Resistance-switching properties of Bi-doped $$\hbox {SrTiO}_{3}$$ films for non-volatile memory applications with different device structures

\(\hbox {SrTiO}_{3}\) and Bi-doped \(\hbox {SrTiO}_{3}\) films were fabricated with different device structures using the sol–gel method for non-volatile memory applications, and their resistance-switching behaviour, endurance and retention characteristics were investigated. \(\hbox {SrTiO}_{3}\) and \(\hbox {Sr}_{0.92}\hbox {Bi}_{0.08}\hbox {TiO}_{3}\) films grown on Si or Pt have the same phase structure, morphologies and grain size; however, the grain size of the \(\hbox {Sr}_{0.92}\hbox {Bi}_{0.08}\hbox {TiO}_{3}\) films grown on Si is slightly larger than those of the \(\hbox {SrTiO}_{3}\) films grown on Si and the \(\hbox {Sr}_{0.92}\hbox {Bi}_{0.08}\hbox {TiO}_{3}\) films grown on Pt. The \(\hbox {SrTiO}_{3}\) or \(\hbox {Sr}_{0.92}\hbox {Bi}_{0.08}\hbox {TiO}_{3}\) films grown on Si or Pt all exhibit bipolar resistive-switching behaviour and follow the same conductive mechanism; however, the \(\hbox {Ag}/\hbox {Sr}_{0.92}\hbox {Bi}_{0.08}\hbox {TiO}_{3}/\hbox {Si}\) device possesses the highest \(R_{\mathrm{HRS}}{/}R_{\mathrm{LRS}}\) of \(10^{5}\) and the best endurance and retention characteristics. The doping of Bi is conducive to enhance the \(R_{\mathrm{HRS}}{/}R_{\mathrm{LRS}}\) of the \(\hbox {SrTiO}_{3}\) films; meanwhile, the Si substrates help improve the endurance and retention characteristics of the \(\hbox {Sr}_{0.92}\hbox {Bi}_{0.08}\hbox {TiO}_{3}\) films.     

Effects of electrolyte concentration and current density on the properties of electro-deposited NiFeW alloy coatings

NiWP alloy coatings were prepared by electrodeposition, and the effects of ferrous chloride (\(\hbox {FeCl}_{2})\), sodium tungstate (\(\hbox {Na}_{2}\hbox {WO}_{4})\) and current density (\(D_{\mathrm{K}}\)) on the properties of the coatings were studied. The results show that upon increasing the concentration of \(\hbox {FeCl}_{2}\), initially the Fe content of the coating increased and then tended to be stable; the deposition rate and microhardness of coating decreased when the cathodic current efficiency (\(\eta \)) initially increased and then decreased; and for a \(\hbox {FeCl}_{2}\) concentration of \(3.6\, \hbox {g\,l}^{-1}\), the cathodic current efficiency reached its maximum of 74.23%. Upon increasing the concentration of \(\hbox {Na}_{2}\hbox {WO}_{4}\), the W content and microhardness of the coatings increased; the deposition rate and the cathode current efficiency initially increased and then decreased. The cathodic current efficiency reached the maximum value of 70.33% with a \(\hbox {Na}_{2}\hbox {WO}_{4}\) concentration of 50 g \(\hbox {l}^{-1}\), whereas the deposition rate is maximum at 8.67 \(\upmu \hbox {m}\,\hbox {h}^{-1}\) with a \(\hbox {Na}_{2}\hbox {WO}_{4}\) concentration of \(40\, \hbox {g\,l}^{-1}\). Upon increasing the \(D_{\mathrm{K}}\), the deposition rate, microhardness, Fe and W content of the coatings increased, the cathodic current efficiency increases first increased and then decreased. When \(D_{\mathrm{K}}\) was 4 A dm\(^{-2}\), the current efficiency reached the maximum of 73.64%.     

