The structure of amorphous carbon tetrachloride by neutron diffraction

A vapour-deposited sample of amorphous CCl₄ at 10 K has been studied by neutron diffraction. The measured structure factor confirms that the basic molecular unit is retained in the amorphous phase and a form-factor fit to the high Q-value data gives a CCl bond length of (1.770±0.002) Å. The inter-molecular function, D_M(Q) shows more structure than for the liquid phase and transformation to a real-space distribution function confirms that this is due to a much stronger orientational correlation between adjacent molecules in the amorphous solid. The density is found to be (25±5)% higher than in the liquid and the structural properties can be well described using a reference interaction site model (RISM).     

Structural analysis of amorphous Ge0.5Te0.5 by neutron diffraction

Neutron diffraction measurements have been made on a sputtered sample of amorphous Ge_0.5Te_0.5. Analysis of the radial distribution function derived from Fourier inversion of the measured structure factor gives a nearest neighbor coordination number n = 2.49. This result, compared with coordination models proposed for this composition, favors the chemically ordered 3t2-3 model (where each Ge and Te atom is threefold coordinated by the other one) analogous to a-As with n = 2.78 over the 4-2 models with n > 3.20. More detailed analysis including second neighbor atoms confirms the ordered threefold a-As model.     

Study by x-ray and neutron diffraction of the structure of ex-carbonyl amorphous iron

Ex-carbonyl amorphous iron is a heterogeneous finely powdered material. Its texture established by standard physico-chemical analysis is compatible with the diffraction data: two phases have been identified, an amorphous ferromagnetic phase homogeneous up to 300 Å containing less than 1% carbon in solution and an unstable phase coming from a part of the CO from the decomposition of carbonyl and representing 7.2% by weight. The pair distances from both X-ray and neutron diffraction spectra are identical after taking into account measurement error: the shorter pair distances are those already found in icosahedral structures, the higher distances, identified up to 19 Å^?1, are simple exact combinations of the shorter ones.     

Structure of amorphous LaNi5D3.3 studied by neutron and X-ray diffraction

In situ neutron and X-ray diffraction measurements in a D₂ gas atmosphere at a constant pressure of 1 MPa were performed on amorphous LaNi₅D_3.3, which was prepared by mechanical alloying in a D₂ gas atmosphere. Reverse Monte Carlo (RMC) simulation based on the neutron and X-ray diffraction data was applied to construct a three-dimensional atomic arrangement of this amorphous alloy. The RMC model shows that more than 90% of the deuterium atoms occupy tetrahedral sites consisting of La and/or Ni atoms. Furthermore, the local environments around the Ni and La atoms were investigated by Voronoi polyhedral analysis of the RMC configuration of the metal atoms. The results show the presence of a number of prismatic-like polyhedra around a Ni atom.     

The structural characteristics of amorphous D2O ice by neutron diffraction

Neutron diffraction measurements have been made at several wavelengths for vapor-deposited D₂O ice at 10 K. The observed structure factor exhibits more oscillatory features than corresponding measurements on liquid D₂O water, indicating an ammorphous phase which has strong intermolecular spatial correlations. A detailed examination of the data shows that this is strongly influenced by hydrogen-bonding effects and that the local environment for each molecule is very similar to that in crystalline ice. The predictions of Boutron and Alben, based on a continuous random network model, are found to be in excellent agreement with the data.     

Structural observation of amorphous (Ti0.676Zr0.324)D0.31 by neutron and X-ray diffraction

Neutron and X-ray diffraction were used to elucidate the structure of amorphous (Ti_0.676Zr_0.324)D_0.31 prepared by mechanical milling under a deuterium gas atmosphere. Moreover, reverse Monte Carlo modeling was employed to obtain further insight into the location of the deuterium atoms. The results informed us that deuterium atoms are located in the tetrahedral sites formed by Ti and Zr. Additionally, it was found that about 93% of the deuterium atoms locate in the tetrahedral sites and about 40% occupy the holes of tetrahedral units consisting of 3Ti + 1Zr.     

Dark field microscopy for diffraction analysis of amorphous carbon solids

Diffraction methods for determining structure in non-crystalline materials often rely solely on the determination of pair correlation functions, extracted from measurements of the diffracted intensity. A dark field image of a non-crystalline solid taken with a conventional transmission electron microscope contains phase information lost in the measurement of the diffracted intensity which can be accessed by evaluating a variance function. This variance function is defined in terms of spherical averages of the diffracted intensity and the mean square of the diffracted intensity. The latter contains higher order correlation information derived from correlations between two pairs of atoms. We examine the sensitivity of the variance function, to subtle atomic structural differences between carbon network structures. The structures have similar pair correlations, but different levels of diamond like bonding. The variance function is shown to give improved discrimination between the networks.     

