AgNO<Subscript>3</Subscript> spray tests: advantages,weaknesses, and various applications to quantify chloride ingress into concrete. Part 2: Non-steady-state migration tests and chloride diffusion coefficients

This paper forms the second part of a series devoted to the analysis of the capabilities of AgNO₃ spray tests, in view of using them for various issues, within the framework of the evaluation and the prediction of chloride-induced corrosion risks. More precisely, the Maultzsch procedure (spraying of 0.1-N AgNO₃ solution + K₂CrO₄) and the use of AgNO₃ alone have been investigated on a broad range of concretes. In this second part, the feasibility of colorimetric techniques on saturated specimens cast in laboratory, after non-steady-state migration tests carried out in various conditions is discussed. Colorimetric methods have been applied to the determination of the average penetration depth. In addition, the detection threshold of these techniques has been investigated. Moreover, colorimetric methods have been applied to the calculation of apparent and effective chloride diffusion coefficients from non-steady-state diffusion and migration tests. The results then obtained have been compared to the values obtained by other types of methods.     

Phonons in mixed superionic fluorites (BaF<Subscript>2</Subscript>)<Subscript>1-x</Subscript>(LaF<Subscript>3</Subscript>)<Subscript>x</Subscript>

In recent years, the fluorite-structured solid solutions with the general formula, (MF₂)_1-x(RF₃)_x (M = Ca, Sr, Ba, Pb and R is a rare-earth element or Y), have been the subject of numerous experimental studies focussed on their superionic properties. The overall cubic crystal symmetry (space group Fm3m) is conserved up to x ≶ x_max, where x_max ⊁ 0.4-0.5 depending on M and R. The zone centre phonons and phonon dispersion along three symmetry directions of the mixed superionic compound (BaF₂)_1-x(LaF₃)_x have been investigated by applying de Launey angular force model for x ≶ x_max. The calculated results are compared and explained with available experimental results.     

Influence of transition metal element (Co,Ni, Cu) doping on structural,electrical and magnetic properties of Bi<Subscript>0.9</Subscript>Ca<Subscript>0.1</Subscript>FeO<Subscript>3</Subscript> nanoparticles

The multiferroic Bi_0.9Ca_0.1FeO₃, Bi_0.9Ca_0.1Fe_0.9Co_0.1O₃, Bi_0.9Ca_0.1Fe_0.9Ni_0.1O₃, Bi_0.9Ca_0.1Fe_0.9Cu_0.1O₃ samples were prepared by a simple sol–gel method. Rietveld refinement of X-ray diffraction data and Raman spectra reflect a structural phase transition from single phase (rhombohedral, pure BiFeO₃) to two phase coexistence (rhombohedral R3c and cubic Fm-3 m). The structural distortion of Bi_0.9Ca_0.1Fe_0.9Ni_0.1O₃ is very marked. SEM images show the co-doped nanoparticles having an average size of 50 nm. A contribution from the leakage current have been observed in the P–E loops. XPS results reveal that the concentration of Fe²⁺ and oxygen vacancy decreased after transition metal elements (Co, Ni, Cu) doped into Bi_0.9Ca_0.1FeO₃. Moreover Co, Ni doping can enhance the saturation magnetization, while Cu doping can enhance the coercive field in Bi_0.9Ca_0.1FeO₃.     