Rectifying resistance-switching behaviour of Ag/SBTO/STMO/$$\hbox {p}^{+}$$-Si heterostructure films

The \(\hbox {Sr}_{0.88}\hbox {Bi}_{0.12}\hbox {TiO}_{3}/\hbox {SrTi}_{0.92}\hbox {Mg}_{0.08}\hbox {O}_{3}\) (SBTO/STMO) heterostructure films were prepared on \(\hbox {p}^{+}\hbox {-Si}\) substrates by sol–gel spin-coating technique, and the films had good crystallinity and uniform grain distribution. The heterostructure films with a structure of Ag/SBTO/STMO/\(\hbox {p}^{+}\hbox {-Si}\) exhibited a bipolar, remarkable resistance-switching characteristic, and \(R_{\mathrm{HRS}}/R_{\mathrm{LRS}}\,\,{\sim }10^{4}\). More importantly, the heterostructure films showed rectifying characteristic in the low resistance state (LRS), and the rectification ratio can reach \(10^{2 }\) at \(\pm 1\hbox { V}\). The dominant resistive-switching conduction mechanism of high resistance state (HRS) was Ohmic behaviour, and the LRS changed to space charge-limited current (SCLC).     

Microwave dielectrics: solid solution,ordering and microwave dielectric properties of $$(1{-}x)\hbox {Ba}(\hbox {Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}{-}x\hbox {Ba(Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}$$ ceramics

The effect of Ba(\(\hbox {Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}\) phase on structure and dielectric properties of \(\hbox {Ba(Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}\) was studied by synthesizing \((1{-}x)\hbox {Ba(Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}{-}x\hbox {Ba}(\hbox {Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}\) (\(x = 0\), 0.005, 0.01 and 0.02) ceramics. Superlattice reflections due to 1:2 ordering appear as low as \(1000^{\circ }\hbox {C}\). \(\hbox {Ba}(\hbox {Mg}_{1/3}\hbox {Nb}_{2/3})\hbox {O}_{3}\) forms solid solution with \(\hbox {Ba}(\hbox {Mg}_{1/8}\hbox {Nb}_{3/4})\hbox {O}_{3}\) for all ‘x’ values studied until \(1350^{\circ }\hbox {C}\). Ordering was confirmed by powder X-ray diffraction pattern, Raman study and HRTEM. Ceramic pucks can be sintered to density \({>}92\%\) of theoretical density. Temperature and frequency-stable dielectric constant and nearly zero dielectric loss (tan \(\delta \)) were observed at low frequencies (20 MHz). The sintered samples exhibit dielectric constant (\(\varepsilon _{\mathrm{r}})\) between 30 and 32, high quality factor between 37000 and 74000 GHz and temperature coefficient of resonant frequency (\(\tau _{\mathrm{f}})\) between 21 and \(24\hbox { ppm }^{\circ }\hbox {C}^{-1}\).     

Electrical and Thermal Characteristics of the Insulator–Metal Transition in Crystalline $$\hbox {V}_{2}\hbox {O}_{5}$$ Films

The electrical and thermal properties with respect to the crystallization in \(\hbox {V}_{2}\hbox {O}_{5}\) thin films were investigated by measuring the resistance at different temperatures and applied voltages. The changes in the crystal structure of the films at different temperatures were also explored using Raman measurements. The thermal diffusivity of the crystalline \(\hbox {V}_{2}\hbox {O}_{5}\) film was measured by the nanosecond thermoreflectance method. The microstructures of amorphous and crystalline \(\hbox {V}_{2}\hbox {O}_{5}\) were observed by SEM and XRD measurements. The temperature-dependent Raman spectra revealed that a structural phase transition does not occur in the crystalline film. The resistance measurements of an amorphous film indicated semiconducting behavior, whereas the resistance of the crystalline film revealed a substantial change near \(250\,{^{\circ }}\hbox {C}\), and Ohmic behavior was observed above \(380\,{^{\circ }}\hbox {C}\). This result was due to the metal–insulator transition induced by lattice distortion in the crystalline film, for which \(T_{\mathrm{c}}\) was \(260\,{^{\circ }}\hbox {C}\). \(T_{\mathrm{c}}\) of the film decreased from 260 \({^{\circ }}\hbox {C}\) to \(230\,{^{\circ }}\hbox {C}\) with increasing applied voltage from 0 V to 10 V. Furthermore, the thermal diffusivity of the crystalline film was \(1.67\times 10^{-7}\,\hbox {m}^{2}\cdot \hbox {s}^{-1}\) according to the nanosecond thermoreflectance measurements.     

