Charge interaction of low generation dendrimers during zeolite formation

A Small Angle X-ray Scattering (SAXS) investigation has been performed to study the self-assembly process generated by the addition of a low generation G1.5 polyamidoamine dendrimer during the zeolite LTA formation process. The presence of a condensed cationic Na⁺ charge all around the dendrimers, which is responsible for the intense electrostatic interparticle interaction potential, stimulate the condensed growth of the zeolitic phase onto the dendrimer substrate. The screening produced by the zeolite grown on the dendrimer surface promote also an entanglement process between the primary units with the formation of large clusters as evidenced by Scanning Electron Microscopy (SEM), and Energy Dispersive X-ray (EDX) microprobe spectroscopy experiments. The current investigation emphasizes the potentials of using hybrid organic-inorganic networks in the synthetic construction of functional materials with high-order structures for application in material science and biotechnology.     

Structural study of fractal silica humid gels

The structures of gels of silica obtained from solutions of TMOS, methanol and water have been studied by small angle X-ray scattering (SAXS) using synchrotron radiation. The SAXS results indicate that all the gels studied exhibit fractal structures. It is inferred that gels obtained under basic conditions are volume fractals built up by surface and volume fractal units for high and low water content, respectively. The gels obtained under acidic conditions are all volume fractals having structural units much smaller than those of basic gels. The influence of aging on the structure of basic gels has also been established.     

In situ study of the state of lysozyme molecules at the very early stage of the crystallization process by small-angle X-ray scattering

The molecular state of hen egg white lysozyme in solution has been studied by small-angle X-ray scattering (SAXS) combined with molecular simulation. The addition of a precipitant is shown to change the state of the protein molecules in solution. The SAXS data were processed using the constructed models of different oligomers. Under the crystallization conditions, lysozyme is shown to be present in solution as monomers (96.0%), dimers (1.9%), and octamers (2.1%), whereas tetramers and hexamers are not found. The modeled structure of the octamer is not consistent with the commonly accepted unit cell containing eight lysozyme molecules. Meanwhile, the modeled octamers are well-fitted to the crystal structure and can serve as building blocks in the course of crystal growth.     

USAXS studies of monosaccharide gels. II. The common features of structural changes

The results of SAXS studies are compared for two groups of samples: (i) obtained by in situ process of gelation of α-galactose-based gel with benzene as solvent, (ii) gels of various concentrations prepared from glucofuranose-based gelator with toluene. The experimental conditions of sample preparation and SAXS measurements were very similar for both groups. The results include fractal analysis of aggregates, and – for aggregate envelopes – the radii of gyration, pair functions, and simulated models. For both groups only two aggregate types were found to be formed: the first – of simple, loose fractal structure and disk-like shape, and the second – smaller aggregates, of well-developed fractal structure and cylinder-like shape. The conditions of the change from the first type to the second one are discussed. In addition, it was verified by the SAXS method on the basis of kind of fractal analysis for the loose structure that the fractal aggregate is built of gelator molecules joined by hydrogen interaction.     

Voids in amorphous semiconductors

Small angle X-ray scattering (SAXS) has been used to investigate density fluctuations occurring in amorphous semiconductors prepared by sputtering, evaporation and electrodeposition. Correlations of the total number of dangling bonds determined by SAXS, optical absorption, and ESR signals have been made. The density deficits from the density of the FC-2 crystal are in some cases accounted for by the voids. It is argued that models based on domains 10–15 Å in size are not supported by the SAXS data.     

Positron annihilation study of pore size in ordered SBA-15

Ordered mesoporous materials such as SBA-15 possess a network of channels and pores with a well-defined size in the nanoscale range (2–50 nm). This particular pore architecture makes them suitable candidates for a variety of applications. Different techniques have been used to measure pore diameters. PALS (positron annihilation lifetime spectroscopy) nanoprobe has been used to investigate free volume in several materials, including mesoporous silica. PALS can be used to find out if the micropore and mesopore structures of samples prepared under different experimental conditions are different. Indeed, considering that the pores present a cylindrical shape, an equation was developed that uses specific pore volumes, theoretical density, and specific surface measurements to evaluate structural connectivity. Our goal is to determine the influence of aging temperature on the porous structure of SBA-15 samples. The structural evolution was studied by PALS, small-angle X-ray (SAXS), N₂ adsorption desorption isotherms and computational modeling to evaluate connectivity. The variation of aging temperature changes the pore structure, indicating the presence of micropores and connections between mesopores. Materials aged at high temperatures present the lowest microporosity.     