On the synthesis,characterization and photocatalytic applications of nanostructured TiO<Subscript>2</Subscript>

Nanocrystalline semiconducting materials are attracting much attention due to their potential applications in solar energy conversion, nonlinear optics, and heterogeneous photocatalysis. In the present investigation, we have synthesized nanostructured TiO₂ photocatalysts, which have been used in the photocatalytic degradation of phenol (one of the most common water pollutants). These catalysts have been prepared through sol-gel technique using titanium tetra-isopropoxide as a raw material for synthesis. Characterization techniques such as XRD, SEM and TEM have been employed for structural/microstructural investigations. XRD results show that the as synthesized TiO₂ nanopowder exhibit anatase phase, TiO₂. The average sizes of the TiO₂ nanopowders are ∼ 5–10 nm. The optical properties of the samples were investigated through UV-visible and fluorescence techniques. It has been observed that absorption edge corresponds to ∼ 410 nm (bandgap, ∼ 3.02 eV). The emission peak in the fluorescence spectrum at ∼ 418 nm corresponds to the bandgap energy of ∼ 2.97 eV. Concentration of phenol (initial concentration, ∼ 100 ppm) with illumination time was monitored by measuring the absorbance of pure and illuminated phenol through UV-visible spectrophotometer. Salient feature of this study relates to the fact that the present sol-gel synthesized TiO₂ nanopowders have been found to be better photocatalysts for phenol degradation than the presently employed commercial TiO₂ (P-25, Degussa) photocatalyst. Thus, whereas phenol concentration, with the presently synthesized TiO₂ nanopowders, the concentration of phenol decreases up to ∼ 32% but for commercial TiO₂ nanopowder (P-25, Degussa), it decreased only up to ∼ 25%. The improved surface area is considered as an important factor for the aforesaid decrease in phenol concentration.     

Li-storage and cycling properties of spinel,CdFe<Subscript>2</Subscript>O<Subscript>4</Subscript>, as an anode for lithium ion batteries

Cadmium ferrite, CdFe₂O₄, is synthesized by urea combustion method followed by calcination at 900°C and characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM) and selected area electron diffraction (SAED) techniques. The Li-storage and cycling behaviour are examined by galvanostatic cycling, cyclic voltammetry (CV) and impedance spectroscopy in the voltage range, 0·005–3·0 V vs Li at room temperature. CdFe₂O₄ shows a first cycle reversible capacity of 870 (± 10) mAhg⁻¹ at 0·07C-rate, but the capacity degrades at 4 mAhg⁻¹ per cycle and retains only 680 (± 10) mAhg⁻¹ after 50 cycles. Heat-treated electrode of CdFe₂O₄ (300°C; 12 h, Ar) shows a significantly improved cycling performance under the above cycling conditions and a stable capacity of 810 (± 10) mAhg⁻¹ corresponding to 8·7 moles of Li per mole of CdFe₂O₄ (vs theoretical, 9·0 moles of Li) is maintained up to 60 cycles, with a coulombic efficiency, 96–98%. Rate capability of heat-treated CdFe₂O₄ is also good: reversible capacities of 650 (± 10) and 450 (± 10) mAhg⁻¹ at 0·5 C and 1·4 C (1 C = 840 mAg⁻¹) are observed, respectively. The reasons for the improved cycling performance are discussed. From the CV data in 2–15 cycles, the average discharge potential is measured to be ∼0·9 V, whereas the charge potential is ∼2·1 V. Based on the galvanostatic and CV data, ex situ-XRD, -TEM and -SAED studies, a reaction mechanism is proposed. The impedance parameters as a function of voltage during the 1st cycle have been evaluated and interpreted. Dedicated to Prof. C N R Rao on his 75th birthday, and his contributions to science for the past 56 years     

Electrical properties of In<Subscript>2</Subscript>Se<Subscript>3</Subscript> layered crystals doped with cadmium,iodine, or copper

The electrical properties of nominally undoped and doped (0.1 wt % Cd, I, and Cu) In₂Se₃ single crystals have been studied in the range 80–400 K. Only iodine doping has been found to have a significant effect on the carrier concentration in In₂Se₃, raising it from 4.9 × 10¹⁷ to 1.6 × 10¹⁸ cm^?3 at 300 K. The observed temperature variation of in-plane electron mobility is interpreted in terms of acoustic phonon and neutral impurity scattering. The three dopants have the strongest effect on the out-of-plane conductivity of In₂Se₃.     