High-pressure studies of superconductivity in $$\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}$$

\(\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}\) crystallizes in tetragonal CeOBiS\(_{2}\) structure (S. G. P4/nmm). We have investigated the effect of pressure on magnetization measurements. Our studies suggest improved superconducting properties in polycrystalline samples of \(\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}\). The \(T_{\mathrm{c}}\) in our sample is 5.3 K, at ambient pressure, which is marginal but definite enhancement over \(T_{\mathrm{c}}\) reported earlier (= 5.1 K). The upper critical field \(H_{\mathrm{c}2}\)(0) is greater than 3 T, which is higher than earlier report on this material. As determined from the M–H curve, both \(H_{\mathrm{c}2}\) and \(H_{\mathrm{c}1}\) decrease under external pressure P (0 \(\le P \le \) 1 GPa). We observe a decrease in critical current density and transition temperature on applying pressure in \(\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}\).     

Canadian Field Soils IV: Modeling Thermal Conductivity at Dryness and Saturation

The thermal conductivity data of 40 Canadian soils at dryness \((\lambda _{\mathrm{dry}})\) and at full saturation \((\lambda _{\mathrm{sat}})\) were used to verify 13 predictive models, i.e., four mechanistic, four semi-empirical and five empirical equations. The performance of each model, for \(\lambda _{\mathrm{dry}}\) and \(\lambda _{\mathrm{sat}}\), was evaluated using a standard deviation (SD) formula. Among the mechanistic models applied to dry soils, the closest \(\lambda _{\mathrm{dry}}\) estimates were obtained by MaxRTCM \((\textit{SD} = \pm ~0.018\,\hbox { Wm}^{-1}\cdot \hbox {K}^{-1})\), followed by de Vries and a series-parallel model (\(\hbox {S-}{\vert }{\vert }\)). Among the semi-empirical equations (deVries-ave, Advanced Geometric Mean Model (A-GMM), Chaudhary and Bhandari (C–B) and Chen’s equation), the closest \(\lambda _{\mathrm{dry}}\) estimates were obtained by the C–B model \((\pm ~0.022\,\hbox { Wm}^{-1}\cdot \hbox {K}^{-1})\). Among the empirical equations, the top \(\lambda _{\mathrm{dry}}\) estimates were given by CDry-40 \((\pm ~0.021\,\hbox { Wm}^{-1}\cdot \hbox {K}^{-1}\) and \(\pm ~0.018\,\hbox { Wm}^{-1}\cdot \hbox {K}^{-1}\) for18-coarse and 22-fine soils, respectively). In addition, \(\lambda _{\mathrm{dry}}\) and \(\lambda _{\mathrm{sat}}\) models were applied to the \(\lambda _{\mathrm{sat}}\) database of 21 other soils. From all the models tested, only the maxRTCM and the CDry-40 models provided the closest \(\lambda _{\mathrm{dry}}\) estimates for the 40 Canadian soils as well as the 21 soils. The best \(\lambda _{\mathrm{sat}}\) estimates for the 40-Canadian soils and the 21 soils were given by the A-GMM and the \(\hbox {S-}{\vert }{\vert }\) model.     

Effect of CTAB coating on structural,magnetic and peroxidase mimic activity of ferric oxide nanoparticles

In the present work, pristine and cetyl trimethyl ammonium bromide (CTAB)-coated ferric oxide nanoparticles \((\hbox {CTAB@Fe}_{2}\hbox {O}_{3} \hbox { NPs})\) were synthesized and studied as enzyme mimics. The w/w ratio of \(\hbox {Fe}_{2}\hbox {O}_{3}\) to CTAB was varied as 1:1 and 1:2. Transmission electron microscopic analysis revealed that pristine NPs had an average size of 50 nm, whereas the presence of CTAB resulted in the formation of nanorods with length of 130 nm. BET studies confirmed enhancement of surface area on CTAB coating, which was maximum for w/w ratio 1:1. The synthesized pristine NPs and CTAB-coated NPs were evaluated for their peroxidase mimic activity using o-dianisidine dihydrochloride as substrate. Optimum pH, temperature, substrate and NPs concentration for the reaction were 1, \(25^{\circ }{\mathrm{C}}\), \(0.16~\hbox {mg}~\hbox {ml}^{-1}\) and \(1~\hbox {mg}~\hbox {ml}^{-1}\), respectively. Peroxidase mimic activity of \(\hbox {CTAB@Fe}_{2}\hbox {O}_{3}\hbox { NPs}\) (w/w 1:1) was higher than that of pristine NPs. However, further increase in CTAB coating (w/w 1:2) resulted in lowering of peroxidase mimic activity. Kinetic analysis was carried out at optimized conditions; maximum velocity (\(V_{\mathrm{max}})\) and Michaelis constant (\(K_{\mathrm{m}})\) value of \(\hbox {CTAB@Fe}_{2}\hbox {O}_{3}\hbox { NPs}\) at 1:1 w/w ratio were 7.69 mM and \(1.12~\upmu \hbox {mol}~\hbox {s}^{-1}\), respectively.     

