel: A small-angle neutron scattering investigation

This paper deals with the small-angle neutron scattering (SANS) investigation on solution-quenched PH13-8 Mo stainless steel. From the nature of the variation of the functionality of the profiles for varying specimen thickness and also from the transmission electron microscopy (TEM), it has been established that the small-angle scattering signal predominantly originates from the block-like metallic carbide precipitates in the specimen. The contribution due to double Bragg reflection is not significant in the present case. The single scattering profile has been extracted from the experimental profiles corresponding to different values of specimen thickness. In order to avoid complexity and non-uniqueness of the multi-parameter minimization for randomly oriented polydisperse block-like precipitate model, the data have been analyzed assuming randomly oriented polydisperse cylindrical particle model with a locked aspect ratio.     

Characterization of the structure of ultradispersed diamond using X-ray diffractometry and small-angle X-ray scattering

Two samples of detonation-synthesized ultradispersed diamond have been studied using X-ray diffractometry and small-angle X-ray scattering. It has been shown based on the X-ray diffractometry data that two samples contain regions with both the diamond and graphite-like lattices. Grain radii inside both samples are evaluated from the small-angle scattering data as 30–50 nm. The samples also contain low-dimensional components. A broad Bragg peak corresponding to a set of interplanar distances from 5 to 15 nm is revealed in the small-angle scattering curve of sample no. 1. A structural model of ultradispersed diamond particles, which represents the diamond core surrounded by concentric graphite shells similar to the onionskin, is confirmed.     

Asymptotic behavior of neutron small-angle multiple scattering spectra

The asymptotic behavior of the spectra for large values of the scattering vector for the case of elastic multiple small-angle neutron scattering (SANS) is investigated theoretically and experimentally. An expansion of the spectrum in terms of the reciprocal of the magnitude of the momentum transfer is obtained taking account of the influence of the instrumental line. It is shown that, to within some factor, the leading term of the expansion is identical to the differential single-scattering cross section averaged over a statistical ensemble of particles; several subsequent terms in the expansion are calculated and the range of applicability of the resulting expressions is determined. The asymptotic behavior of the multiple SANS spectrum is measured, using a two-crystal neutron spectrometer, for samples of an HTSC ceramic, the alloy Fe-Ni, and Al powder. The agreement between the experimental results and the theoretical predictions is analyzed. Zh. éksp. Teor. Fiz. 114, 2194–2203 (December 1998)     

Structure of amyloid aggregates of lysozyme from small-angle X-ray scattering data

The structure of filament amyloid aggregates of hen egg white lysozyme in water has been investigated by the small-angle X-ray scattering method. The experimental data are described by different cylindrical models, among which the best agreement is reached with the long helix model. A comparison of the results with the small-angle neutron scattering data reveals the influence of the heavy component of the solvent (a H₂O/D₂O mixture) on the structure of the filaments.     

Study of multiple small-angle neutron scattering by the warren method

A procedure for studying multiple small-angle neutron scattering using a double-crystal spectrometer is presented. It is based on measuring the linear coefficient of beam attenuation caused by smallangle scattering. The method has been substantiated theoretically, and the range of its applicability has been determined.     

Study of quasi-two- and three-dimensional ordered porous structures by means of small-angle X-ray scattering in the grazing incidence geometry

The structure of surface layers of thin metal inverse opals has been studied first by the grazing-incidence small-angle X-ray scattering technique. Contributions of the form factor and structure factor to the small-angle diffraction pattern have been separated using a numerical model of the scattering process. The complementary use of the small-angle X-ray scattering and grazing-incidence small-angle X-ray scattering techniques has provided independent information about the bulk and surface properties of the samples and allowed a type of defect in the investigated structures to be determined. The measurement results have been verified by atomic force microscopy.

     

Development of methods for processing spectra of multiple small-angle neutron scattering

A method has been developed for processing spectra of multiple small-angle neutron scattering (MSANS) to obtain information about substance heterogeneities, namely, their size and concentration. A method has been proposed for constructing the dependence of the MSANS line width on the sample thickness starting from the angular neutron distribution measured for one sample. The standard method for processing this dependence has been improved for application at any scattering multiplicity and complete account for the instrumental line of the double-crystal spectrometer. The method has been tested for the MSANS spectra of the samples of the Fe-Ni ferromagnet, Al powders, and HTSC ceramics.     

