Young's modulus as a function of composition for an n-type lead–antimony–silver–telluride (LAST) thermoelectric material

For 17 cast lead–antimony–silver–telluride (LAST) thermoelectric specimens (representing 14 different chemical compositions), a combination of Vickers and Knoop microindentation techniques were used to determine the composition-dependent Young's modulus, E, which ranged from 24 to 68?GPa. Following microindentation, independent nanoindentation measurements were also performed on 10 of the 17 specimens. In the literature, for pseudobinary joins in ternary or quaternary compounds (with the compositions A _x B_{1– x} C or A _x B_{1– x} CD, respectively), changes in the Young's modulus have been expressed as quadratic functions of the compositional parameter x. In this study, we extend the quadratic functional form to a paraboloid in four composition variables to describe composition-dependent changes in E for the LAST compounds. Also, the composition-dependent changes in LAST are compared to the trends observed in the literature for E and bulk modulus for systems described by a single compositional variable.     

Temperature-dependent thermal expansion of cast and hot-pressed LAST (Pb–Sb–Ag–Te) thermoelectric materials

The thermal expansion for two compositions of cast and hot-pressed LAST (Pb–Sb–Ag–Te) n-type thermoelectric materials has been measured between room temperature and 673 K via thermomechanical analysis (TMA). In addition, using high-temperature X-ray diffraction (HT-XRD), the thermal expansion for both cast and hot-pressed LAST materials was determined from the temperature-dependent lattice parameters measured between room temperature and 623 K. The TMA and HT-XRD determined values of the coefficient of thermal expansion (CTE) for the LAST compositions ranged between 20 × 10^?6 K^?1 and 24 × 10^?6 K^?1, which is comparable to the CTE values for other thermoelectric materials including PbTe and Bi₂Te₃. The CTE of the LAST specimens with a higher Ag content (Ag_0.86Pb₁₉Sb_1.0Te₂₀) exhibited a higher CTE value than that of the LAST material with a lower Ag content (Ag_0.43Pb₁₈Sb_1.2Te₂₀). In addition, a peak in the temperature-dependent CTE was observed between room temperature and approximately 450 K for both the cast and hot-pressed LAST with the Ag_0.86Pb₁₉Sb_1.0Te₂₀ composition, whereas the CTE of the Ag_0.43Pb₁₈Sb_1.2Te₂₀ specimen increased monotonically with temperature.     

Characterization of bismuth–tin–lead and bismuth–tin–lead–cadmium fusible alloys

Microstructure, electrical, mechanical and thermal properties of quenched bismuth–tin eutectic, Rose (Bi₅₀Sn_22.9Pb_27.1) and Wood’s (Bi₅₀Sn_12.5Pb₂₅Cd_12.5) alloys have been investigated using scanning electron microscopy, X-ray diffraction analysis, the double bridge method, the dynamic resonance method, Vickers hardness measurement and thermal analysis. Wood’s alloy (Bi–Pb–Sn–Cd) has low electrical resistivity and melting point but a high elastic modulus and internal friction when compared with the Rose (Bi–Pb–Sn) alloy. The presence of cadmium in Wood’s alloy decreases its melting point and electrical resistivity with an increase in its elastic modulus, which improves the mechanical properties. Wood’s alloy (Bi–Pb–Sn–Cd) has better properties, which make it useful in various applications such as in protection shields for radiotherapy, locking of mechanical devices and welding at low temperature.     

Formation of sub-surface silver nanoparticles in silver-doped sodium–lead–germanate glass

The formation of silver nanoparticles in 60GeO₂–20PbO–20Na₂O bulk glass doped with 0.15 wt% of Ag has been studied by optical methods in the near ultraviolet-to-near infrared and mid-infrared ranges. A clear optical absorption band, which grows when increasing the annealing temperature, is observed around 460 nm, as a consequence of the surface plasmon resonance in the Ag nanoparticles. From the simultaneous analysis of optical transmittance and spectroscopic ellipsometry spectra in the near ultraviolet-to-near infrared range, it is demonstrated that the nanoparticles are surprisingly formed only in a thin layer (some tens of nm thick) underneath the sample surfaces. The potential of such a simultaneous optical analysis for determining the localization of the nanoparticles in glasses of any nature is underlined. Based on the results of a complementary mid-infrared spectroscopy characterization, the processes involved in silver migration to the surfaces and further aggregation to form nanoparticles are discussed.     