Characterization and optical properties of $$\hbox {Pr}_{2}\hbox {O}_{3}$$-doped molybdenum lead-borate glasses

\(\hbox {Pr}^{3+}\) doped molybdenum lead-borate glasses with the chemical composition 75PbO?[25–(x \(+\) y)\(\hbox {B}_{2}\hbox {O}_{3}]\)–\(y\hbox {MoO}_{3}\)–\(x\hbox {Pr}_{2}\hbox {O}_{3}\) (where \(x = 0.5\) and 1.0 mol% and \(y = 0\) and 5 mol%) were prepared by conventional melt-quenching technique. Thermal, optical and structural analyses are carried out using DSC, UV and FTIR spectra. The physical parameters, like glass transition \((T_{\mathrm{g}})\), stability factor \((\Delta T)\), optical energy band gap \((E_{\mathrm{gopt}})\), of these glasses have been determined as a function of dopant concentration. The \({T}_{\mathrm{g}}\) and optical energy gaps of these glasses were found to be in the range of 290–350\({^{\circ }}\hbox {C}\) and 2.45–2.7 eV, respectively. Stability of the glass doped with \(\hbox {Pr}^{3+}\) is found to be moderate (\(\sim \)40). The results are discussed using the structural model of Mo–lead-borate glass.     

Estimating the Kinematic Viscosity of Petroleum Fractions

Kinematic viscosity correlation has been developed for liquid petroleum fractions at 37.78\(\,^{\circ }\hbox {C}\) and \(98.89\,^{\circ }\hbox {C}\) (100 and \(210^{\circ }\hbox {F})\) standard temperatures using a large variety of experimental data. The only required inputs are the specific gravity and the average boiling point temperature. The accuracy of the correlation was compared with several other correlations available in the literature. The proposed correlations proved to be more accurate in predicting the viscosity at 37.78\(\,^{\circ }\hbox {C}\) and \(98.89\,^{\circ }\hbox {C}\) with average absolute deviations of 0.39 and \(0.72\hbox { mm}^{2}/\hbox {s}\), respectively. Another objective was to develop a relation for the variation of viscosity with temperature to predict the viscosity of petroleum fraction at a certain temperature from the knowledge of the viscosity for the same liquid at two other temperatures. The newly developed correlation represents a wide array of temperatures from 20 \(^{\circ }\hbox {C}\) to 150 \(^{\circ }\hbox {C}\) and viscosities from 0.14\(\hbox { mm}^{2}/\hbox {s}\) to 343.64\(\hbox { mm}^{2}/\hbox {s}\). The results have been validated with experimental data consisting of 9558 data points, yielding an overall deviation of \(0.248\hbox { mm}^{2}/\hbox {s}\) and \(\hbox {R}^{2}\) of 0.998. In addition, new formulas were developed to interconvert the viscosity of petroleum fractions from one unit of measure to another based on finding the best fit for a set of experimental data from the literature with \(R^{2}\) as high as 1.0 for many cases. Detailed analysis showed good agreement between the predicted values and the experimental data.     

