Effect of uni-axial loading on the nanostructure of silica aerogels

Aerogels are unique materials offering a combination of remarkable properties that make them useful in a wide range of applications. However, aerogel materials can be difficult to work with because they are fragile. The intent of the work presented here was to study the relationship between axial loading and pore structure in aerogel material. Silica aerogel samples with a bulk density of 0.1 g/mL were compressed by uni-axial force loads from 1 to 5 kN which resulted in stress levels up to 23 MPa. The resulting change in the pore distribution was observed using nitrogen desorption analysis and scanning electron microscopy. Uncompressed aerogel samples exhibit peak pore volume at diameters of about 20 nm. As the aerogels are subjected to increased loading, the location of the peak volume moves to smaller diameters with a reduced volume of pores occurring above this diameter. The peak diameter, the average pore diameter and pore volume all decrease and scale with increasing maximum stress while the surface area of the aerogel samples remains unaffected at about 520 m²/g. When combined with data from the literature, the relation between maximum pore diameter and applied stress suggests a failure mechanism dominated by bending induced fracture.     

Physical aging effect on the boson peak and heterogeneous nanostructure of a silicate glass

The effect of physical aging on a silicate glass has been investigated by low-frequency Raman scattering. It was observed that the low-frequency side of the excess of Raman scattering, or boson peak, due to harmonic vibration modes decreases in intensity with the thermal annealing (aging) at a temperature lower than the glass transition temperature (T_g), after quenching (rejuvenation) from a temperature higher than T_g. Moreover, it was found that the lowering of the very low-frequency scattering mainly due to anharmonic modes becomes more pronounced when the aging temperature is decreased. These observations are interpreted in the frame of the energy landscape, and by considering the model of the glass heterogeneous cohesion at the nanometric scale.     

Indications of the magnetic state in the charge distributions of MnO,CoO, and NiO. III. Antiferromagnetism of NiO

X-ray diffraction intensities were measured from antiferromagnetic NiO. The data were submitted to a nonparametric multipole analysis aimed at formulation of experimentally valid statements on the nature of charge distribution. Strong “bonding maxima” appear between the Ni〈100〉O nearest neighbors in the region of the oxygen atoms involving NiO coupling. An electronic cage structure is also observed. This is parallel to the observations on MnO and CoO but different in nature, being formed by separate cubic cages for the cations instead of the oxygen, and without a clear indication of an extended network buildup.     

Indicators of the magnetic state in the charge distributions of MnO, CoO, and NiO. II: Para-and antiferromagnetism of CoO

X-ray diffraction intensities from CoO were measured above and below the Néel temperature. The data were submitted to a non-parametric multipole analysis aiming at formulation of experimentally valid statements on the nature of the charge distribution. Strong “bonding maxima” are seen between the Co 〈110〉O nearest neighbors. In the paramagnetic state they are formed by the Co-ion alone, in the antiferromagnetic state they involve a strong CoO coupling. The outer electrons of oxygen give rise to slight maxima in the 〈110〉 directions, making the atom into an O^2? ion. In the paramagnetic state, their coupling with the bonding feature forms an octahedral electron cage around each oxygen atom. Broad density maxima between the atoms in 〈111〉 directions are present in both states. They connect the “bonding maxima” in the 〈110〉 directions, more strongly in the antiferromagnetic state, building up an interatomic three-dimensional network. Such electron network structures seem to be characteristic of metal oxides more generally.     

Growth and crystal structure of the layered compound TlGaSe2

The semiconducting compound TlGaSe₂ was grown by solid state reaction technique. The crystal structure of this material was confirmed by single‐crystal X‐ray diffraction. TlGaSe₂ crystallizes in the monoclinic system with space group C2/c (No. 15), Z = 16 and unit cell parameters a = 10.779(2) Å, b = 10.776(1) Å, c = 15.663(5) Å, β = 99.993(6)°. The structural refinement converged to R(F) = 0.0719, R(F²) = 0.0652 and S = 1.17. The structure consists of a three‐dimensional arrangement of distorted TlSe₈ and GaSe₄ polyhedrons. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Indications of the magnetic state in the charge distributions in MnO, CoO, and NiO. I: Para-and antiferromagnetism of MnO

