Effect of instrumental particle sizing resolution on the modelling of aerosol radiative parameters

A more realistic estimation of the scattering and hemispheric backscattering coefficients, σ_sp and σ_bsp, and their respective optical cross section, C_sca and C_bk, of aerosol particles is presented on the basis of the exact resolution of the width of the size bins of the particle counter instruments when size distribution measurements are used, and, with the exact optical detector instruments ability. The scattering and hemispheric backscattering cross sections, C_sca and C_bk, of the particles are averaged over the full size bins of the particle counter instrument, while these quantities are usually estimated only on the value of the mean geometric diameter of each size bin. Six instruments, the APS, ASASP-X, DMPS, FSSP-100, ELPI, and SMPS frequently used in particle size distribution measurements are reviewed, for spherical sea-salt particles at a wavelength λ=0.55 μm. The comparison using the conventional geometric mean diameter versus the use of the full size bin leads to large amount of errors for the optical cross section with non-negligible effects on their respective optical coefficients. The maximal accuracy expected for these optical quantities depend on the particle diameter as well as on the channel width of the instruments, and are also function of the angular detector probe used to measure them.     

The shape influence on the overall single scattering properties of a sample in random orientation

In order to identify the type of scattering profile that corresponds to some specific shapes, we have performed calculations of some scattering properties for those shapes with a fixed size distribution. Aggregates of different numbers of spheres have been used to fit the laboratory measurements of fly ashes. The results for other shapes, such as rectangular prisms with different axial proportions, particles made of joined cubes, and particles with different fluffiness, are also shown. From all these calculations, it is concluded that the size-averaged scattering matrix elements resembles Rayleigh features, for the size distribution stopping at , when either the number of spheres or cubes of the aggregates is increased, the shape becomes flatter or the particles become fluffier. We also show the effect of the refractive index on the Q_sca vs. X curve in the case of strongly absorbing particles. A tendency to reach the geometric optic regime is observed instead of the Rayleigh regime using the same size distribution.     

Order-disorder transformation in FePt nanoparticles studied by ferromagnetic resonance

We have investigated the ferromagnetic resonance (FMR) response of as-made and temperature annealed FePt magnetic nanoparticles. The as-made nanoparticles, which have been fabricated by a chemical route, crystallize in the low magnetic anisotropy fcc phase and have a diameter in the range of 2-4 nm. The annealing of the particles at high temperatures (T_A=550, 650 and C) in an inert Ar atmosphere produces a partial transformation to the high magnetocrystalline anisotropy L1₀ phase, with a significant increase in particle size and size distribution. FMR measurements at X-band (9.5 GHz) and Q-band (34 GHz) show a single relatively narrow line for the as-synthesized particles and a structure of two superimposed lines for the three annealed samples. The origin of this line shape has been attributed to the presence of the disordered fcc phase. Assuming that the system consists of a collection of identical particles with a random distribution of easy axes, we have been able to estimate a mean value for the magnetic anisotropy constant of the particles in the fcc phase, K∼2×10⁶ erg/cm³. The measured line shape in the annealed samples can be explained if we consider that the magnetic anisotropy of the particles has a gaussian distribution with a relatively broad width.     

Particle counting and numerical models: Effect of instrumental size resolution and particle shapes on optical cross-sections

The effect of instrumental size resolution measurements on numerical calculations of optical cross-sections is investigated. The particle counting instruments considered are a FSSP-300, a large scattering angle probe instrument similar to a ASASP-X, and, an aerodynamical system ELPI instrument. The scattering and hemispheric backscattering cross-sections, C_sca and C_bk, are calculated on the basis that the full width of the instrumental size bin should be considered in modeling. An average process is applied on these quantities over the full size bin of the instrument; they are then compared to their usual estimation on the single mean diameter D_p per channel. The effect of particle shape is investigated with ellipsoids and spheres. Results show sensitivity of the optical cross-sections to the shape of the particles as well as position of the mean geometrical diameter D_p of the channels within the interferences modes of the scattering efficiencies. The value of the width of the size bins, d log D, of each channel is crucial in the results. This comparison gives a useful estimation of error important in optical particle counting instruments based on inversion process of optical quantities. In addition, accuracy of size distribution measurements is found not to be representative of accuracy in the calculations of optical cross-sections.     