Structural,dielectric and piezoelectric study of Ca-, Zr-modified $$\hbox {BaTiO}_{3}$$ lead-free ceramics

We prepared a lead-free ceramic (\(\hbox {Ba}_{0.85}\hbox {Ca}_{0.15})(\hbox {Ti}_{1-x}\hbox {Zr}_{x})\hbox {O}_{3}\) (BCTZ) using the conventional mixed oxide technique. The samples were prepared by an ordinary mixing and sintering technique. In this study we investigated how small amounts of \(\hbox {Zr}^{4+}\) can affect the crystal structure and microstructure as well as dielectric and piezoelectric properties of \(\hbox {BaTiO}_{3}\). X-ray diffraction analysis results indicate that no secondary phase is formed in any of the BCTZ powders for \(0 \le x \le 0.1\), suggesting that \(\hbox {Zr}^{4+}\) diffuses into \(\hbox {BaTiO}_{3}\) lattices to form a solid solution. Scanning electron microscopy micrographs revealed that the average grain size gradually increased with \(\hbox {Zr}^{4+}\) content from 9.5 \(\upmu \!\hbox {m}\) for \(x = 0.02\) to 13.5 \(\upmu \!\hbox {m}\) for \(x = 0.1\); Curie temperature decreased due to the small tetragonality caused by \(\hbox {Zr}^{4+}\) addition. Owing to the polymorphic phase transition from orthorhombic to tetragonal phase around room temperature, it was found that the composition \(x = 0.09\) showed improved electrical properties and reached preferred values of \(d_{33} = 148\) pC \(\hbox {N}^{-1}\) and \(K_{\mathrm{p}} = 27\%\).     

Thermal Conductivity of Pyroclastic Soil (<Emphasis Type="BoldItalic">Pozzolana</Emphasis>) from the Environs of Rome

The paper reveals the experimental procedure and thermo-physical characteristics of a coarse pyroclastic soil (Pozzolana), from the neighborhoods of Rome, Italy. The tested samples are comprised of 70.7 % sand, 25.9 % silt, and 3.4 % clay. Their mineral composition contained 38 % pyroxene, 33 % analcime, 20 % leucite, 6 % illite/muscovite, 3 % magnetite, and no quartz content was noted. The effective thermal conductivity of minerals was assessed to be about \(2.14\,\hbox {W}{\cdot } \hbox {m}^{-1}{\cdot } \hbox {K}^{-1}\). A transient thermal probe method was applied to measure the thermal conductivity (\(\lambda \)) over a full range of the degree of saturation \((S_{\mathrm{r}})\), at two porosities (n) of 0.44 and 0.50, and at room temperature of about \(25\,^{\circ }\hbox {C}\). The \(\lambda \) data obtained were consistent between tests and showed an increasing trend with increasing \(S_{\mathrm{r}}\) and decreasing n. At full saturation (\(S_{\mathrm{r}}=1\)), a nearly quintuple \(\lambda \) increase was observed with respect to full dryness (\(S_{\mathrm{r}}=0\)). In general, the measured data closely followed the natural trend of \(\lambda \) versus \(S_{\mathrm{r}}\) exhibited by published data at room temperature for other unsaturated soils and sands. The measured \(\lambda \) data had an average root-mean-squared error (RMSE) of \(0.007\,\hbox {W}{\cdot } \hbox {m}^{-1}{\cdot } \hbox {K}^{-1}\) and \(0.008\,\hbox {W}{\cdot } \hbox {m}^{-1}{\cdot } \hbox {K}^{-1}\) for n of 0.50 and 0.44, respectively, as well as an average relative standard deviation of the mean at the 95 % confidence level \((\hbox {RSDM}_{0.95})\) of 2.21 % and 2.72  % for n of 0.50 and 0.44, respectively.     

Photoacoustic Study on the Structural Variation of Titania Nanomaterials Using the Pr (III) Ion as a Spectral Probe

In this work, \(\hbox {Pr}^{3+}\)-doped titania nanomaterials were prepared by a sol–gel method. The structural variations of the samples during the phase transitions were studied by using the \(\hbox {Pr}^{3+}\) ion as a photoacoustic spectral probe. The result shows that for the gel sample heated at \(80\,^{\circ }\hbox {C}\), the coordination environment of \(\hbox {Pr}^{3+}\) is similar to that of its aqueous ion. The f–f transitions of \(\hbox {Pr}^{3+}\) exhibit a continuous red shift along with the gel-to-anatase transition, indicating an increase of the ‘degree of covalency’ for the \(\hbox {Pr}^{3+}\) bonding. For the sample calcined at \(1100\,^{\circ }\hbox {C}\), however, the f–f transitions of \(\hbox {Pr}^{3+}\) show obvious blue shift. This can be attributed to the segregation of \(\hbox {Pr}^{3+}\) ions to the external surface during the anatase-to-rutile transition, forming \(\hbox {Pr}_{4}\hbox {Ti}_{9}\hbox {O}_{24}\). The stabilization effect of the doped \(\hbox {Pr}^{3+ }\)ions on the anatase phase of the samples is also discussed.     