Phase formation of superconducting MgB<Subscript>2</Subscript> at ambient pressure

MgB₂ superconductor has been synthesized using a simple technique at ambient pressure. The synthesis was carried out in helium atmosphere over a wide range of temperatures. Magnesium was employed in excess to the stoichiometry to prevent the decomposition of MgB₂. Samples of MgB₂ thus prepared have been almost free from MgO as compared to other methods. Resistivities of the samples are quite low with residual resistivity ratio (RRR) of around 3.T _c (R = 0) is 38.2-38.5 K with ΔT _C of 0.6–1.0 K. Comparative studies of various methods of low pressure synthesis have been presented.     

Phenomenological model of the magnetocaloric effect and its correlation with critical behavior near room temperature in La<Subscript>0.7</Subscript>Ca<Subscript>0.2</Subscript>Sr<Subscript>0.1</Subscript>MnO<Subscript>3</Subscript> manganite

In this paper, we investigate the field dependence of the magnetocaloric properties of La_0.7Ca_0.2Sr_0.1MnO₃ powder sample using a phenomenological model. Our compound was elaborated by the conventional solid state reaction. The model parameters were determined from the magnetization data and were used to give better fits to magnetic transition and to calculate the magnetocaloric quantities. The magnetocaloric parameters such as the maximum of the magnetic entropy change \(\Delta S_M^{max}\) and the relative cooling power RCP, have been determined from the calculation of the magnetization as a function of temperature under several magnetic applied field. Thus, from the magnetocaloric results, such as RCP?≈?b(μ₀H)^1+1/δ and T_peak???T_C ≈ b (µ₀H)^1/Δ, the critical exponents values related to the magnetic transition have been determined. The estimated results are close to those expected by the tricritical mean-field model. Furthermore, the values of the ferromagnetic transition temperature T_C, as well as the critical exponents β, γ and δ obtained by the theoretical model, are compared with those obtained by other various techniques (such as the modified Arrott plots, the Kouvel–Fisher method and the critical isotherm analysis). A good agreement has been found in the vicinity of the Curie temperature.     

Effect of very low to high Sb-doping on the structural,electrical, photo-conductive and thermoelectric properties of fluorine-doped SnO<Subscript>2</Subscript> (FTO) thin films prepared by spray pyrolysis technique

Transparent conducting fluorine and Sb-doped [SnO₂: (F, Sb)] thin films have been deposited onto preheated glass substrates using the spray pyrolysis technique by the various dopant quantity of spray solution. The effect of antimony impurities on the structural, morphological, electrical, Thermo-electrical, optical and photoconductive properties of films has been investigated. The [F/Sn] atomic concentration ratio (x) in the spray solution is kept at value of 0.7 and the [Sb/Sn] atomic ratio (y) varied at values of 0, 0.0005, 0.001, 0.002, 0.01, 0.03, 0.05, 0.07 and 0.10. It is found that the films are polycrystalline in nature with a tetragonal crystal structure corresponding to SnO₂ phase having orientation along the (110) and (200) planes. SEM images indicated that nanostructure of the films has a particle type growth. The average grain size increases with increasing spraying quantity of Sb-dopant. The compositional analysis of SnO₂: (F, Sb) thin films were studied using EDAX. SEM and AFM study reveals the surface of SnO₂: (F, Sb) to be made of nanocrystalline particles. The Hall Effect measurements have shown n-type conductivity in all deposited films. The lowest sheet resistance and highest the carrier concentration about 7.7 Ω/□ and 6.6 × 10²², respectively, were obtained for the film deposited with y = [Sb/Sn] = 0.001 and x = [F/Sn] = 0.7. The maximum of the Seebeck coefficient equal to 12.8 μV K^?1 was obtained at 400 K for the film deposited with y = [Sb/Sn] = 0.10. The average transmittance of films varied over the range 10–80 % with change of Sb-concentration. The band gap values of samples were obtained in the range of 3.19–3.8 eV. From the photoconductive studies, the Sb-doped films exhibited sensitivity to incident light especially in y = 0.001. The electrical resistivity and carrier concentration vary in range 5.44 × 10^?4 to 1.02 × 10^?2Ω cm and 2.6 × 10²²–6.6 × 10²² cm^?3, respectively.     