Three-body interaction-induced light scattering in krypton gas: a computer simulation of the spectral line shapes

The two-, three- and four-body effective collision induced scattering spectral line shapes are calculated for dense gaseous krypton using the pairwise additivity (PA) approximation and different polarizability models. These spectra and several interaction induced spectra calculated at various densities are compared with the experimental measurements of Barocchi et al. [1988, Europhys. Lett., 5, 607]. The potential effect on the spectrum is found to be weak. The results obtained with the Meinander et al. [1986, J. chem. Phys., 84, 3005] empirical polarizability model and molecular dynamics fit well the experimental two- and three-body spectral shapes. The irreducible contribution to the spectral shape is evaluated using the dipole induced dipole irreducible polarizability [buckingham, A. D., and Hands, I. D., 1991, Chem. Phys. Lett., 185, 544]. This contribution is found to be relatively weak for the anisotropic spectra in the frequency and density range studied, explaining the good agreement between the pairwise approximation calculations and the experimental data. The spectra radiated by the quasi-molecules Kr₂, Kr₃, and Kr₄ (the total spectrum within the PA approximation) are also simulated.     

Pion small-angle multiple scattering at energies spanning the (3,3) resonance

The small-angle multiple scattering of positive and negative pions has been measured for C, Al, Cu and Pb targets throughout an energy range spanning the (3, 3) resonance. The measurements were made using two-dimensional multiwire proportional counters placed in the pion beam. All previous multiple scattering data for electrons and protons as well as these new data for pions are used to recalculate the empirical terms in the Moliere theory of multiple scattering. A second-order Born approximation multiple scattering theory has been devised for spin zero particles. Modified Moliere theory gives a better fit to the experimental data than the second-order Born calculation. Because the updated Moliere theory contains much simpler equations and gives closer agreement with experiment, it is recommended in place of the more sophisticated theory for the interpretation of new experimental data.     

Investigation of multiple ultrasmall-angle neutron scattering with the aid of a double-crystal diffractometer

A method of multiple small-angle neutron scattering (MSANS), used to obtain information about inhomogeneities of substances, is considered. Experimental schemes and theory of a double-crystal diffractometer intended for measuring multiple small-angle neutron scattering are described. Methods used to approximate MSANS angular distributions at a low concentration of inhomogeneities and based on Moliére’s theory are reviewed. Their applicability is demonstrated for the examples ofMSANS spectra of samples from ferromagnetic iron-nickel alloys, aluminum powders, and high-T _c superconductor ceramic materials. Theoretical and experimental investigations of interference effects that manifest themselves in multiple small-angle neutron scattering on systems containing high concentrations of scatterers are reported.     

Resonant scattering of an X-ray photon by a heavy atom

The influence of many-body and relativistic effects on the absolute values and shape of the double differential cross section for the resonant scattering of a linearly polarized X-ray photon by a free xenon atom near the K-shell ionization threshold has been theoretically analyzed. The evolution of the spatially extended structure of the scattering cross section to the K _{α, β} structure of the X-ray spectrum of the xenon atom emission has been demonstrated. The calculations have been performed in the dipole approximation for the anomalous dispersion component of the total inelastic scattering amplitude and in the impulse approximation for the contact component of this amplitude. The contribution of the Rayleigh (elastic) scattering component is taken into account using the methods developed in Hopersky et al., J. Phys. B 30, 5131 (1997). The effects of the radial relaxation of the electron shells, spin-orbit splitting, double excitation/ionization of the atomic ground state, as well as the Auger and radiative decays of the produced main vacancies, are considered. Using the results obtained by Tulkki, Phys. Rev. A 32, 3153 (1985) and Biggs et al., At. Data Nucl. Data Tables 16, 201 (1975), the nonrelativistic Hartree-Fock wavefunctions are changed to the relativistic Dirac-Hartree-Fock wavefunctions of the single-particle scattering states when constructing the process probability amplitude. The calculations are predicting and are in good agreement with the synchrotron experiment on the measurement of the absolute values and shape of the double differential cross section for the resonant scattering of an X-ray photon by a free xenon atom reported by Czerwinski et al., Z. Phys. A 322, 183 (1985).