X-ray diffraction intensities from MnO and CoO were measured above and below their Néel temperatures and from NiO, below the Néel temperature. To detect possible characteristics of the paramagnetic and antiferromagnetic states of the crystals, the data were subjected to direct multipole analysis of the atomic-charge densities. For MnO, both spherical and nonspherical accumulation-of-charge densities indicate the exchange of the roles played by manganese and oxygen in the magnetic phase transition. Both spherical and nonspherical features characteristic of the ionic nature are inherent in both states. The electron counts of the density peaks correspond to Mn²⁺ and O^1?, with the tenth electron of O2? being distributed in a wider region. In the paramagnetic state, there is an electronic Mn-Mn bond which seems to be formed due to coupling with the tenth electron of O^2? and builds up a three-dimensional net of the charge density with the “cages” surrounding oxygen atoms. In the antiferromagnetic state, some Mn-Mn bonds disappear, while the preserved nonspherical ionic features enhance the role of oxygen atoms in electronic coupling.     

Influence of stacking disorder on the electronic properties of layered semiconductors

It is shown that stacking disorder in layered semiconductors leads to a localization of the electronic wavefunctions over a finite number of layers. The electronic transport across the layers is described in terms of a hopping model. The experimentally observed strong anisotropy of the de-conductivity for low temperatures is explained as a consequence of the stacking disorder.     

Dielectric properties of thallium gallium diselenide layered crystal in the incommensurate phase

The dielectric measurements of the layered crystal were studied in temperature range of successive phase transitions. The measurements revealed that the phase transition occurred in 242 K is an incommensurate phase transition. When the sample is annealed at a stabilized temperature in the incommensurate phase, a remarkable memory effect has been observed on cooling run. The mechanism of the memory effect in the incommensurate phase of the semiconducting ferroelectric TlGaSe₂ can be interpreted in the frame of the theory of defect density waves. This theory claims that the memory effect is the result of pinning of the incommensurate structure by the lattice inhomogeneities. With decreasing the annealing temperature the phase transition temperature shifts to lower temperatures gradually. Moreover, the peak intensities also increase gradually. In addition to these effects, the phase transition temperature shifts to lower temperatures with increasing annealing time. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Numerical simulation of heat conduction for the growth of anisotropic layered GaSe crystals

In this report, we present the usage of a second rank cylindrical conductivity tensor which we derived to simulate the crystal growth processes of a layered compound GaSe in a cylindrical enclosure by directional solidification. Use of such a tensor is inevitable in the simulations of the growth of highly anisotropic crystals having layered structure, since the crystallographic orientation of the grown material is not necessarily aligned with the ampoule symmetry. Using the finite difference control volume approach in 3D, we solved transient heat conduction equation for a highly anisotropic solid in a cylindrical enclosure. We obtained sloped thermal fields and isothermal surfaces and the magnitudes of the slopes are strong functions of both azimuthal angle and growth orientation. The results showed that the orientation of the crystallographic axes of GaSe in the enclosure is quite effective in the steady and the transient fields, isotherms, and axial and radial temperature gradient within the material. Increase of Bi number decreases the magnitude of the slope of isothermal surface. Anisotropy of the conductivity seems to be effective in the orientation of the growth direction of the resulting crystal within the cylindrical ampoule. (© 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Anisotropy of the optical absorption in layered single crystals of MoRe0.001Se1.999

Energy gap of MoRe_0.001Se_1.999 single crystal has been determined by fundamental absorption methods. The incident light was polarized along c‐axis of the crystals. The interpretion of the data is given within frameworks of two and three dimensional models. Both direct and indirect transitions are involved in the absorption process. The indirect transition was found to be allowed with two phonons participating in the process. The three dimensional model could be used to describe the optical properties of the single crystal. The energy gaps depend upon the amount of the intercalating Re material, which show the anisotropy of the chemical bonds. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Resonance excitation of polaritons by bulk electromagnetic waves in the layered systems with anisotropic substrates

The possible resonance excitation of surface electromagnetic waves by the bulk waves at the interface between a positive transparent uniaxial crystal and an isotropic medium has been predicted. The existence of the surface waves is provided by anisotropy of one of the boundary media. The tensor relation between the vector amplitudes of an exciting bulk electromagnetic wave and the excited surface wave is established. The ratio of the moduli of the tangential components of these amplitudes is analyzed as a function of the angle of incidence and the polarization of the bulk wave. The numerical calculations are performed for the surface waves at the interface between paratellurite TeO₂ and a KRS-6 (TlBr 30%-TlCl 70%) crystal.     