Superconducting Properties of Iodine-Intercalated Bi<Subscript>2</Subscript>Sr<Subscript>2</Subscript>Ca<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>10+<Emphasis Type="Italic">x</Emphasis></Subscript>

The superconducting properties of iodine-intercalated high-temperature superconducting Bi₂Sr₂Ca₂Cu₃O_10+x phase (Bi-2223) were systematically studied. It was found that for samples containing a significant amount of Bi₂Sr₂CaCu₂O_8+x , iodine intercalation results in the dramatic decrease of the inter-granular critical current density, as well as a significant decrease of the critical temperature (T _c), the critical current density in the grains (J _cg), and of the amount of Bi-2223. For samples with a large amount of Bi-2223, T _c changes insignificantly, whereas J _cg can even increase. We argue that the different behavior of the superconducting parameters is the result of various oxygen concentrations, and we explain the effect of iodine intercalation based on the parabolic dependence between T _c and the number of holes per CuO₂ layer. The H(T) curves (determined from the peak position in the loss signal of ac susceptibility) for intercalated samples deviate significantly from the quasi 2D-like behavior, pointing toward an enhancement of the 3D fluctuations of vortices. For the change in the values and dimensionality of the flux pinning in the process of the intercalation, we attempted a qualitative explanation based on the models proposed in literature.     

Characterization of spray deposited CoWO<Subscript>4</Subscript> thin films for photovoltaic electrochemical studies

Preparation of Cobalt tungstate (CoWO₄) thin film by spray pyrolysis with ammonical solution as a precursor is presented. The phase and surface morphology characterizations have been carried out by XRD and SEM analysis. The study of optical absorption spectrum in the wavelength range 350 – 850 nm shows direct as well as indirect optical transitions in the thin film material. The d. c. electrical conductivity measurements in the temperature range 310–500 K indicate semiconducting behavior of the thin film. The thin films deposited on fluorine doped tin oxide (FTO) coated conducting glass substrates were used as a photoanode in photovoltaic electrochemical (PVEC) cell with configuration: CoWO₄ | Ce⁴⁺, Ce³⁺ | Pt; 0.1 M in 0.1 N H₂SO₄. The PVEC characterization reveals the fill factor and power conversion efficiency to be 0.36 and 0.62%, respectively. The flat band potential is found to be −0.18 V (SCE).     

Untersuchung der Einflüsse von Substratrauheit und Spritzpartikelgröße auf die Haftung thermisch gespritzter Schichten

About the influence of substrate roughness and spray particle size on the adhesion of thermal spray coatings The influence of substrate roughness and spray particle size on the adhesion of thermal spray coatings was researched systematically. In addition to established spray materials (Cr₂O₃, WCCo, NiCr) and spraying processes (atmospheric plasma spraying (APS), high velocity flame spraying (HVOF)) different substrate materials (steel, stainless steel, aluminum) were included in the research work as well.     

The Multiferroic Properties of (Bi<Subscript>0.9</Subscript>Ba<Subscript>0.1</Subscript>)(Fe<Subscript>0.95</Subscript>Mn<Subscript>0.05</Subscript>)O<Subscript>3</Subscript> Films

(Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ films were prepared on LaNiO₃-coated surface oxidized Si substrates. XRD and Raman measurements confirm that the (Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ film has pure R3c structure. Clear ferromagnetism with saturated magnetization of about 25 emu/cm³ has been observed at room temperature. The ferroelectric properties of the (Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ film was confirmed by the observation of the ferroelectric domains and the converse piezoelectric coefficient d ₃₃ versus applied voltage hysteresis loops by piezoelectric force microscopy (PFM). The observation of ferromagnetism and ferroelectricity in (Bi_0.9Ba_0.1)(Fe_0.95Mn_0.05)O₃ films indicates the potential multiferroic applications.     