A study of primary crystallization in Fe40Ni38Mo4B18 glassy alloy by small angle x-ray scattering

The primary crystallization of the Fe₄₀Ni₃₈Mo₄B₁₈ glassy alloy was followed with a Kratky SAXS camera. By using SAXS conventional treatments of the experimental data, an interconnected structure was found distinctive of the underlying texture in the early stage of the phase decomposition. At higher temperature treatments and well inside the DSC peak relevant to the solid solution appearance, the structural inhomogeneities reach a more defined morphology with a clear interphase boundary. Nevertheless, during this nucleation stage no distinctive crystalline states were detectable in the wide angle patterns as remarked by the authors in a previous work [4]. The particle size evolution points out that a coarsening mechanism starts with the achievement of the steady value of the SAXS integrated intensity and concurrently with the long range order establishment.     

SAXS and DSC studies on the structural characteristics of siliconized s-triazine glassy hybrid materials

Three hybrid materials composed of planar s-triazine rings and polyhedral silica (SiO₂), phenylsilsesquioxane (PhSiO_1.5) and diphenylsiloxane (Ph₂SiO) building blocks were investigated by differential scanning calorimetry (DSC) and small angle X-ray scattering (SAXS) techniques. These measurements revealed that the geometrically dissimilar components were fully integrated into intact glassy hybrid structures. Their DSC thermograms showed that these hybrids are thermally stable below 350 °C with moderate glass transition temperatures (T_g) of 56–110 °C consistent with the increasing structural connectivity of the silicone component. The SAXS data was analyzed to obtain different structural information using Porod, Guinier and Kratky approximations. The general features of each of the SAXS profiles of these hybrids are very similar to those of polyphenylsilsesquioxane (PPhSQ). The SAXS profiles reveal that these hybrids can be described as nano-scale primary particles that are self-organized in macromolecular ensembles to form extended unfolded textures of varying scattering lengths (91–168 Å). The obtained hybrid particles adopt either 3-D bulk fractals with open structures or 2-D surface fractals with dense cores. The short interfacial thickness (< 3 Å) and the low thermal fluctuation parameters strongly suggest that these particles are held together by substantial cohesion forces.     

SAXS investigation of porous nanostructures

Fractal and aggregate structures of aerogels were investigated by small angle X-ray scattering in order to analyze the various evaluation methods of the SAXS data for porous nanostructures. Scattering data (SAXS, USAXS) for aerogels measured with laboratory equipment as well as synchrotron technique were interpreted in the terms of Guinier, Porod, Freltoft, Teixeira, and Emmerling theories. We modified the Freltoft fit in order to get information about the structure of elementary units. The performances of the evaluation programs were studied for different aerogels structures such as fractal of wide range, fractal of limited size, and aggregate systems. The evaluation of the scattering measurements resulted in fractal dimensions, sizes of the elementary units, sizes of the fractal domains or aggregates. Quality of the fits to SAXS data was characterized by a mathematical parameter and proved by TEM photography. TEM images confirmed the sizes of the elementary building units and clusters.     

Liquid–liquid transitions,crystallization and long range fluctuations in supercooled yttrium oxide–aluminium oxide melts

Employing small angle X-ray scattering (SAXS) and wide angle X-ray scattering (WAXS) combined with laser-heated aerodynamic levitation has enabled different transitions in supercooled yttrium oxide–aluminium oxide to be distinguished. These include liquid–liquid phase transitions as well as high temperature crystallization for different compositions. Prerequisites for avoiding crystallization in order to reveal polyamorphic phase separation in the supercooled state are established. We also show how the rise in SAXS intensity at low wavevectors can be used to identify correlation distances in long range fluctuations in high temperature melts. These distances appear to scale with melt viscosity and to extend temporarily during liquid–liquid transitions.     

Cationic motifs in corundum,spinel, and amesite homologous structural classes

The coordinate spectra of the cationic motifs for 132 structural types in hexagonal and cubic crystal systems are analyzed. The homologous classes—polysome series of structural minals (modules)—are revealed. It is established that structural types of different compositions are characterized by similar structural cationic motifs and, hence, the growth and structure formation occur through the mechanism of ordered isomorphism.     

Crystal Structure of t‐boc‐O‐benzyl‐L‐tyrosyl‐D‐alanyl‐L‐(O‐benzyl)‐glutamate : monohydrate

The crystal structure of a tripeptide, t‐boc‐O‐benzyl‐L‐tyrosyl‐D‐alanyl‐L‐(O‐benzyl)‐glutamate has been determined by direct methods, and refined by full‐matrix least squares procedures to a final R‐index of 0.060. The peptide conformation corresponds to a reverse turn — Type II , stabilized by a 4 — 1 N‐H...O hydrogen bond, with the amide proton also forming a bifurcated hydrogen bond to an oxygen atom from the C‐terminus of a neighbouring molecule.     

