Vibration eigenmodes and size of microcrystallites in glass: Observation by very-low-frequency Raman scattering.
TL;DR: It is shown that vibrational surface modes of particles are responsible for this Raman scattering and the frequency of the maximum of scattering is proportional to the inverse diameter of the particles, which are spherical spinel microcrystallites.
Abstract: The observation of very-low-frequency bands by Raman scattering in a nucleated cordierite glass is described. The frequency of the maximum of scattering is proportional to the inverse diameter of the particles, which are spherical spinel microcrystallites. It is shown that vibrational surface modes of particles are responsible for this Raman scattering.
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TL;DR: The onset of a sharp change in ddT( is the Debye-Waller factor and T is temperature) in proteins, which is controversially indentified with the glass transition in liquids, is shown to be general for glass formers and observable in computer simulations of strong and fragile ionic liquids, where it proves to be close to the experimental glass transition temperature.
Abstract: Glasses can be formed by many routes. In some cases, distinct polyamorphic forms are found. The normal mode of glass formation is cooling of a viscous liquid. Liquid behavior during cooling is classified between "strong" and "fragile," and the three canonical characteristics of relaxing liquids are correlated through the fragility. Strong liquids become fragile liquids on compression. In some cases, such conversions occur during cooling by a weak first-order transition. This behavior can be related to the polymorphism in a glass state through a recent simple modification of the van der Waals model for tetrahedrally bonded liquids. The sudden loss of some liquid degrees of freedom through such first-order transitions is suggestive of the polyamorphic transition between native and denatured hydrated proteins, which can be interpreted as single-chain glass-forming polymers plasticized by water and cross-linked by hydrogen bonds. The onset of a sharp change in d dT( is the Debye-Waller factor and T is temperature) in proteins, which is controversially indentified with the glass transition in liquids, is shown to be general for glass formers and observable in computer simulations of strong and fragile ionic liquids, where it proves to be close to the experimental glass transition temperature. The latter may originate in strong anharmonicity in modes ("bosons"), which permits the system to access multiple minima of its configuration space. These modes, the Kauzmann temperature T(K), and the fragility of the liquid, may thus be connected.
4,016 citations
TL;DR: In this article, the authors provide a basic understanding of the information micro-Raman Spectroscopy (mRS) may yield when applied to nanomaterials, a generic term for describing nano-sized crystals and bulk homogeneous materials with a structural disorder at the nanoscale.
905 citations
Cites background or methods from "Vibration eigenmodes and size of mi..."
...Their relative intensity is variable but only the first order "surface" ones, those shown in Figure 8, have significant contributions [258,261-263]....
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...These equations were used to measure the radius of silver clusters in ancient and advanced materials [264-267] or particles size in cordierite [262], TiO2 [268-270], silicon [271,272], PbSe [273], etc....
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TL;DR: In this article, the authors present a complete Raman spectrum analysis of SnO2 nanoparticles, which comprises modification of the normal vibration modes active in Raman when the spectra are obtained from nanocrystals of Sn O 2 nanoparticles in the region around 475 −775 cm 21, and the appearance of the acoustic modes in the low-frequency region of the spectrum.
