Synthesis and structural characterization of amorphous nano-sized SiBONC ceramic powders via polymer pyrolysis

SiBONC ceramic powders have been prepared via a polymer pyrolysis route using silicon tetrachloride (SiCl₄), benzaldehyde (PhCHO), boron trichloride (BCl₃) and aniline (PhNH₂) as starting materials. Fourier transform infrared spectra (FT-IR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and transmission electron microscopy (TEM) were performed to investigate the structural characteristics of the polymer precursor and the ceramic powders. The SiBONC ceramic powders in spherical shape with a mean diameter of 50 nm are amorphous and composed of B-N, Si-O, Si-C, and SiON_x groups. The SiBONC ceramic powders were sintered at 1700 °C to a dense material which still remained amorphous.     

Structural characterization of silicon nanocrystals from amorphous silicon oxide materials

Silicon nanocrystals have been produced by disproportionation reaction of bulk silicon monoxide at temperatures higher than 1073 K. More specific, samples annealed at 1123, 1173, 1223 and 1323 K as well as the starting material SiO have been examined. X-ray diffraction, high-resolution transmission electron microscopy and infrared spectroscopy have been employed in order to investigate the structure of the produced silicon nanocrystals. Photoluminescence measurements reveal a three band emission with maxima positioned at 1.33, 1.52 and 1.67 eV. The intensity of the photoluminescence emission increases with the annealing temperature exponentially. This fact can be directly correlated with the disproportionation reaction which results in bigger amounts of silicon nanocrystals by increasing the annealing temperature and is discussed here. Also a possible explanation is given for the origin of each emission band.     

Structural characterization of amorphous silicon nitride by molecular dynamics simulation

Computer simulation, using the molecular dynamics (MD) technique, has been carried out on amorphous silicon nitride (a-Si₃N₄) with simple Busing-type potentials. From the MD simulation, the following points have been deduced. (1) The average Si---N bond length obtained from MD results is r_Si---N=1.74 Å, and its coordination number, N_Si---N, is 3.95. The bond angles around a Si and a N atom, N---Si---N and Si---N---Si, are found to be 109.8° ± 12.36° and 127.08° ± 16.63°, respectively. The N---Si---N value obtained is in very good agreement with the tetrahedral bond angle (= 109.47°). Hence, the short-range structural arrangement of a-Si₃N₄ comprises tetrahedral SiN₄ units. The MD results presented in this study also indicate that there exist only a small number of defects such as dangling bonds. (2) These MD results are in good agreement with the reported X-ray and neutron data. The a-Si₃N₄ structure can be reproduced by the MD simulation given in this study.     

Structural relaxation and crystallization of amorphous Ge films

The irreversible changes in conductivity occurring in evaporated amorphous Ge films just after deposition and during annealing are investigated in detail. Their analysis leads to a model for the structural relaxation of real amorphous networks. Electron diffraction and electron microscope experiments provide additional information on annealing effects and crystallization processes.     

Synthesis and characterization of bulk amorphous steels

Bulk amorphous steels (BASs) are a novel class of advanced materials having very attractive physical, thermal and mechanical properties and have applications as structural materials. Two BASs Fe₅₀Cr₁₄Mo₁₄C₁₄B₆M₂ (M = Y and Dy) were designed following the Greer’s confusion principle and cylinders of thickness 3-5 mm were synthesized by Cu mold casting technique. Characterization was carried out by techniques of X-ray diffraction (XRD), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) with attachment of energy dispersive spectroscopy (EDS). The alloys show high glass-forming ability (GFA) as well as high thermal stability. Hardness and elastic moduli of the present steels were found to be about 3-4 times higher as compared to the conventional steels. Steel containing Dy has superior mechanical and thermal properties as compared to the steel containing Y.     

Structural and luminescence properties of amorphous SiO2 nanoparticles

We report an experimental study on the photoluminescence band peaked at 2.7 eV (blue band) induced by thermal treatments in nanometric amorphous SiO₂. In particular the emission dependence on the nanometric particles size as a function of their mean diameter from 7 nm up to 40 nm is investigated. We found that the emission amplitude increases on decreasing the particle diameter, showing a strong correlation between the blue band and the nanometric nature of the particles. By Raman spectroscopy measurements it is evidenced that the SiO₂ nanoparticles matrix is significantly affected by the reduction of size. Basing on the shell-like model, these findings are interpreted assuming that the defects responsible for the photoluminescence are localized on a surface shell of the particles and not simply on their surface. In addition it is found that the generation efficiency of these defects depends on the structural properties of the SiO₂ matrix in the surface shell.     

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.     

Structural behavior of amorphous and liquid metallic alloys at elevated temperatures

The thermal behavior of the short-range order of Pd₄₀Cu₃₀Ni₁₀P₂₀ bulk metallic glasses has been investigated in situ by means of high-temperature X-ray synchrotron diffraction. The dependence of the X-ray structure factor S(q) of the glassy state on temperature follows the Debye theory up to the glass transition. Above the glass transition temperature T_g, the temperature dependence of S(q) is altered toward a continuous development of structural changes in the liquid state with temperature. The behavior of the structure factor during heating and cooling through the glass transition gives experimental evidence for melting the glass, and for freezing the liquid, respectively at the caloric glass temperature.     