Light scattering modeling of small feldspar aerosol particles using polyhedral prisms and spheroids

The use of simplified particle shapes for modeling scattering by irregularly shaped mineral-dust particles is studied using polyhedral prisms and spheroids as model particles. Simulated phase matrices averaged over shape and size distributions at wavelength 633 nm are compared with a laboratory-measured phase matrix of feldspar particles with known size distribution with effective radius of . When an equi-probable shape distribution is assumed, prisms and oblate spheroids agree with measurements to a similar degree, whereas prolate spheroids perform markedly better. Both spheroids and prisms perform much better than spheres. When an automatic fitting method is applied for finding optimal shape distributions, it is found that the most elongated spheroids are most important for good fits, whereas nearly-spherical spheroids are generally of very little importance. The phase matrices for the different polyhedral prisms, on the other hand, are found to be similar, thus their shape-averaged phase matrices are insensitive to the shape distribution assumed. For spheroids, a simple parameterization for the shape distribution, where weights increase with increasing departure from spherical shape, is proposed and tested. This parameterization improves the fit of most phase matrix elements attained with an equi-probable shape distribution, and it performs particularly well for reproducing the measured phase function.     

团簇自然气溶胶散射相函数的数值分析

针对不同比例的灰尘和海盐团簇自然气溶胶,利用离散偶极子近似(DDA)法,通过考察成分的影响,使用波长为0.55 m,尺度参数变化范围为0.1~25时,研究了散射相函数和激光雷达比的影响,结果表明二者的变化趋势大体相同。尺度参数为13~24时,团簇自然气溶胶散射相函数有明显的后向散射加强,其中尺度参数为18附近,后向散射加强效应最明显。灰尘比海盐对散射相函数影响更大,二者的影响主要集中在尺度参数为15~25范围内,但除了散射角为180附近的后向外,影响的散射角方向略有不同。不同比例下的团簇自然气溶胶激光雷达比在尺度参数为3左右有最大值,其值约为180。在尺度参数为0.2~25范围内,成分对激光雷达比的影响不大,相对偏差小于10%,特别是尺度参数为0.5~2时的影响可以忽略,相对偏差小于1%。     

The scattering matrix of transparent particles of random shape in the geometrical optics approximation

A numerical model that allows one to calculate elements of the scattering matrix for transparent particles of random shape in the geometrical optics approximation is presented. It is shown that a deviation from sphericity, which, in particular, is modeled by a reduction of the number of triangular facets approximating a sphere, essentially affects the magnitude, position, and width of peaks of the photometric and polarimetric indicatrices. Thus, when 1500 facets were used for the approximation, the amplitude of the polarimetric peak associated with the first rainbow, which is located close to the scattering angle 160°, decreases by a factor of two. Calculations showed that, in the region of backscattering, for particles of an arbitrary shape, the linear polarization ?F ₁₂/F ₁₁ has no negative branch, which is well observed for spherical particles. In going from spherical to nonspherical particles, the backscattering peak also disappears. The indicatrices for particles of irregular shape that were calculated for small distances from the center of a particle noticeably differ from the indicatrices at infinity. Thus, when simulating multiple scattering in dense powderlike media, the use of particle scattering indicatrices that were calculated for infinite distances is incorrect even in the geometrical optics approximation.     

Equilibrium structure in the presence of internal rotation: A case study of cis-methyl formate

The Born-Oppenheimer (BO) equilibrium molecular structure () of cis-methyl formate has been determined at the CCSD(T) level of electronic structure theory using Gaussian basis sets of at least quadruple-ζ quality and a core correlation correction. The quadratic, cubic and semi-diagonal quartic force field in normal coordinates has also been computed at the MP2 level employing a basis set of triple-ζ quality. A semi-experimental equilibrium structure () has been derived from experimental ground-state rotational constants and the lowest-order rovibrational interaction parameters calculated from the ab initio cubic force field. To determine structures, it is important to start from accurate ground-state rotational constants. Different spectroscopic methods, applicable in the presence of internal rotation and used in the literature to obtain “unperturbed” rotational constants from the analysis and fitting of the spectrum, are reviewed and compared. They are shown to be compatible though their precision may be different. The and structures are in good agreement showing that, in the particular case of cis-methyl formate, the methyl torsion can still be treated as a small-amplitude vibration. The best equilibrium structure obtained for cis-methyl formate is: r(C_m-O) = 1.434 Å, r(O-C_c) = 1.335 Å, r(C_m-H_s) = 1.083 Å, r(C_m-H_a) = 1.087 Å, r(C_c-H) = 1.093 Å, r(CO) = 1.201 Å, ∠(COC) = 114.4°, ∠(CCH_s) = 105.6°, ∠(CCH_a) = 110.2°, ∠(OCH) = 109.6°, ∠(OCO) = 125.5°, and τ(H_aCOC) = 60.3°. The accuracy is believed to be about 0.001 Å for the bond lengths and 0.1° for the angles.     

Effects of nondiffusive wave propagation upon coherent backscattering by turbid media

The nondiffusive contribution to the coherent backscattering intensity is calculated for the media with relatively large particles (size a is greater than wavelength λ). The results are in good agreement with the experimental data at the wings of the angular spectrum of the coherent backscattering. The shape of the backscattering peak is analyzed for strongly absorbing media. The correlation function of the intensity fluctuations is calculated for the scattering by Brownian particles at relatively large time shifts.     