Mesoscale evolution of non-graphitizing pyrolytic carbon in aligned carbon nanotube carbon matrix nanocomposites

Polymer-derived pyrolytic carbons (PyCs) are highly desirable building blocks for high-strength low-density ceramic meta-materials, and reinforcement with nanofibers is of interest to address brittleness and tailor multi-functional properties. The properties of carbon nanotubes (CNTs) make them leading candidates for nanocomposite reinforcement, but how CNT confinement influences the structural evolution of the PyC matrix is unknown. Here, the influence of aligned CNT proximity interactions on nano- and mesoscale structural evolution of phenol-formaldehyde-derived PyCs is established as a function of pyrolysis temperature (\(T_{\mathrm {p}}\)) using X-ray diffraction, Raman spectroscopy, and Fourier transform infrared spectroscopy. Aligned CNT PyC matrix nanocomposites are found to evolve faster at the mesoscale by plateauing in crystallite size at \(T_{\mathrm {p}}\) \(\sim\)800 \(^{\circ }\hbox {C}\), which is more than \(200\,\,^{\circ }\hbox {C}\) below that of unconfined PyCs. Since the aligned CNTs used here exhibit \(\sim\)80 nm average separations and \(\sim\)8 nm diameters, confinement effects are surprisingly not found to influence PyC structure on the atomic-scale at \(T_{\mathrm {p}}\) \(\le \)1400 \(^{\circ }\hbox {C}\). Since CNT confinement could lead to anisotropic crystallite growth in PyCs synthesized below \(\sim\)1000 \(^{\circ }\hbox {C}\), and recent modeling indicates that more slender crystallites increase PyC hardness, these results inform fabrication of PyC-based meta-materials with unrivaled specific mechanical properties.     

Small Multiple Fixed-Point Cell as Calibration Reference for a Dry Block Calibrator

A small multiple fixed-point cell (SMFPC) was designed to be used as in situ calibration reference of the internal temperature sensor of a dry block calibrator, which would allow its traceable calibration to the International Temperature Scale of 1990 (ITS-90) in the operating range of the block calibrator from \(70\,^{\circ }\hbox {C}\) to \(430\,^{\circ }\hbox {C}\). The ITS-90 knows in this temperature range, three fixed-point materials (FPM) indium, tin and zinc, with their respective fixed-point temperatures (\(\vartheta _\mathrm {FP}\)), In (\(\vartheta _\mathrm {FP}\,{=}\,156.5985\,^{\circ }\hbox {C}\)), Sn (\(\vartheta _\mathrm {FP}\,{=}\,231.928\,^{\circ }\hbox {C}\)) and Zn (\(\vartheta _\mathrm {FP}\,{=}\,419.527\,^{\circ }\hbox {C}\)). All of these FPM are contained in the SMFPC in a separate chamber, respectively. This paper shows the result of temperature measurements carried out in the cell within a period of 16 months. The test setup used here has thermal properties similar to the dry block calibrator. The aim was to verify the metrological properties and functionality of the SMFPC for the proposed application.     

Elastic and thermodynamic properties of zirconium- and hafnium-doped $$\hbox {Rh}_{3}\hbox {V}$$ intermetallic compounds: potential aerospace material