Synthesis and properties of solid electrolyte Ce<Subscript>0.9</Subscript>Gd<Subscript>0.1</Subscript>O<Subscript>2–δ</Subscript> with Co,Cu, Mn,Zn doping

The influence of small additions (1, 3, 5 mol %) of transition metal (Co, Cu, Mn, Zn) oxides on the properties of solid electrolyte Ce_0.9Gd_0.1O_2–δ (GDC) have been investigated. It has been shown that the addition of dopants results in intensification of GDC sintering and reduction of the shrinkage end temperature by 300–400°C, which decreases in the sequence Zn–Mn–Co–Cu. The ultimate dopant concentration above which the further activation of GDC sintering does not occur is about 3 mol % for Co, Cu, and Mn and about 1 mol % for Zn. It has been shown that Co and Cu increase the total conductivity of GDC, while Mn and Zn decrease it.     

Synthesis,characterization and application of semiconducting oxide (Cu<Subscript>2</Subscript>O and ZnO) nanostructures

In the present study, we report the synthesis, characterization and application of nanostructured oxide materials. The oxide materials (Cu₂O and ZnO) have been synthesized by electrolysis based oxidation and thermal oxidation methods. Cuprous oxide (Cu₂O) nanostructures have been synthesized by anodic oxidation of copper through a simple electrolysis process employing plain water (with ionic conductivity, ～6 μS/m) as electrolyte. In this method no special electrolytes, chemicals and surfactants are needed. The method is based on anodization pursuant to the simple electrolysis of water at different voltages. Two different types of Cu₂O nanostructures have been found. One type got delaminated from copper anode and was collected from the bottom of the electrochemical cell and the other was located on the copper anode itself. The nanostructures collected from the bottom of the cell are either nanothreads embodying beads of different diameters, ～ 10–40 nm or nanowires (length, ～ 600–1000 nm and diameter, ～ 10–25 nm). Those present on the copper anode were nanoblocks with preponderance of nanocubes (nanocube edge, ～ 400 nm). The copper electrode served as a sacrificial anode for the synthesis of different nanostructures. Aligned ZnO nanorod array has been successfully synthesized by simple thermal evaporation catalyst free method. Detailed structural characterizations revealed that the as synthesized aligned ZnO nanorods are single crystalline, with a hexagonal phase, and with growth along the [0001] direction. The room-temperature photoluminescence spectra showed a weak ultraviolet emission at 380 nm, a broad blue band at 435 nm and a strong orange-red emission at 630 nm. Structural/microstructural characterization of these nanomaterials have been carried out employing scanning (XL-20) and transmission electron microscopic (Philips EM, CM-12 and Technai 20G²) techniques and X-ray diffraction techniques having graphite monochromater with CuKα radiation (λ =1.54439 Å) (X’Pert PRO PAN analytical). The UV-visible absorption spectra were recorded on Model-VARIAN, Cary 100, and Bio UV-visible spectrophotometer. The photoluminescence (PL) measurement was carried out at room temperature with a He-Cd, a laser excited at 325 nm.     

Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript>/TiC composites prepared by PDS

Synthesis of composite materials with improved mechanical properties is considered. Pulse discharge sintering (PDS) technique was utilized for consolidation and synthesis of double phase Ti₃SiC₂/TiC composites from the initial powders TiH₂/SiC/TiC. Scanning electron microscopy with energy-dispersive spectrometry (SEM with EDS) and X-ray diffractometry (XRD) were exploited for the analysis of the microstructure and composition of the sintered specimens. Mechanical tests showed high bending and compression strength and low Vickers hardness of Ti₃SiC₂-rich specimens. The reasons of this behaviour are in the features of the textured microstructure of Ti₃SiC₂ phase.     