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.     

Preparation of amorphous carbon tetrachloride and characterization by neutron diffraction

A 5 g sample of carbon tetrachloride (CCl₄) deposited from the vapour on to a cadmium substrate at 5 K is shown to be amorphous by the absence of Bragg peaks in its neutron diffraction spectrum. Simple analysis shows that the range of correlations in amorphous CCl₄ extends only to next-nearest neighbours.     

Synthesis and characterization of a multicomponent Fe-based bulk amorphous alloy

A new bulk metallic glass (BMG) Fe₆₀B₁₅Zr₁₀Co₇Mo_5.5Y₂Si_0.5 was synthesized by Cu mold casting. The alloy was characterized by X-ray diffraction (XRD), differential scanning calorimetry (DSC), scanning electron microscopy (SEM) and energy dispersive spectrometry (EDS) techniques. The thermal stability and glass-forming ability (GFA) of the alloy have been discussed by evaluating a number of thermal parameters. The maximum values of the key thermal parameters like T_rg (T_g/T_m, T_g/T_l), γ, δ and β parameters were found to be ～(0.66, 0.64), 0.407, 1.84 and 3.83, respectively. The alloy showed double stage crystallization process. The activation energies for crystallization were found to be 606.6 and 623.1 kJ/mol by Kissinger and Ozawa equations, which indicate the high thermal stability. Crystallization behavior of the alloy was explored by XRD. Mechanical properties like Vicker’s hardness, nanohardness and elastic modulus are found to be very promising.     

Optical properties and chemical bonding characteristics of amorphous SiNX:H thin films grown by the plasma enhanced chemical vapor deposition method

Amorphous silicon nitride (SiN_X:H) thin films grown by the plasma enhanced chemical vapor deposition (PECVD) method are presently the most important antireflection coatings for crystalline silicon solar cells. In this work, we investigated the optical properties and chemical bonding characteristics of the amorphous SiN_X:H thin films deposited by PECVD. Silane (SiH₄) and ammonia (NH₃) were used as the reactive precursors. The dependence of the growth rate and refractive index of the SiN_X:H thin films on the SiH₄/NH₃ gas flow ratio was studied. The chemical bonding characteristics and the surface morphologies of the SiN_X:H thin films were studied using the Fourier transform infrared spectroscopy and atomic force microscopy, respectively. We also investigated the effect of rapid thermal processing on the optical properties and surface morphologies of the SiN_X:H thin films. It was found that the rapid thermal processing resulted in a decrease in the thickness, increase in the refractive index, and coarser surfaces for the SiN_X:H thin films.     

Structural difference of surface and sub-surface native oxides of evaporated amorphous silicon

Evaporated amorphous silicon (a-Si) films, oxidized in air or O₂ at room temperature, present two native oxides with different structures. The surface oxide is constructed from SiO₄-tetrahedron structural units with a 110° O---Si---O angle, which is the common structural unit of stable silicon oxides. The internal oxide has a different structure having a 120° O---Si---O angle. The results of molecular orbital (MO) calculations for (SiO₃)^m− and (SiO₄)ⁿ⁻ anionic clusters support the presence of the two stable structures of silicon oxides and also reveal the importance of the ionic character of the oxidized sites.     

Structural studies of amorphous CoP and NiP by EXAFS

The EXAFS spectra of amorphous CoP and NiP alloys have been recorded and analyzed on both edges of the metal and metalloid. The spectra cannot be directly fitted by the classical neutrons or X-rays results: these appear to be the average values of asymmetric radial distribution functions that we have to use in EXAFS analysis. Then we show that the environment of the phosphorus atoms in the amorphous state is very reminiscent of that of the Co2P or Ni3P crystalline materials.     

Structural characterization of Elisabatin B and Elisabatin C

X-ray structures of Elisabatin B (1) and Elisabatin C (2) have been determined. Crystal data for 1: Triclinic, P (No. 2), a = 7.528(2) Å, b = 9.404(2) Å, c = 11.414(2) Å, = 75.363(3)°, = 86.668(4)°, = 89.683(4)°, and Z = 2. Crystal data for 2: Monoclinic, P2₁/c (No. 14), a = 8.242(2) Å, b = 14.870(2) Å, c = 13.060(2) Å, = 101.458(3)°, and Z = 4. Both compounds are highly unsaturated leading to extended aromatic conjugation. They show different intermolecular O–HO hydrogen bonds, via which 1 forms dimers, and 2 zig-zag polymeric chains.     