Structural, electronic, mechanical and thermodynamic properties of \(\hbox {Rh}_{3}\hbox {Zr}_{x}\hbox {V}_{1-x}\) and \(\hbox {Rh}_{3}\hbox {Hf}_{x}\hbox {V}_{1-x}\) (\(x = 0\), 0.125, 0.25, 0.75, 0.875 and 1) combinations are investigated by means of first-principles calculations based on the density functional theory within the generalized gradient approximation. Here, \(\hbox {Rh}_{3}\hbox {V}\) is chosen as the parent binary compound and the doping elements are zirconium and hafnium with the above-mentioned concentrations. The calculated lattice parameters and elastic modulus of binary \(\hbox {Rh}_{3}\hbox {Hf}\), \(\hbox {Rh}_{3}\hbox {V}\) and \(\hbox {Rh}_{3}\hbox {Zr}\) are in good agreement with the available experimental and other theoretical results. In this study, the following ternary materials viz., \(\hbox {Rh}_{3}\hbox {Zr}_{0.75}\hbox {V}_{0.25}\), \(\hbox {Rh}_{3}\hbox {Hf}_{0.25}\hbox {V}_{0.75}\) and \(\hbox {Rh}_{3}\hbox {Hf}_{0.75}\hbox {V}_{0.25}\) are found to be brittle/more brittle than the parent binary compound \(\hbox {Rh}_{3}\hbox {V}\), whereas the other ternary combinations, namely \(\hbox {Rh}_{3}\hbox {Zr}_{0.125}\hbox {V}_{0.875}\), \(\hbox {Rh}_{3}\hbox {Zr}_{0.25}\hbox {V}_{0.75}\), \(\hbox {Rh}_{3}\hbox {Zr}_{0.875}\hbox {V}_{0.125}\), \(\hbox {Rh}_{3}\hbox {Hf}_{0.125}\hbox {V}_{0.875}\) and \(\hbox {Rh}_{3}\hbox {Hf}_{0.875}\hbox {V}_{0.125}\) are found to be more ductile than \(\hbox {Rh}_{3}\hbox {V}\). The more brittle ternary combination, namely \(\hbox {Rh}_{3}\hbox {Hf}_{0.75}\hbox {V}_{0.25}\) (\(B = 229.32\,\hbox {GPa}\)) has the maximum Young’s modulus, shear modulus and hardness values; whereas the more ductile ternary \(\hbox {Rh}_{3}\hbox {Zr}_{0.25}\hbox {V}_{0.75}\) combination (\(B = 243.54\,\hbox {GPa}\)) is found to have the least values of Young’s modulus, shear modulus and hardness. The band structure, density of states histograms and charge density plots are drawn and discussed. Computed Debye temperature (\(\theta _{\mathrm{D}}\)), Grüneisen parameter (\(\zeta \)) and melting temperature (\(T_{\mathrm{m}})\) of the parent binary compound \(\hbox {Rh}_{3}\hbox {V}\), the more brittle \(\hbox {Rh}_{3}\hbox {Hf}_{0.75}\hbox {V}_{0.25}\) combination and the more ductile \(\hbox {Rh}_{3}\hbox {Zr}_{0.25}\hbox {V}_{0.75}\) combination are given by (895 K, 1.3491, 2788 K), (790 K, 1.2701, 2736 K) and (698 K, 1.7972, 2529 K), respectively.     

Role of MnO in manganese–borate binary glass systems: a study on structure and thermal properties

Structural and thermal properties of \(x\hbox {MnO}-(100-x)\hbox {B}_{2}\hbox {O}_{3}\) (where \(x=40\), 50 and 60 mol%) glass samples have been investigated with the employment of various techniques. Fourier transform infrared spectroscopy results revealed the influence of MnO on glass matrix. Decrease of B–O bond-related band intensities has been observed. MnO addition was found to introduce broken [\(\hbox {BO}_{2}\hbox {O}^{-}\)]\(_{{n}}\) chains. Differential scanning calorimetry (DSC) measurements presented decreasing \(T_{\mathrm{g}}\) that indicates depolymerization of glass matrix in the considered compositional range. Moreover, thermal stability (TS) parameter has been evaluated using the DSC technique. It slightly decreased with MnO content. X-ray photoelectron spectroscopy results provided the evidence for \(\hbox {Mn}^{2+}\) and \(\hbox {Mn}^{3+}\) presence. Multiplet splitting, close to that of MnO, has been observed. It has been concluded that most of the manganese ions existed in the divalent state. Photoluminescence study revealed that manganese ions are tetragonally co-ordinated in a glassy matrix.     