A SAXS study of the nanometer scale hybrid structure of Si---Ti---C---O amorphous fibers

A small-angle X-ray scattering (SAXS) study was performed to reveal the nanometer scale hybrid structure of Si---Ti---C---O fibers prepared by the pyrolysis of polytitanocarbosilane. The SAXS profile for Si---Ti---C---O fibers is attributed to two different types of scattering entities: an anisotropic contribution from long filaments with diameters hundreds to thousands of Ångströms and an isotropic contribution from β-SiC fine clusters of about a nanometer in diameter. A drastic degradation in the tensile strength of the fibers is correlated to the characteristic variations in their long-and medium-range structure.     

Growth and melting of metallic nanoclusters in glass: A review of recent investigations

The mechanisms of nucleation and growth and the solid-to-liquid transition of metallic nanoclusters embedded in sodium borate glass were recently studied in situ via small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS). SAXS results indicate that, under isothermal annealing conditions, the formation and growth of Bi or Ag nanoclusters embedded in sodium borate glass occurs through two successive stages after a short incubation period. The first stage is characterized by the nucleation and growth of spherical metal clusters promoted by the diffusion of Bi or Ag atoms through the initially supersaturated glass phase. The second stage is named the coarsening stage and occurs when the (Bi-or Ag-) doping level of the vitreous matrix is close to the equilibrium value. The experimental results demonstrated that, at advanced stages of the growth process, the time dependence of the average radius and density number of the clusters is in agreement with the classical Lifshitz-Slyozov-Wagner (LSW) theory. However, the radius distribution function is better described by a lognormal function than by the function derived from the theoretical LSW model. From the results of SAXS measurements at different temperatures, the activation energies for the diffusion of Ag and Bi through sodium borate glass were determined. In addition, via combination of the results of simultaneous WAXS and SAXS measurements at different temperatures, the crystallographic structure and the dependence of melting temperature T _m on crystal radius R of Bi nanocrystals were established. The experimental results indicate that T _m is a linear and decreasing function of nanocrystal reciprocal radius 1/R, in agreement with the Couchman and Jesser theoretical model. Finally, a weak contraction in the lattice parameters of Bi nanocrystals with respect to bulk crystals was established. The text was submitted by the authors in English.     

Core-Shell-Structures in Multiphase Dielectric Ceramics

Developments in the field of multilayer capacitors (MLC) still require investigations of the micro-structure-property relationships of the dielectric materials. Multiphase ceramic dielectrics with “core-shell” micro-structure obviously are best suited for a “flat”, i.e. nearly constant temperature behavior of the dielectric constant (DC), which is of the order of 2000—4000. A general demand is that the DC-reduction within the temperature range —55 °C to +125 °C should be less than 15% (X7R classification). In addition to this, the sintering temperature should not exceed 1120 °C. The kind of structure, which is finally obtained is influenced by several factors: the composition of the precursor materials, the mixing procedure, the temperature-time regime during the firing process, and eventually the final annealing treatment. Using barium titanate as core material and mixing it with different perovskite compounds we adopted two different methods of production of the dielectrics, here investigated. They resulted in two different structure forming mechanisms, leading to different micro-structures.     

Structure changes in amorphous silica by neutron irradiation

Wide angle, small angle, and very-small angle X-ray scatterings (WAXS, SAXS and VSAXS) as well as optical microscopy are observed for amorphous silica before and after neutron irradiation [3×10¹⁰n_th/cm², (48±2)°C]. The results are analyzed by employing the continuous random network (CRN) model [Zachariasen, J. Am. Chem. Soc. 54 (1932) 3841] that is topologically equivalent to the dense random packing (DRP) model for metallic glass (hard spheres being replaced by deformable spheres containing Si₂O₄ structural units).The effects of irradiation, as deduced from the broadening of the innermost haloes in WAXS, are interpreted in terms of an enhancement of randomness in the packing of the spheres materializing the structural unit, and in the internal structures of the spheres. This involves the rearrangements of the OSiO network that results in the local invalidation of the CRN-DRP equivalence. Consequently, small (25 Å) and large ($\text{2×10}{}^5\text{A}\text{?}$) structural inhomogeneities are produced that can effectively be disclosed by WAXS, SAXS, VSAXS, and optical microscopy. Arguments are advanced in which these structural changes are viewed as deviations from the DRP-equivalent CRN model in an analogous way as interpreting the radiation effects of amorphous Pd₈₀Si₂₀ (Doi et al., J. Non-Crystalline Solids 34 (1979) 405).     

