Doping-induced formation of bulk nanocrystalline alloy from metallic glass with controllable microstructure and properties

We report the formation of bulk nanocrystalline alloys from a Pr-based bulk metallic glass-forming alloy by doping iron. The microstructure of the alloys can be tuned progressively from full glassy state to composite with nanocrystalline particles in the glassy matrix, and finally into nanostructured state accompanying with the gradual magnetic and mechanical changes. The role of the addition in the control of microstructure and magnetic property, the mechanism for the nanocrystalline formation induced by addition, and the relation between the microstructure and properties are discussed.     

Optical properties of Ag nanocrystals in Sc and O sequentially implanted silica

The implantation of Sc and O results in the modification of the silica with polarizable Sc³⁺ ions. During annealing the Sc ions are incorporated with the O in the network to form a Sc-O-silicate layer. Subsequent implantation of Ag into this layer results in the formation of Ag metal nanocrystals with significantly modified optical properties compared to samples without the Sc ions. The size distribution of the Ag nanocrystals narrowed with increasing Sc concentration, due to the gradual elimination of a band of large Ag clusters. The incorporation of the Sc results in a shift in the wavelength of the surface plasmon resonance of the Ag nanocrystals and a change in the magnitude of the surface plasmon resonance absorption. The results are interpreted using effective medium theory.     

The effect of Ti and O on the optical properties and microstructure of Ag nanocrystals formed in silica by sequential ion implantation

The implantation of Ti and O results in the modification of the silica with polarizable Ti ions. After annealing the Ti ions are incorporated with the O in the network to form a Ti–O–silicate layer. Subsequent implantation of Ag into this layer results in the formation of Ag metal nanocrystals with significantly modified optical properties compared to samples without the Ti ions. The incorporation of the Ti results in a shift in the wavelength of the surface plasmon resonance of the Ag nanocrystals and a change in the magnitude of the surface plasmon resonance absorption. The results are interpreted using effective medium theory.     

Effect of heating and cooling atmospheres on colors of glaze and glass containing copper

ESR and ESCA analyses of a copper red glaze prepared by firing under a strongly reducing atmosphere followed by oxidation during a cooling period showed that Cu¹⁺ and Cu₂O were major species in it. From the investigation of behavior and chemical states of copper and tin under various firing conditions, mechanisms of the formation of Cu₂O and its protection were assumed as follows: Cu²⁺ and Sn⁴⁺ are reduced to metals during reducing firing and then the metals aggregate in the glaze surface layer, forming alloy. In the next oxidation process, metallic copper and tin are oxidized to Cu₂O or Cu¹⁺ and SnO respectively. Due to the affinity of SnO on Cu₂O for glass, glass containing Sn²⁺ surrounds and consequently protects Cu₂O from excessive oxidation.

A colorless copper glass before striking contained copper mainly as Cu¹⁺. ESCA analysis showed that striking of the glass caused the selective formation of Cu₂O.     

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.     

Metallic phase formation in oxide films

Metallic particles embedded in the oxide film play an important role in film’s optical property. In this paper it is demonstrated that metallic phases of Ag, Ti, and Pb, can be formed in different oxide films under heating, X-ray photon, and electron radiation. The metallic phase separated from metal oxide film was investigated by X-ray photoelectron spectroscopy technique. Metal oxygen bond breaking and total energy reduction in the film result in the formation of metal in the film. It is necessary to fully understand the formation mechanism of metallic particles so their shapes and distributions can be tailored to achieve the desired film’s properties.     

Investigation of the crystallization process in oxyfluoride glass ceramics codoped with Er/Yb

The oxyfluoride glass ceramics are important up-conversion luminescent materials. Er³⁺/Yb³⁺-codoped transparent oxyfluoride glasses were prepared by melt-quenching and subsequently heat-treated at different times and temperatures, and the crystallization process of fluoride nanocrystals from the glass was investigated. X-ray diffraction (XRD) and fluorescence spectra investigations reveal that fluoride nanocrystals are distributed homogeneously among the glassy matrix for the sample doped with Er³⁺/Yb³⁺. The crystallization process indicates that heat-treatment temperature influences the size of fluoride nanocrystals, while heat-treatment time influences their concentration. Moreover, the red emission intensities increase due to the incorporation of Er³⁺/Yb³⁺ into the fluoride nanocrystals under different heat-treatment methods, which are studied by fluorescence spectra.     

The effect of annealing on the mechanical properties of a ZrAlNiCu metallic glass

In this paper, the effects of annealing and nanocrystallization on the mechanical properties of a Zr₅₅Al₁₀Ni₅Cu₃₀ metallic glass have been studied. It has been shown that the high volume fractioned nanocrystals facilitate the formation of shear bands and thus decrease the yield stress. At the same time, the nanocrystals also facilitate the formation of interfacial voids during compression, resulting in substantial decrease in the plasticity of the metallic glass.     