Characterization of semiconductor detectors of (1–30)-keV monoenergetic and backscattered electrons

Semiconductor detectors of backscattered electrons are basic elements of all modern scanning electron microscopes. Their quality is determined by the properties of planar p-n junctions and the parameters of the protective layer on the detector surface. The main characteristics of semiconductor detectors are considered, their response functions are calculated, and the threshold signal cutoff energies are found both for a monoenergetic electron beam and for detection of the total energy spectrum of backscattered electrons. The experimental results are in good agreement with the computational model data.     

Characterization of a large core photonic crystal fiber made of lead–bismuth–gallium oxide glass for broadband infrared transmission

We report on characterization of a large solid core, photonic crystal fiber dedicated to broadband transmission range from visible to mid-infrared. We have fabricated a multi-mode photonic crystal fiber, made of a heavy metal-oxide glass based on the $\hbox {PbO}{-}\hbox {Bi}_{2}\hbox {O}_{3}{-}\hbox {Ga}_{2}\hbox {O}_{3}$ system, modified with $\hbox {SiO}_{2}$ and CdO, synthesized in-house, which shows good transmission up to $4.5\,\upmu \hbox {m}$ , as well as good rheological properties that permit multiple thermal processing steps without crystallization. The core of the fiber is created by replacement of central 60 tubes with solid rods. The photonic cladding is composed of 8 rings of air holes with a filling factor of 0.42. Simulation results shows that the fiber can be used for broadband transmission in the range of 430–3,000 nm. Calculated effective mode area of the fiber is $295\,\upmu \hbox {m}^{2}$ . We have measured attenuation of the fiber in the range 800–1,700 nm and its sensitivity to bending losses. Attenuation ranges from 1 to 4 dB/m in the considered range and bending losses are below 0.7 dB.     

Novel fabrication and catalytic application of poly(ethylenimine)-stabilized gold–silver alloy nanoparticles

Novel synthesis of amine-stabilized Au–Ag alloy nanoparticles with controlled composition has been devised using poly(ethylenimine) (PEI) as a reducing and a stabilizing agent simultaneously. The composition of Au–Ag alloy nanoparticles was readily controlled by varying the initial relative amount of HAuCl₄ and AgNO₃. Due to the presence of abundant amine functional groups in PEI, which could act as the dissolving ligand for AgCl, the precipitation problem of Ag⁺ in the presence of Cl⁻ from the gold salt was avoided. On this basis, the relatively high concentrations of HAuCl₄ and AgNO₃ salts were used for the fabrication of Au–Ag alloy nanoparticles. The PEI thus plays triple roles in this study that include the co-reducing agents for HAuCl₄ and AgNO₃, the stabilizing agents for Au–Ag alloy nanoparticles, and even the dissolving agents for AgCl. As a novel material for use in catalysis, the Au–Ag alloy nanoparticles including pure Au and Ag samples were exploited as catalysts for the reduction of 4-nitrophenol in the presence of NaBH₄. As the Au content was increased in the Au–Ag alloy nanoparticles, the rate constant of the reduction was exponentially increased from pure Ag to pure Au.     

Preparation and Characterization of Gelatin–Poly(L-lactic) Acid/Poly(hydroxybutyrate-co-hydroxyvalerate) Composite Nanofibrous Scaffolds

Poly(L-lactic) acid (PLLA) scaffolds, prepared by electrospinning technology, have been suggested for use in tissue engineering. They remain a challenge for application in biological fields due to PLLA's slow degradation and hydrophobic nature. We describe PLLA, PLLA/poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV), and PLLA/PHBV/gelatin (Gt) composite nanofiberous scaffolds (Gt–PLLA/PHBV) electrospun by changing the electrospinning technology. The morphologies and hydrophilicity of these fibers were characterized by scanning electron microscopy (SEM) and water contact angle measurement. The results showed that the addition of PHBV and Gt resulted in a decrease in the diameters and their distribution and greatly improved the hydrophilicity. The in-vitro degradation test indicated that GT–PLLA/PHBV composite scaffolds exhibited a faster degradation rate than PLLA and PLLA/PHBV scaffolds. Dermal fibroblasts viabilities on nanofibrous scaffolds were characterized by [3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide] (MTT) assay and cell morphologies after 7 days culture. Results indicated that the GT–PLLA/PHBV composite nanofibers showed the highest bioactivity among the three scaffolds and increased with increasing time. The SEM images of cells/scaffolds composite materials showed the GT–PLLA/PHBV composite nanofibers enhanced the dermal fibroblasts's adhesion, proliferation, and spreading. It is suggested that the nanofibrous composite scaffolds of GT–PLLA/PHBV composites would be a promising candidate for tissue engineering scaffolds.     