Quasi-Rayleigh waves in sandwich structures: Dispersion equation, eigenmodes, and resonance reflection

The dispersion equation for quasi-Rayleigh acoustic modes in transversely isotropic sandwich-type structures (an elastic layer between two substrates) has been obtained in the analytical form. The equation is analyzed for three types of structures—a layer between two soft substrates, a layer between a soft and a hard substrate, and a structure consisting of two contacting substrates with markedly different values of hardness. Eigenmodes are determined for all three structures. Depending on the combination of the material parameters in these structures, these eigenwaves are either Rayleigh-type waves localized at interfaces in the substrates and accompanying a Lamb wave in the interlayer (in the absence of an interlayer, forming a Stoneley wave) or the leaky modes characterized by a small imaginary addition to the phase velocity and the presence of bulk partial waves of leakage providing some energy removal from the interfaces. Without any calculations, simple criteria were established that allow one to predict the existence of a leaky mode in the given structure and the number of leakage fluxes it contains. The resonance reflection is analized for the case where the incidence angle of the wave in the substrate corresponding to the velocity v of the wave-front propagation along the interface is close to the value of the real part of the phase velocity of the leaky mode.     

Crystallization behaviour of an amorphous Ti50Be40Zr10 alloy

The crystallization behaviour of an amorphous Ti₅₀Be₄₀Zr₁₀ alloy during a continuous heating mode from room temperature to 973 K and isothermal annealing at temperatures above the glass transition temperature is examined by differential scanning calorimetry (DSC), small-angle X-ray scattering (SAXS) measurement and large-angle X-ray diffractometry (LAXD). DSC indicated two well-defined exothermic peaks, a slight shoulder at the higher temperature side of the second peak and a small heat evolution at higher temperature. The Kissinger plot for the first and the second peak gives a straight line, from which the apparent activation energy is estimated to be 269 and 413 kJ/mol respectively; the enthalpies for the first and second crystallization process are 1.04 kJ/mol and 4.39 kJ/mol for a heating rate of 20 K/min. The SAXS intensities increase sharply after annealing at about 673 K (corresponding to the first peak in the DSC curves); the scattering is due to the formation of fine-scale crystalline Ti particles by the LAXD. The size of the particles does not change significantly while the number of scattering particles increases, indicating that the reaction is almost nucleation controlled and the growth is very limited. Another crystalline phase would appear in addition to the Ti particles on annealing at temperatures above about 753 K (corresponding to the second peak in the DSC curves), where the SAXS intensities decrease compared with those for only the first-stage of crystallization. The crystalline phase might be a metastable cubic phase with the lattice parameter a₀?0.2994 nm.The sequence in the crystallization of the initial non-crystalline material is amorphous → microcrystalline (MS I) → crystalline (MS II; S III), although the structure of crystalline phase in the final stage (S III) was not identified. It is also likely that cold-rolling does not have a perceptible effect on the crystallization behaviour of the present amorphous alloy.     

超高压下熔媒法人造金刚石合成机制研究的重要进展

本文对熔媒法人造金刚石的实验、观察和分析,包括熔媒金属(FC或m)、石墨(g)和金刚石(D)存在状态、结晶状况、微观结构和结构特征及其各自结果的分析讨论等研究作了报导.在此基础上对人造金刚石的合成机制作出有机统一整体的讨论如下:(1)形成D结晶基元相变必要条件的特征,可以认为在m熔化过程中发生的助熔激发效应.由于m的d带空穴同g的π-电子相互作用产生各种集团和原子,特别是具有近程有序与密排面结构的原子集团,从而形成一种具有适当尺寸和可变组元的类填隙式固溶体-复合原子集团;(2)形成D结晶基元相变充分条件的特征,可以认为在前述的复合原子集团中的密排面间隙部位发生m的催化激发效应.由于m的价电子处于激发态统计权重增高达到d3s或类sp3状态,诱发处于复合原子集团中类g原子集团实现sp2转移sp3状态.形成一种具有可变组分、不稳定的或部分稳定的类间隙相.这种间隙相式复合原子集团是相变的产物,也是在非平衡态下具有扩散性的主要结晶基底和结晶基元;(3)人造金刚石体系中m/g相互作用的必要和充分条件的特征可用它们的界面结合特征方程作判据来描述.这种判据取决于反映在它们表面和界面上几何结构、电子结构和尺寸等效应(与原子-分子层次结构及相互作用状态有关)的表面能、界面能和有效尺寸.所推导的方程对人造金刚石体系中相互作用,即熔媒激发复合效应的最适合状态提供重要的科学依据和有效技术途径.