Germania nanocrystals in Modified Chemical Vapour Deposition

The Modified Chemical Vapour Deposition process for fabrication of silica-based optical fibres is used to generate nanoscale soot particles which are deposited on a substrate by thermophoresis and then sintered and collapsed into a preform from which optical fibre can be drawn. To increase the refractive index of the fibre core silica and germania soots are often generated together and co-deposited. The silica soot is invariably amorphous in character but for certain configurations of the preform lathe it has been found that germania soot particles may be crystalline. A systematic study has identified parameters controlling germania crystallinity in soot nanoparticles and transition from crystalline germania nanoparticles to glassy germania has been observed. The implications of possible retention of germania nanocrystals in preform and fibre are discussed with regard to fibre quality and optical performance.     

Glasses and glass-ceramics based on GeSe2–Sb2Se3 and halides for far infrared transmission

New glass compositions have been studied by introducing metallic halides into the well known GeSe₂–Sb₂Se₃ system. Glass forming region and thermo-mechanical properties have been investigated for each added constituent. Nanocrystals with controllable size were reproducibly and homogeneously generated in different glassy matrix with different annealing times and temperatures. We have demonstrated that a controlled crystal growth and a molding process can be combined together. The shaped glass-ceramics are still transparent and show improved mechanical properties.     

Self-formation of dielectric layer containing CoSi2 nanocrystals by plasma-enhanced atomic layer deposition

Dielectric layer containing CoSi₂ nanocrystals was directly fabricated by plasma-enhanced atomic layer deposition using CoCp₂ and NH₃ plasma mixed with SiH₄ without annealing process. Synchrotron radiation X-ray diffraction and X-ray photoelectron spectroscopy results confirmed the formation of CoSi₂ nanocrystal. The gate stack composed of dielectric layer containing CoSi₂ nanocrystals with ALD HfO₂ capping layer together with Ru metal gate was analyzed by capacitance–voltage (C–V) measurement. Large hysteresis of C–V curves indicated charge trap effects of CoSi₂ nanocrystals. The current process provides simple route for the fabrication of nanocrystal memory compatible with the current Si device unit processes.     

Structural study of highly porous nanocomposite aerogels

The structural properties of CoFe₂O₄–SiO₂ highly porous nanocomposite aerogels have been investigated by X-ray Absorption Spectroscopy and Transmission Electron Microscopy techniques. The aerogels are obtained by supercritical drying of composite gels obtained using a two step procedure where fast gelation is achieved using urea in the second step. The formation of CoFe₂O₄ nanocrystals in the silica matrix begins after calcination at 750 °C of the parent aerogel and is complete after calcination at 900 °C, while the high porosity of the sample is mostly retained.     

Inline deposited thin-film silicon solar cells on imprinted foil using linear PECVD sources

The standard way to improve the light management of thin film solar cells is to introduce a light scattering structure, either on the front window or at the back reflector. Usually, growth conditions of TCO layers are adjusted to get random surface roughness on the front window. In this paper we present an alternative method, which can be applied both on the front window and at the back reflector. It involves imprinting a UV curable coating layer allowing full control on the texture (random or periodic) to fully optimise the light trapping. Light trapping is even more important for microcrystalline Si solar cells. We have fabricated thin film nip Si solar cells with sputtered Ag/ZnO back contacts on embossed barrier layers on steel foil. We show that the UV curable coating is well-suited as imprintable barrier layer between the steel foil and the active layers. For nip a-Si cells we can obtain light trapping, as measured by the short-circuit current, that is almost as good as that of nip a-Si cells made on Asahi U-type glass, covered with a Ag/ZnO back reflector. Furthermore, we show that dynamically processed a-Si nip cells on foil realised efficiencies of over 7%, which are only slightly less than for cells made in a UHV lab-scale cluster tool in static processing. Finally, a-Si/a-Si tandems and μc-Si/a-Si tandems have been fabricated. Initial efficiencies of around 8% on textured barrier layer on steel foil have been achieved.     

Green synthesis of metal sulfide nanocrystals through a general composite-surfactants-aided-solvothermal process

In this paper, we developed a generalized and greener composite-surfactants-assisted-solvothermal process (CSSP) to produce colloidal nanoparticles of metal sulfides. X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectra (XPS) revealed that single-molecular-layer type of MoS₂ nanoparticles with diameter 6–10 nm were successfully synthesized. The molecular structure model of the capped MoS₂ nanoparticles was suggested through further examination by infrared spectra. Hexagonal CdS nanocrystals with spherical, triangle, and hollow sphere shapes were controllably synthesized by varying the experimental conditions. A possible in-situ reduction–sulfidation mechanism was proposed for the formation of Ag₂S nanocrystals, where the metal ions were reduced to metallic nanoparticles before the generation of sulfides. The obtained nanocrystals through this CSSP approach could provide the building blocks for the bottom-up approach to nanoscale fabrication in nanoscience and nanotechnology.     