Synthesis and Characterization of Terpolymers of poly(L-lactide-glycolide-ε-caprolactone)

Random terpolymers of poly(L-lactide-glycolide-ε-caprolactone) (PLLGC) was prepared by ring-opening polymerization of L-lactide, glycolide and ε-caprolactone monomers initiated with stannous octanoate. Fourier transform infrared spectra, nuclear magnetic resonance and gel permeation chromatography were employed to characterize the obtained PLLGC terpolymers. The effects of polymerization temperature, reaction time, the amount of initiator and the polymerization pressure on the weight average molecular mass and polydispersity index of the PLLGC were investigated. In addition, the water contact angle of the PLLGC was also tested. The characterization of chemical structure showed that the PLLGC was successfully synthesized. For instance, a PLLGC terpolymer with a weight average molecular mass of about 12.435?×?10⁴?Da and a polydispersity index of 1.28 was obtained when the polymerization was conducted with a molar ratio of monomer to initiator ([M]/[I]) of 2000, polymerization temperature of 140?°C, polymerization pressure of 5.0?Pa and reaction time of 24?h. The random incorporation of ε-CL monomer units decreased the wettability of the PLGA copolymers.     

Characterization of NiO–yttria stabilised zirconia (YSZ) hollow fibres for use as SOFC anodes

NiO–yttria stabilised zirconia (YSZ) hollow fibres with varying NiO content and a desired microstructure were prepared using a phase inversion technique and sintering. By controlling the fabrication parameters, microstructures with predominately finger-like pores near the inner and outer surfaces and a denser central layer with sponge-like pores were produced, for use as substrates for anode-supported hollow fibre solid oxide fuel cells (HF-SOFC). The NiO–YSZ fibres were reduced to Ni–YSZ at 250–700 °C in hydrogen flowing at 20 cm³ min^? 1 to produce Ni–YSZ hollow fibres, the mechanical and electrical properties of which were determined subsequently, reduction to Ni being verified by X-ray diffraction. The effects of NiO concentration and sintering temperature of the fibre precursors on the conductivity, strength and porosity of the reduced hollow fibres were investigated to assess their suitability for use as anode substrates. As expected, increasing Ni concentration increased electrical conductivities and decreased mechanical strength. Sintering temperature had a critical effect in producing axially conductive hollow fibres of sufficient mechanical strength for use as SOFC anodes. The hollow fibres retained their initial microstructure through the reduction process, though ca. 41% volume contraction is predicted on reduction of NiO to Ni, producing increased porosity in the reduced fibres. The mean porosity of the Ni–YSZ hollow fibres was ca. 60% and ca. 40% after sintered at 1250 °C and 1400 °C, respectively. The mean pore sizes for all the fibres after reduction varied between ca. 0.3 and 1 µm. The hollow fibres produced with 60% NiO, of length ca. 300 mm, electrical conductivities of ca. (1–2.25) × 10⁵ S m^? 1 and a porosity of ca. 43% are being used currently to construct and test the electrical behaviour of an anode-supported HF-SOFC.     

Synthesis and Characterization of Sol–Gel-Derived SiO2–CaO Particles: Size Impact on Glass (Bio)Properties

Four highly bioactive glasses in a binary SiO₂–CaO system are prepared following a sol−gel method using Ca(OH)₂ as a calcium precursor. In the synthesis of glass according to the modified Stöber method, Ca(OH)₂ suspended in polyethylene glycol allows the elimination of the presence of calcite and the increase of ammonia concentration causes formation of spherical particles with different sizes in the range of 26–266 nm. The relation among the size and properties, including bioactivity, of the glass particles is evaluated. New glasses that vary in composition (10–25 wt% CaO), porosity (15–113 m² g⁻¹), and hydroxyl groups content greatly enhance the formation process of hydroxyapatite (HA) in simulated physiological fluids. For all glasses, superior apatite-mineralization ability in time as short as 2 h in the physiological-like buffer is achieved, thus exceeding the bioactivity of the known bioactive glasses, including 45S5 glass (Bioglass). The assessment of the safety and toxicity profile of the obtained glasses is verified in a wide range of concentrations (1–1000 µg mL⁻¹) against human dermal fibroblasts and MC3T3 mouse osteoblast precursors, but also to human erythrocytes by determining hemocompatibility. Two glasses of different sizes, 73 and 266 nm, are promising and warrant further research.     