Dielectric properties of iron doped calcium copper titanate,CaCu<Subscript>3</Subscript>Ti<Subscript>3.9</Subscript>Fe<Subscript>0.1</Subscript>O<Subscript>12</Subscript> ceramic

Dielectric properties of iron doped CaCu₃Ti₄O₁₂ (CCTO), viz. CaCu₃Ti_3.9Fe_0.1O₁₂ (CCTFO) prepared by a novel semi-wet route have been investigated. X-ray diffraction of powder sintered at 900 °C show formation of single phase solid solution. Energy dispersive X-ray spectroscopy (EDX) confirmed the presence of CuO rich phase at grain boundaries of CCTFO. Nature of dielectric relaxation observed above room temperature is studied using complex plane impedance analysis and modulus spectroscopy. It has been found that out of the two relaxations reported earlier above room temperature, one occurring at lower temperature is due to grainboundaries interfacial polarization.     

Preparation of AgO<Subscript>2</Subscript>/GrO nanocomposites by hydrothermal method and investigation of photoluminescence properties

This paper reports a novel processing route for producing AgO₂/GrO nanocomposites by hydrothermal method. AgO₂/GrO nanocomposites as semiconductor materials have been synthesized via a facile one-step process using AgNO₃ and glucose as starting reagents. We investigated the influence of the thermal decomposition temperature and reaction time, on the morphology and the particle size of AgO₂/GrO nanocomposites. The AgO₂/GrO nanocomposites were characterized by FT-IR, UV–Vis spectra, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy, X-ray photoelectron spectroscopy and energy-dispersive X-ray spectroscopy. The obtained results exhibited that the synthesized nano product by calcining for 4 h showed excellent uniformity and quality.     

Room-Temperature Photomagnetic Effect of Fe<Subscript>3</Subscript>Ga<Subscript>4</Subscript> Grown on GaAs Substrates

Ga–As–Fe composite films prepared by molecular beam epitaxy at 600°C on GaAs(100) substrates with the stacking sequence of [100-nm GaAs/50-nm Fe₃Ga_{2− x} As _x /100-nm GaAs] exhibit the distinct photo-enhanced magnetization at room temperature. Transmission electron microscopy reveals the formation of metamagnetic Fe₃Ga₄ grains on the sample surface. Illumination power dependence of the enhanced magnetization has been carefully compared with the antiferromagnetic-type magnetization–temperature (M–T) curve (Neel temperature of T _N = 340–390 K), from which we have discussed the existence of photon-mode photo-enhanced magnetization of some sort in addition with the enhancement due to the light-induced heating.     

Enhanced Superconducting Properties of Air-Processed GdBa<Subscript>2</Subscript>Cu<Subscript>3</Subscript>O<Subscript>7-δ</Subscript> Single Domains with BaCO<Subscript>3</Subscript>/BaCuO<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript> Addition

Single domain GdBa₂Cu_7-δ (Gd123) bulk superconductors were fabricated in air by top-seeding melt-texture growth. Performance of the air-processed Gd123 was successfully enhanced by addition of both BaCO₃ and BaCuO_2−x , which suppress the formation of Gd_1+x Ba_2−x Cu₃O_7-δ solid solutions. The optimum doping amount ranges from 0.05 to 0.15, M BaCO₃ and 0.05 to 0.1, M BaCuO_2−x per molar Gd123. The distribution of the second phase particles was observed by scanning electron microscopy. A narrow band formed by Gd₂BaCuO₅ particle concentration appeared around the seeding zone in both a–b plane and c-growth sector in Gd123 single grain. Trapped magnetic field density reached 0.67, T for sample with 24 mm in diameter and 8, mm in thickness and a high critical current density J _c up to 91,200, A/cm² was achieved at 77, K under self-field.