陶瓷干法造粒过程坯料颗粒成形与雾化液含量的影响

为研究陶瓷干法造粒制粉过程坯料颗粒成形与雾化液含量的关系,基于欧拉-欧拉双流体模型模拟干法造粒制粉过程坯料颗粒与雾化液混合过程,同时对坯料颗粒流动性、颗粒级配及粗糙度进行实验分析,验证数值模拟结果正确性.仿真结果表明:当雾化液含量分别为100 mL、200 mL、300 mL时,坯料颗粒在造粒室内的分散性无明显差异,团聚现象不明显;当雾化液含量分别为400 mL、500 mL时,坯料颗粒在造粒室内的分散性有明显变化,团聚现象显著.实验结果表明:当雾化液含量分别为100 mL、200 mL、300 mL、400 mL、500 mL时,坯料颗粒的流动性指数依次为63.5;、83.0;、90.0;、77.0;、61.0;,有效坯料颗粒百分比依次为72;、83;、90;、82;、65;,粗糙度系数平均值依次为1.38、1.43、1.26、1.49、1.57.综合分析说明:数值仿真与实验结果基本相吻合,造粒过程中雾化液含量为300 mL时,干法造粒制粉过程造粒室内坯料颗粒的分散性较好,且基本无团聚现象;坯料颗粒的流动性最佳、颗粒级配最均匀、粗糙度整体最优,即造粒效果最好.     

Investigation of the structure and mechanisms of thermal motion in nanostructured undecylenic acid

Abstract

We have compared the structure, phase transitions and the thermal motion mechanisms of the undecylenic acid in bulk and inside a porous matrix using powder X-ray diffraction, calorimetry and IR-spectroscopy methods. The matrix used was a porous silicon with cylindrical pores (D?=?20?nm). The interaction between the walls of the porous silicon and the nanocrystals of the undecylenic acid results in a crystalline structure, which is significantly different from the structure of bulk undecylenic acid. A phase transition in the wall-adjacent layer of the undecylenic acid nanocrystals was shown to take place. The solid-state phase transition temperatures, as well as the melting point, were shown to be lower for nanocrystals. Topological soliton motion mechanism was suggested to explain the thermal motion of the undecylenic acid molecules in the rotator phase.     

钨基陶瓷结晶釉的快速结晶制备及其光催化性能探索

本文通过对钨基陶瓷结晶釉材料进行了快速结晶制备,所得釉层晶相为WOP2O7结构.通过扫描电镜分析发现其表面具有显著地结晶化特征形貌,进一步结合EDS能谱分析发现其表面形貌有钨基结晶釉相和底釉相两种结构构成.在光催化性能探索中发现该釉层材料在紫外可见光照射下展现出一定的催化降解罗丹明B溶液的能力,为陶瓷结晶釉材料的功能化价值提升提供了参考.     

On the photodissolution kinetics of silver in glassy As2S3

The kinetics of the photodissolution of Ag into glassy As₂S₃ films and its dependence on temperature have been studied by monitoring the changes that occur both in their transmission spectra and transmission of weakly absorbed broadband light. It was shown that besides of a low induction period, the photodissolution kinetics consists of two linear steps with different activation energies, followed by a parabolic tail. The transitions between photodissolution steps was found to be not monotonous and explained in terms of Elliott’s model, which asserts a simultaneous ionic and electronic charge transport controlled by chalcogenide properties, illumination and temperature. The evidence is given that the islanding of Ag layer in the course of photoreaction, results in an inversion of maxima and minima of transmission spectra. It is suggested that the islanding of Ag layer is not a consequence of a non-uniform dissolution but arises itself at critical thickness, at which Ag forms a continuous film.     

Composition and morphological characteristics of sialoliths

Sialolithiasis refers to pathological minerilazation in the salivary glands and ducts. Aiming to a better understanding of the formation phenomena, structural and morphological analysis of a relatively large ensemble of sialoliths extracted from 22 patients via sielendoscopy was performed. Characterization methods, including Fourier Transform Infrared (FTIR) Spectroscopy, X‐Ray Diffraction, Raman spectroscopy and Scanning Electron Microscopy (SEM), showed that the large majority of 90% of sialoliths were composed of carbonate apatite as the inorganic phase, while SEM imaging revealed the presence of bacteria in 13 cases. Furthermore, carbonate apatite crystals in the form of parallel or randomly oriented sheets were observed and in some cases rhombohedral calcite‐type nanocrystals were detected. The present findings may contribute to a better understanding of the formation mechanisms in vivo and and contribute to the treatment of sialolithiasis.     

Crystallization and spectroscopic properties of Eu-doped CaF2 nanocrystals in transparent oxyfluoride glass-ceramics

Transparent oxyfluoride glass-ceramic in the system SiO₂–Al₂O₃–CaF₂–EuF₂ containing Eu-doped CaF₂ nanocrystals were produced by using the controlled crystallization of melt-quenched glass. X-ray diffraction and transmission electron microscopy data have revealed the formation of the CaF₂ nanocrystals of about 65 nm size. Photoluminescence spectra have shown an increase of the splitting of the luminescences associated to the Eu³⁺ ion along with annealing time which is consistent with the Eu³⁺ environment evolving from a glassy to a crystalline state.