Calorimetric and single crystal X-ray study of the phase transition of (PyH)2PdCl4

Polymorphic transition of pyridinium tetrachloropalladate(II) was investigated by heat capacity measurements and by single crystal X-ray structural analysis. A large λ-type anomaly was detected at 240 K in the temperature dependence of the heat capacity. The low-temperature phase (LTP) belongs to the triclinic space group with a=6.856(1), b=7.293(1), c=7.721(1) Å, α=75.180(2)°, β=71.081(2)°, γ=81.109(3)° at 100 K, and the high-temperature phase (HTP) to the same space group with a=7.217(2), b=7.470(2), c=7.880(2) Å, α=73.438(3)°, β=65.195(3)°, γ=82.727(4)° at 293 K. The pyridinium cations are ordered antiferroelectrically in LTP. In HTP, however, an orientational disorder of the cation was observed. The energy difference between potential wells for the reorientation of pyridinium ion in HTP is discussed referring to the results of the present single crystal X-ray and heat capacity as well as the previous ¹H NMR measurements. A five-site disorder model is shown to be consistent with both of the observations of ¹H NMR and X-ray study.     

A new polar nephelometer for measurement of atmospheric aerosols

The angular dependence of light scattered by aerosol particles in the atmosphere—the aerosol phase function—is one of the key properties of every radiative transfer and climate model. Side-scattering in the atmosphere is currently believed to be underestimated by most of the radiative transfer models in certain cases. The aerosol phase function can be measured with polar nephelometers.An innovative polar nephelometer able to measure the phase function of ambient aerosol directly is presented in this publication. The performance of the device was simulated completely using ray-tracing techniques. The results of these simulations are used to interpret the measurement data precisely. The measurements with the new polar nephelometer are fully automated. The quality of the measurement results was verified using different approaches. The values of the statistical and systematic error in measuring atmospheric aerosol are about 4% each. Scattering angles from 10° to 160° were measured and it is shown that with the same design this range can be extended to 3-177° in steps of 0.16° with an aperture of less than 1.8°.Measurements of the aerosol phase function are presented and compared with data taken with an integrating nephelometer and measurements of the particulate matter concentration. All data correlate very well. The described polar nephelometer can measure the phase function and the scattering coefficient of atmospheric aerosol with high accuracy and can be used for continuous monitoring measurements as well as in field campaigns.     

Crystal orientation dependence of ferromagnetism in Fe-implanted MgO single crystals

Single crystals of MgO with (100), (110) and (111) orientations were implanted with 64 keV Fe ions at a dose of 1.9×10¹⁷ ions/cm² by using metal-vapor vacuum arc ion source (MEVVA). The magnetic properties were investigated by a superconducting quantum interference device magnetometer and Rutherford backscattering spectrometry (RBS) was used to analyze the Fe concentration and distribution. The presence of Fe nanoparticles in MgO matrix was verified by magnetization measurements. Results show that all the samples behave with ferromagnetism at 5 K and 300 K, and the coercive field, H_C, follow well the relation: at measured temperatures. The orientation dependence of the coercive field may result from the different distribution of Fe nanoparticle size.     

The study on magnetite particles coated with bilayer surfactants

Magnetite particles were prepared by co-precipitation, then sodium oleic (SO) and sodium dodecyl benzene sulfonate (SDBS) were applied as inner and outer surfactants, respectively. IR and TG were used to study the surface adsorption of SO and SDBS on magnetite particles. The experimental results demonstrated that SO molecules were linked to the magnetite particles through chemical bond and SDBS coated on the surface of magnetite particles covered with SO by means of Van der Waals attraction. Furthermore, based on the adsorption isotherms of surfactants on the magnetite particles and the dependence of Zeta potential of particles on the surfactants concentrations, the adsorption mechanisms of these two surfactants on the magnetite particles were studied. The isotherm adsorption model for SO on magnetite particles showed excellent correlation to Langmuir type and the adsorption equation was (25 °C), while that for SDBS on magnetite particles coated with SO showed excellent consistence with Freundlich type and the adsorption equation was Γ = 0.32c^0.475 (25 °C). In addition, the results demonstrated that both SO and SDBS formed monolayer adsorption on the surface of magnetite particles.     