Formation of the nanocrystalline state by twinning crystals

The formation of the nanocrystalline state under the action of a concentrated load applied to crystals is studied. It is established that the relaxation of the enormous stresses (on the order of the shear modulus) arising under the indenter proceeds through twinning, which results in the fragmentation of the structure into nanoblocks. The properties of the nanocrystalline material thus obtained are explained based on the consideration of grain boundaries as twin boundaries that represent another phase of the material.     

Formation of oxygen-deficient type structural defects and state of ions in SiO2 glasses implanted with transition metal ions

The properties and concentrations of oxygen-deficient type structural defects in type III SiO₂ glasses implanted with Ti⁺, Cr⁺, Mn⁺, Fe⁺, or Cu⁺ to doses from 0.5×10¹⁶ to 6×100¹⁶ ions/cm² at an energy of 160 keV have been measured by using vacuum UV and EPR spectroscopies. An intense absorption band centered around 7.5 eV is observed in all the samples except for Cu-implanted ones and is attributed primarily to Si---Si homo-bonds with the bond distance close to that of the Si₂H₆ molecule. The homo-bond and implanted ion concentrations are of the same order of magnitude in the implanted layers. An E′ type center associated with the homo-bond is observed in all the samples except for Cu-implanted ones. Anomalous behaviors of the Cu-implanted samples are attributed to the formation of Cu-colloids. An enhanced formation of metallic particles or colloids is suggested for the samples implanted with Cr, Mn or Fe to doses higher than 3×10¹⁶ ions/cm².     

Determination of the magnetic contribution to the YFe2 susceptibility by means of X-ray resonant magnetic reflectivity

The reflectometry curves of an Nb(4 nm)/YFe₂(40 nm, 〈110〉)/Fe(1.5 nm)/Nb(50 nm) sample measured in the synchrotron radiation of right- and left-handed circular polarization for a set of wavelengths near the Y L _2,3 absorption edges have been used to determine the energy dependences of the component magnitudes for the X-ray susceptibility tensor of YFe₂ near the yttrium absorption edges, including off-diagonal magnetic additives. Our result is in good agreement with the normalized experimental absorption and circular dichroism spectra and their Kramers-Kronig transformations.     

Effect of the charge state on the photoluminescence spectra of melanin

Abstract

Steady-state and time-resolved photoluminescence (PL) spectra of natural and synthetic melanin, as well as melanin composites with surfactant, sodium dodecylbenzenesulfonate, and polymethine dye, astraphloxin, have been studied. The melanin molecules having differently charged peripheral groups with terminal O atoms and OH groups mixed with the negatively charged surfactant or positively charged astraphloxin dye feature new PL spectral bands. The kinetics of PL and time-resolved emission spectra for the melanin and the composites were also investigated and discussed in terms of intermolecular complexation, nano-aggregation and formation of charge-transfer states. The studies are aiming to understand the electronic properties of various melanins, particularly natural ones.     

Features of bicrystal growth during the directional crystallization of metal melts

The factors responsible for the formation of different configurations of boundaries between adjacent crystallites during their growth from melt by Bridgman and Czochralski methods have been considered by an of example Fe–20 wt % Ga alloy and Ni bicrystals. It is found that the configuration of intercrystallite boundary is related to the features of crystallite growth, caused by the strained state of intercrystallite and interphase (crystal–melt) boundaries, the difference in the linear thermal expansion coefficients of the crystallite boundaries and bulk, and the shape (geometry) of the bicrystal cross section. It is suggested that the strained state of boundaries and the formation of substructure in crystallites during directional crystallization from metal melt are significantly affected by their deformation under the melt weight.

     

On the state of Mn impurity implanted in Si

The state of manganese impurity in implanted silicon at implantation doses of up to 5 × 10¹⁶ cm^?2 has been investigated by X-ray diffraction and transmission electron microscopy. It is established that, after short-term vacuum annealing at 850°C, most of the implanted manganese impurities are in microinclusions up to 20 nm in size formed by a tetragonal silicide phase of the Mn₁₅Si₂₆ type.