Abstract: 14 and space group P4 2 /mnm. The unit cell consists of two metal atoms and four oxygen atoms. Each metal atom is situated amidst six oxygen atoms which approximately form the corners of a regular octahedron. Oxygen atoms are surrounded by three tin atoms which approximate the corners of an equilateral triangle. The lattice parameters are a5b 54.737 A, and c53.186 A. The ionic radii for O 22 and Sn 41 are 1.40 and 0.71 A, respectively. 1 The 6 unit cell atoms give a total of 18 branches for the vibrational modes in the first Brillouin zone. The mechanical representation of the normal vibration modes at the center of the Brillouin zone is given by 2,3 G5G 1 ~ A1g!1G 2 ~ A2g!1G 3 ~ B1g!1G 4 ~ B2g! 1G 5 ~ Eg!12G 1 ~ A2u!12G 4 ~ B1u!14G 5 ~ Eu!, ~1! using the Koster notation with the commonly used symmetry designations listed in parenthesis. The latter will be used throughout this article. Of these 18 modes, 2 are active in infrared ~the single A2u and the triply degenerate Eu), 4 are Raman active ~three nondegenerated modes, A1g , B1g , B2g , and a doubly degenerate Eg), and two are silent ( A2g , and B1u). One A2u and two Eu modes are acoustic. In the Raman active modes oxygen atoms vibrate while Sn atoms are at rest ~see Fig. 1 in Ref. 4!. The nondegenerate mode, A1g , B1g , and B2g , vibrate in the plane perpendicular to the c axis while the doubly degenerated E g mode vibrates in the direction of the c axis. The B 1g mode consists of rotation of the oxygen atoms around the c axis, with all six oxygen atoms of the octahedra participating in the vibration. In the A2g infrared active mode, Sn and oxygen atoms vibrate in the c axis direction, and in the Eu mode both Sn and O atoms vibrate in the plane perpendicular to the c axis. The silent modes correspond to vibrations of the Sn and O atoms in the direction of the c axis (B1u) or in the plane perpendicular to this direction ( A2g). According to the literature, the corresponding calculated or observed frequencies of the optical modes are presented in Table I. When the size of the SnO2 crystal is reduced, the infrared spectrum is modified because the interaction between electromagnetic radiation and the particles depends on the crystal’s size, shape, and state of aggregation. 8‐1 0 Experiments using Raman spectroscopy have also reported spectrum modification, at least partially. Low frequency bands have been observed previously in SnO2, 11 and several authors have reported the existence of bands not observed in single-crystal or polycrystalline SnO 2 which have been found to be closely related to grain size. 12‐15 However, some of these reports do not adequately explain the origin of the abnormal spectrum. The aim of this article is to present a complete Raman spectrum of SnO2 nanoparticles. The analysis comprises ~i! modification of the normal vibration modes active in Raman when the spectra are obtained from nanocrystals of SnO2 ~‘‘classical modes’’ !, ~ii! the disorder activated surface modes in the region around 475‐775 cm 21 , and ~iii! the appearance of the acoustic modes in the low-frequency region of the spectra.
669 citations
TL;DR: In this paper, the authors take familiar inorganic oxide glasses and non-oxide glasses and the liquids from which they derive to review the current understanding of their atomic structure, ranging from the local environments of individual atoms to the long-range order which can cover many interatomic distances.
Abstract: We take familiar inorganic oxide glasses and non-oxide glasses and the liquids from which they derive to review the current understanding of their atomic structure, ranging from the local environments of individual atoms to the long-range order which can cover many interatomic distances. The structural characteristics of important glasses and melts, like silicates, borates, alumino-silicates, halides and chalcogenides, are drawn from the results of recent spectroscopy and scattering experiments. The techniques include Nuclear Magnetic Resonance (NMR) and X-ray Absorption Fine Structure (XAFS), Neutron Scattering (NS) and Small- and Wide-angle X-ray Scattering measurements (SAXS/WAXS), and are often combined with computer simulation experiments in order to obtain detailed images of structure and diffusion in the glassy as well as in the molten state. We then review the current understanding of relaxation in glasses, liquids and polyamorphic states. This includes phenomenological models and theories of rela...
477 citations
TL;DR: Various aspects of the micro-/nano-structured materials as mechanical metamaterials, potential tools for their multidimensional fabrication, and selected methods for their structural and performance characterization are described, as well as some prospects for the future developments in this exciting and emerging field.
Abstract: Mechanical properties of materials have long been one of the most fundamental and studied areas of materials science for a myriad of applications. Recently, mechanical metamaterials have been shown to possess extraordinary effective properties, such as negative dynamic modulus and/or density, phononic bandgaps, superior thermoelectric properties, and high specific energy absorption. To obtain such materials on appropriate length scales to enable novel mechanical devices, it is often necessary to effectively design and fabricate micro-/nano- structured materials. In this Review, various aspects of the micro-/nano-structured materials as mechanical metamaterials, potential tools for their multidimensional fabrication, and selected methods for their structural and performance characterization are described, as well as some prospects for the future developments in this exciting and emerging field.
441 citations