Crystal structure and compressibility of a high-pressure Ti-rich oxide, (Ti0.50Zr0.26Mg0.14Cr0.10)O1.81, isomorphous with cubic zirconia

A Ti-rich oxide, (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)_∑=1.0O_1.81, was synthesized at 8.8 GPa and 1600 °C using a multi-anvil apparatus. Its crystal structure at ambient conditions and compressibility up to 10.58 GPa were determined with single-crystal X-ray diffraction. This high-pressure phase is isomorphous with cubic zirconia (fluorite-type) with space group Fm3¯m and unit-cell parameters a=4.8830(5) Å and V=116.43(4) Å³. Like stabilized cubic zirconia, the structure of (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 is also relaxed, with all O atoms displaced from the (, , ) position along 〈1 0 0〉 by 0.319 Å and all cations from the (0, 0, 0) position along 〈1 1 1〉 by 0.203 Å. No phase transformation was detected within the experimental pressure range. Fitting the high-pressure data (V vs. P) to a third-order Birch-Murnaghan EOS yields K₀=164(4) GPa, K′=4.3(7), and V₀=116.38(3) Å³. The bulk modulus of (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 is significantly lower than that (202 GPa) determined experimentally for cubic TiO₂ or that (~210 GPa) estimated for cubic ZrO₂. This study demonstrates that cubic TiO₂ may also be obtained by introducing various dopants, similar to the way cubic zirconia is stabilized below 2370 °C. Furthermore, (Ti_0.50Zr_0.26Mg_0.14Cr_0.10)O_1.81 has the greatest ratio of Ti⁴⁺ content vs. vacant O²⁻ sites of all doped cubic zirconia samples reported thus far, making it a more promising candidate for the development of electrolytes in solid oxide fuel cells.     

Experimental and theoretical analyses on the microwave backscattering ability and differential radar reflectivity of non-spherical hydrometeors

This paper experimentally and theoretically examines the scattering properties of simulated non-spherical hydrometeors including water oblates, ice oblates and ice sphere-cone-oblates, in terms of the backscattering cross-section and the differential reflectivity. The experimental measurements of the backscattering cross-sections of non-spherical hydrometeor samples were performed in the Electromagnetic Scattering Laboratory of China National Space Industrial Corporation. Meanwhile, the backscattering cross-sections have been computed with the transition (T) matrix method. The theoretical results are compared with the experimental data, showing that the calculations are consistent with the observations in general. Experimental and theoretical analyses indicate that the backscattering cross-section of non-spherical particles increases as the particle size parameter increases, and fluctuates when the sizes are larger under the effect of resonance scattering. Differential reflectivity Z_DR of water oblates in natural rainfall is always greater than 0 dB whereas Z_DR of hailstones may be negative. There is a good linear relationship between differential reflectivity and aspect ratio of a particle. These derivations agree with the literature and can be used to identify the presence of hail particles and distinguish between plate-type and columnar-type hydrometeors. In this study, the measuring experiment and the T-matrix method calculations for the scattering of simulated raindrop and ice particles are also briefly described.     

Magnetic and transport properties of UPd2Sb

A new compound UPd₂Sb was prepared and studied by means of X-ray diffraction, magnetization, electrical resistivity, magnetoresistivity, thermoelectric power and specific heat measurements. The phase crystallizes with a cubic structure of the MnCu₂Al-type (s.g. ). It orders antiferromagnetically at T_N=55 K and exhibits a modified Curie-Weiss behaviour with reduced effective magnetic moment at higher temperatures. The electrical resistivity behaves in a manner characteristic of systems with strong electronic correlations, showing Kondo effect in the paramagnetic region and Kondo-like response to the applied magnetic field. The Seebeck coefficient exhibits a behaviour expected for scattering of conduction electrons on a narrow quasiparticle band near the Fermi energy. The low-temperature electronic specific heat in UPd₂Sb is moderately enhanced being about 81 mJ/mol K².     

Mössbauer and magnetic studies in nickel ferrite nanoparticles: Effect of size distribution

The magnetic properties of nickel ferrite nanoparticles in the form of powders, prepared by the sol-gel process and subjected to different annealing temperatures, were investigated using both static and dynamic measurements namely hysteresis, zero field cooled-field cooled magnetization (ZFC-FC) measurements and Mössbauer spectroscopy. The Transmission Electron Microscopy (TEM) studies reveal particle sizes for the as-prepared particles which increases upto 52 nm with annealing. A bimodal distribution, upto an annealing temperature of was observed. ZFC-FC measurements for the as-prepared samples reveal twin peaks, indicative of the bimodal size distribution. ZFC-FC measurements performed for fields varying from 100 Oe to 3 kOe show a superparamagnetic phase with blocking temperatures between 320 and . Numerical simulations for the ZFC-FC studies indicate that the signature of the bimodal size distribution can be seen only at very low fields. The variation of coercivity with particle size, as determined from the hysteresis measurements, shows a transition from a single domain to a multi domain state for particle sizes larger than 35 nm. Mössbauer measurements performed at room temperature for the as-prepared sample shows a six finger pattern for the samples with higher particle size and a doublet pattern for the samples with smaller particle size, which is indicative of their superparamagnetic nature.