Synthesis and characterization of tin oxide (SnO2) nanocrystalline powders by a simple modified sol–gel route

This paper reports the synthesis and characterization of nanocrystalline tin oxide (SnO₂) powders by a simple method using a chitosan–polymer complex solution. To obtain SnO₂ nanocrystalline powders, the precursor was calcined at 500–600 °C in air for 2 h. The phase composition of calcined samples was studied by X-ray diffraction (XRD). The XRD results confirmed the formation of a SnO₂ phase with tetragonal structure. The particle sizes of the powder were found to be 22–23 nm as evaluated by the XRD line broadening method. TEM investigation revealed that the SnO₂ samples consist of crystalline particles of 19–21 nm. The corresponding selected area electron diffraction analysis further confirmed the formation of the tetragonal structure of SnO₂ without any impurity phases. The optical properties of the samples were explored by Fourier transform infrared spectroscopy, optical absorption and Raman studies. The estimated band gaps of the samples were in the range of 3.44–3.73 eV.     

Structural,optical and photocatalytic properties of (Mg,Al)-codoped ZnO powders prepared by sol–gel method

Structural and optical properties of 1 at % Al-doped Zn_1−xMg_xO (x=0–8%) powders prepared by sol–gel method were systematically investigated by means of X-ray diffraction, scanning electron microscopy, ultraviolet–visible absorbance measurement, photoluminescence and Raman scattering spectra. All the powders retained the hexagonal wurtzite structure of ZnO. The band gap and near band emission energies determined from absorbance and photoluminescence spectra increased linearly with increasing Mg content, respectively, which implied that the Mg worked effectively on ZnO band gap engineering, irrespective of Al codoping. However, according to the PL and Raman scattering studies, for the sample of x=8%, the Al doping efficiency was decreased by higher Mg codoping. On the other hand, the effect of Mg codoping on photocatalytic degradation of methylene orange was explored experimentally. The substitution of Mg ions at Zn sites shifted the conduction band toward higher energies and then enhanced the photocatalytic activity, while the incorporation of interstitial Mg ions and decreased Al doping efficiency for higher Mg doping sample (x=8%) reduced the photocatalytic activity.     

Synthesis and Reactivity of Mg(II)–Fe(II)–Fe(III) Hydroxycarbonates

Green rust-like compounds (GRs) were discovered as natural minerals in various hydromorphic soils, where anoxic conditions allow their stability. They may control some redox processes in aquifers and participate to the transformation of various pollutants. Since Mg(II) cations are present in the fields where GRs were discovered, a partial substitution of Mg(II) to Fe(II) leading to intermediate compounds between GRs and usual Mg(II)–Fe(III) hydroxysalts is suspected. Mg(II)–Fe(II)–Fe(II) hydroxycarbonates can be obtained as intermediate oxidation products of (Mg, Fe)(OH)₂ in carbonate-containing aqueous media obeying to [Fe^II _4(1–x)Mg^II _4x Fe^III ₂(OH)₁₂]²⁺ [CO₃ ^2– nH₂O]^–2. TMS spectra at 12 K are similar to those of GRs, i.e., two quadrupole doublets, one due to Fe(II) with a large isomer shift =1.29 mms^–1 (with respect to -iron at room temperature) and quadrupole splitting E _Q=2.76 mms^–1, the other one due to Fe(III) with smaller hyperfine parameters =0.49 mms^–1 and E _Q=0.44 mms^–1. Fe(II) ions oxidise rapidly into Fe(III) with dissolved O₂. The reactivity is similar to that of Fe(II)–Fe(III) hydroxysalts GR, and thus the potential of Mg(II)–Fe(II)–Fe(III) compounds for reducing pollutants.     

Improvement of the zirconium diffusion barrier between lanthanide (La–Ce) and a clad material by hydrothermal crystallization

Hydrothermal crystallization was conducted to improve the diffusion barrier performance of Zr thin films to prevent a fuel clad chemical interaction (FCCI) at the interface between a clad material and lanthanide elements (Mischmetal: 75Ce–25La; intermetallic compound) as fission product. The crystalline phase and size of Zr thin films deposited on a HT9 disk by RF magnetron sputtering were varied by hydrothermal crystallization in an autoclave at 393 K, 423 K and 453 K. Diffusion couple tests of the clad with and without a Zr diffusion barrier were performed at 933 K for 25 h with mischmetal, which have diffusion properties similar to uranium metal composite fuel. While substantial FCCI occurred at the interface between the mischmetal and clad in the specimen without hydrothermal crystallization, the Zr barrier with hydrothermal crystallization showed excellent resistance to FCCI. The performance of the Zr FCCI barrier was improved due to a decrease in interdiffusion by the grain boundary, which can increase the FCCI in the Zr barrier.