Structure of chalcogenide glasses by neutron diffraction

The purpose of this work is to study the change in the structure of the Ge–Se network upon doping with Ag. We report here a neutron diffraction study on two glasses of the system Ag_x(Ge_0.25Se_0.75)_100−x with different silver contents (x = 15 and 25 at.%) and for two different temperatures (10 and 300 K). The total structure factor S(Q) for the two samples has been measured by neutron diffraction using the two-axis diffractometer dedicated to structural studies of amorphous materials, D4, at the Institut Laue Langevin. We have derived the corresponding radial distribution functions for each sample and each temperature, which gives us an insight about the composition and temperature dependence of the correlation distances and coordination numbers in the short-range. Our results are compatible with the presence of both GeSe_4/2 tetrahedra and Se–Se bonds. The Ag atoms are linked to Se in a triangular environment. Numerical simulations allowing the identification of the main peaks in the total pair correlation functions have complemented the neutron diffraction measurements.     

Preparation and characterization of amorphous cadmium–selenium ribbons

Chalcogenide glasses based on the cadmium–selenium system, with the selenium composition varying from 0 to 7.5 wt% have been prepared using melt-quenching method i.e., single-roller quenching technique. The X-ray diffraction (XRD) and selected area electron diffraction (SAD) patterns of the CdSe ribbons indicate that the ribbons are amorphous. The transmission electron microscopy (TEM) studies carried out on these ribbons reveal that the constituents are inhomogeneously distributed in these ribbons. The temperature dependence of the electrical resistivity, ρ and thermoelectric power (TEP) of these ribbons has been studied in the temperature range 30–350 °C. The sudden jump in the values of electrical resistivity at a specific temperature for each case in these ribbons has been correlated with the phase transition i.e., the onset of crystallization in these materials during heating. The crystallization temperature, T_c has been found to be a function of Se content of these ribbons. The phase change in these ribbons as a result of heating does not seem to affect the variation of TEP with temperature. However, the slope of TEP versus temperature curves depends on Se content in these ribbons. The differential scanning calorimetry (DSC) of these ribbons indicates that the supercooled region in these ribbons extends from 50 to 70 °C. The composition CdSe ribbon with 0.5 wt% Se has the highest value of T_c and glass forming ability, K_g = 0.7.     

Preparation and characterization of amorphous silica nanowires from natural chrysotile

By chemical dispersing and acid leaching, silica nanowires have been prepared from the natural mineral, chrysotile. X-ray fluorescence analysis (XRF), thermogravimetric analysis and differential thermogravimetric analysis (TGA–DTA), powder X-ray diffraction (XRD), fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM) were used to characterize the silica nanowires. The results indicate that the chemical composition of the silica nanowires is SiO_1.8 · 0.6H₂O, and although the silica is amorphous, its structure is regular to some extent. The structural unit of the silica nanowires is the [SiO₄] tetrahedron and six-member silicon–oxygen ring with the tetrahedral positioned alternately up and down in the six-member ring. The silica nanowires are well-dispersed and have cylindrical morphology and smooth surface, with lengths over 10 μm and diameters of 30–60 nm.     

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).     

Structure of rare-earth phosphate glasses by X-ray and neutron diffraction

Previous diffraction studies of the structures of rare-earth phosphate glasses (R₂O₃)_x(P₂O₅)_1−x are extended to glasses with smaller R³⁺ ions with R = Sm, Gd, Dy, Er, Yb, Y for x = ∼0.25 and with R = Nd, Sm, Gd for x = ∼0.15. Parameters for the P–O, R–O and O–O first-neighbor peaks were obtained by Gaussian fitting. P–P and R–P distances were estimated from the positions of peak maxima. Effects of residual silica or alumina contents present as a result of glass processing were taken into account for selected samples. The P–O coordination number, N_PO, and the P–O, O–O, P–P distances are consistent with the presence of phosphate tetrahedra and are insensitive to the R species and the R₂O₃ content. Rare-earth coordination numbers, N_RO, decrease from ∼8 to ∼6.5 when x is increased from ∼0.15 to ∼0.25. N_OO and N_PP decrease with increasing R₂O₃ content indicating the network disintegration. The numbers N_RO of the metaphosphate glasses (x = ∼0.25) decreases from ∼7 to ∼6 when R is changed from La to Yb. This change is also indicated by the behavior of the R–O distances and by constant number densities of atoms. The decrease in N_RO with increasing R₂O₃ content is due to the reduction in the number of terminal O (O_T) available for coordination of the R³⁺ ions (six at metaphosphate composition). Especially for smaller R³⁺ ions sharing O_T between two R sites is not favored. The decrease by ∼0.04 nm of the prominent R–R first-neighbor distance with a change of R from La to Yb at the metaphosphate composition is indicated by a shift to higher magnitude of scattering vector of the shoulder occurring in front of the first main diffraction peak.     