Structural relaxation and optical properties in amorphous Ge33As12Se55 films

Amorphous Ge₃₃As₁₂S₅₅ films prepared by ultra fast pulsed laser deposition (PLD) have been vacuum annealed over a range of different temperatures. Raman scattering measurements indicated that the features corresponding to Ge–Se and As–Se clusters increase in intensity with increasing annealing temperature (T_a) up to their respective glass transition temperature, and then decrease with further increasing T_a up to 300 °C. Optical property measurements showed that the refractive index deceases but the optical band gap increases with increasing T_a, and both of them could be fitted by the exponential function. The corresponding characteristic time extracted was found not to obey Arrhenius behavior, which is consistent with the existence of a broken network cut by cross-linking bonds and different clusters in films.     

Structural and vibrational characterization of medieval like glass samples

Within the framework of a project aimed to develop protective coatings for antique glass windows, three glass varieties of medieval-like composition were prepared using recipes deduced from archaeometric studies and different amounts of potassium for fluxing (15–20–25 K₂O wt.%). Batches were melted in mullite crucibles using an electric furnace at 1350 °C, the glass was fast cooled in air and annealed at temperatures 20 °C higher than the sample glass transition temperatures (726, 702 and 683 °C for V1, V2 and V3, respectively). The chemical composition of the glass was determined by X-Ray Fluorescence Spectroscopy (XRF) and the glass transition temperature was checked by differential thermal analysis (DTA). X-Ray Powder Diffraction (XRPD) data and vibrational spectroscopic experiments (FT-IR and Raman) revealed a direct dependence of glass de-polymerization on potassium content. In particular, the Raman data were interpreted on the basis of SiO₄ structural units Qⁿ and the polymerization index I_p.     

Structural characterization of heteroepitaxial films of CdSe and ZnTe

The effects of composition, orientation and temperature of substrate on the structure and morphology of epitaxial CdSe and ZnTe films are analyzed. Single crystal wafers of zinc telluride and zinc selenide oriented along (110) and natural cleaved mica were used as substrates. This paper presents a complex investigation of the growth mechanism and crystal perfection of the films by optical microscopy, X-ray and electron diffraction, and by electron microscopy. The structure of the transient region of the film substrate interface was studied by X-ray microanalyzer and by scanning electron microscope. Cadmium selenide layers grown on mica had hexagonal structure and were oriented in the (0001) plane, those grown on zinc telluride crystals had cubic structure and orientation along (110). Zinc telluride layers were cubic and were oriented parallel the (111) plane when deposited on mica, and parallel to (110) when deposited on zinc selenide substrates. It is shown that the layers grew by a layer mechanism. Epitaxial growth of cubic cadmium selenide layers on zinc telluride single crystals, as well as of ZnTe layers on ZnSe substrates, made it possible to grow heterojunctions with a low density of misfit dislocations at the interface; this gave rise to intensive injection electroluminescence and effective separation of non-equilibrium charge carriers in such structures.     

Preparation and characterization of amorphous,I and II forms of clopidogrel hydrogen sulfate

In this work the amorphous, I and II forms of clopidogrel hydrogen sulfate (CHS) were prepared and characterized by use of powder X‐ray diffraction (PXRD), Fourier transform infrared spectroscopy (FTIR) and differential scanning calorimetry (DSC). The labile precipitate and oiling out during reactive crystallization were also firstly reported. Based on the solubility and thermochemical data, the amorphous form and I form is found to be monotropically related, while the I form and II form are enantiotropically related. In addition, both transformations from anhydrous form to I form and from I form to II form are greatly temperature‐dependent, which gives us a window to prepare each pure form. These results will contribute a better understanding about the polymorphic nature and crystallization mechanism of clopidogrel hydrogen sulfate. (© 2012 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthesis, characterization, and crystal structures of two strained cyclic diacetylenes and their precursors

The synthesis, characterization, and crystal structures of two novel strained cyclic diacetylenes are reported. A discussion is presented about the relative bond distances of the diacetylenes compared to a previously reported strained cyclic diacetylene to further determine the degree of aromaticity of that compound. 1,2:5,6:9,10:13,14-Tetrabenzo-3,7,11,15,17-pentadehydro[18] annulene (5) is triclinic, P ^–1, with = 9.489(5), b = 10.550(5), c = 12.155(6) Å, = 100.50(4), = 106.50(4), = 100.85(4)°. 1,2:5,6:9,10:13,14:17,18-Pentabenzo-3,7,11,15,19,23,25-heptadehydro[26]annulene (7) is triclinic, P ^–1, with a = 9.611(2), b = 10.388(3), c = 15.963(3) Å, = 88.67(2), = 76.25(1), = 68.69(2). In addition, two precursors of 5, 3 and 4 which have a helical twist, are reported. [1,2-ethynediyl-bis(2,1-phenylene-2,1-ethynediyl-2,1-phenylene-2,1-ethynediyl]bis[trimethyl-silane] (3) is monoclinic, P2₁/c, with a = 13.682(4), b = 9.787(2), c = 13.448(4) Å, = 112.37(2)°. 1,1-(1,2-ethynyldiyl)bis[2-[(2-ethynylphenyl)ethynyl]-benzene (4) is monoclinic, P2₁/n, with a = 15.951(3), b = 3.999(1), c = 18.168(4) Å, = 99.05(3)°.