Structure of titanophosphate glasses studied by X-ray and neutron diffraction

The structure of binary (TiO₂)_x(P₂O₅)_1−x glasses with x = 0.60, 0.65 and a ternary K₂O–TiO₂–P₂O₅ (KTP) glass were studied by X-ray and neutron diffraction. The experiments were performed at the high-energy beamline BW5 of the synchrotron DORIS (Hamburg/Germany) and at the GEM instrument of the neutron source ISIS (Chilton/UK). Gaussian fitting of well-resolved first-neighbor peaks in the correlation functions of the binary glasses with TiO₂ contents of 0.65 and 0.60 result in Ti–O coordination numbers of 5.65 ± 0.2 and 5.9 ± 0.2, respectively. Distorted TiO₆ octahedra and isolated PO₄ units form the glassy networks, with a small number of lower coordinated Ti sites for the 0.65 TiO₂ glass. For comparison, only TiO₆ octahedra are found for a ternary K₂O–TiO₂–P₂O₅ glass. The Ti–O coordination numbers are compared with a structural model where all oxygen atoms occupy sites in Ti–O–Ti, Ti–O–P or P–O–P bridges. The presence of three-coordinated oxygens must be assumed for the binary glasses, whereas a structure with nearly all oxygen atoms forming network bridges exists for the ternary KTP glass.     

Structural studies of amorphous solids by small-angle neutron scattering

Sophisticated new methods of preparation developed over the last decade have considerably extended the range and nature of amorphous materials, many of which have a microstructure on a scale of 10–1000 Å. Whilst in some cases this is due to the composition, in others it is a direct result of the preparation technique. This paper reviews the present state of small-angle scattering as a tool to study the microstructure in the four main classes of amorphous materials: bulk glass, metal ribbons, thin films and inorganic gels. The techniques specific to neutron scattering, which have been developed to separate the various components of the scattering curves, are reviewed.     

Investigation of the lithium-nitrogen melt microstructure by neutron diffraction

The microstructure of Li-N melts with nitrogen impurity contents of 1.3 and 3.5 at % has been investigated by neutron diffraction. The main microstructural characteristic of the material (total structure factor) and the partial structure factors of the melt components and the radial distribution functions of particles have been obtained. It is established that there is no prepeak in the structure factor of Li-N melts, which indicates the existence of clusters of a certain size in the melt. Analysis of the partial structural characteristics suggests the existence of nitrogen impurity in Li-N melts in the form of lithium nitride Li₃N.     

Preparation of amorphous carbon nanotubes using attapulgite as template and furfuryl alcohol as carbon source

Amorphous carbon nanotubes were synthesized by vapor deposition polymerization (VDP) method using attapulgite as template and furfuryl alcohol as carbon source. The morphology and microstructure analysis of the as-prepared samples showed that highly pure amorphous carbon nanotubes were obtained, and determined by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SEAD) and energy dispersive X-ray (EDX) spectrum. The Brunauer–Emmett–Teller (BET) surface area analysis indicated that the specific surface area of the as-prepared amorphous carbon nanotubes reaches up to 503.1 m²/g. A hypothesis about the formation mechanism of the amorphous carbon nanotubes was also proposed accordingly.     

Preparation and characterization of carbon aerogel microspheres by an inverse emulsion polymerization

Carbon aerogel (CA) microspheres have been successfully synthesized by an inverse emulsion polymerization and characterized by scanning electron microscopy (SEM), N₂ sorption isotherm and X-ray diffraction (XRD). The results show that the size and pore characteristics of carbon microsphere obviously depend on stirring speed and concentration of surfactant in the emulsion polymerization process. The resultant CA microspheres are amorphous carbon structure with the size ranging from about 2 to 50 μm by changing the stirring speed. CA microspheres with S_BET of 414-603 m² g^− 1 and V_meso of 0.028-0.432 cm³ g^− 1 are synthesized using different SPAN80 concentrations. The results of cyclic voltammetry indicate that the CA microspheres prepared at a stirring speed of 480 rpm and at V_s/V_h = 0.01 have ideal supercapacitive behavior in 6 M KOH electrolyte, the maximum specific capacitance of the electrode reaches 180 F g^− 1.