Role of reactive species in the photocatalytic degradation of amaranth by highly active N-doped $$\mathbf{WO}_{\mathbf{3}}$$

A novel, highly visible light active N-doped \(\hbox {WO}_{3}\) (\(\hbox {N}\)-\(\hbox {WO}_{3})\) is successfully synthesized via thermal decomposition of peroxotungstic acid–urea complex. The photocatalytic activity of \(\hbox {N}\)-\(\hbox {WO}_{3}\) is evaluated for the degradation of amaranth (AM) dye under visible and UVA light along with the role of reactive species, which has not yet been studied for \(\hbox {N}\)-\(\hbox {WO}_{3}\) photocatalysts. Doping of N into substitutional and interstitial sites of \(\hbox {WO}_{3}\) is confirmed by X-ray photoelectron spectroscopy and X-ray absorption near-edge spectroscopy. At a pH of 7, 1 g \(\hbox {l}^{-1}\) of \(\hbox {N}\)-\(\hbox {WO}_{3}\) can completely degrade \(10\,\hbox {mg } \hbox {l}^{-1}\) of AM within 1 h under visible and UVA light. For the degradation of AM by \(\hbox {N}\)-\(\hbox {WO}_{3}\) under visible and UVA light, \(\hbox {h}^{+}\) is found to be the main reactive species, while \(\cdot \hbox {OH}\) contributes to a lesser extent. On the contrary, \(^{1}\hbox {O}_{2}, \cdot \hbox {O}_{2}^{-}\) and \(\hbox {e}^{-}\) show negligible roles. The crucial role of \(\hbox {h}^{+}\) indicates effective suppression of electron–hole recombination after N doping. Dye sensitization and oxidation by reactive species are found to be the major pathway for the degradation of AM under visible and UVA light, respectively.     

Thermo-transport properties of Zn-substituted layered Li-nickel oxide, $$\hbox {LiNiO}_{2}$$

The layered Li-TM-\(\hbox {O}_{2}\) materials have been investigated extensively due to their application as cathodes in Li batteries. The electrical properties of these oxides can be tuned or controlled either by non-stoichiometry or substitution. Hence the thermo-transport properties of Zn-substituted \(\hbox {LiNi}_{1-x}\hbox {Zn}_{x}\hbox {O}_{2}\) for \(0 \le x \le 0.16\) have been investigated in the temperature range of 300–900 K for potential application as a high-temperature thermoelectric material. For \(x < 0.08\), the compounds were of single phase belonging to the space group R-3mH while for \(x > 0.08\) an additional minority phase, ZnO forms together with the main layered phase. All the compounds exhibit a semiconducting behaviour with electrical resistivity, varying in the range of  \(\sim 10^{-4}\) to \(10^{-2}\,\,\Omega \hbox {m}\) between 300 and 900 K. The electrical resistivity is found to increase with increasing Zn-substitution predominantly due to a decrease in the charge carrier hole mobility. The activation energy remains constant, \(\sim \)10  meV, with Zn-substitution. The Seebeck coefficient of the compounds is found to decrease with increasing temperature and increase with increasing Zn-substitution. The Seebeck coefficient decreases from \(\sim \)95 to \(35\ \upmu \hbox {V K}^{-1}\) and the corresponding power factor is \(\sim \)12\(\ \upmu \hbox {W m}^{-1}\ {\hbox {K}}^{-2}\) for the \(x = 0.16\) compound.     

Synthesis,characterization and electrochemical performance of $$\hbox {Li}_{2}\hbox {Ni}_{x}\hbox {Fe}_{1-x}\hbox {SiO}_{4}$$ cathode materials for lithium ion batteries

\(\hbox {Li}_{2}\hbox {Ni}_{x}\hbox {Fe}_{1-x}\hbox {SiO}_{4}\) (\(x = 0\), 0.2, 0.4, 0.6, 0.8 and 1) samples were prepared by a sol–gel process. The crystal structure of prepared samples of \(\hbox {Li}_{2}\hbox {Ni}_{x}\hbox {Fe}_{1-x}\hbox {SiO}_{4}\) was characterized using an X-ray diffractometer. Different crystallographic parameters such as crystallite size and lattice cell parameters have been calculated. Scanning electron microscopy and Fourier transform infrared spectroscopy investigations were carried out, which reveal the morphology and function groups of the synthesized samples. Furthermore, electrochemical impedance spectra measurements are performed. The obtained results indicated that the highest conductivity is achieved for the \(\hbox {Li}_{2}\hbox {Ni}_{0.4}\hbox {Fe}_{0.6}\hbox {SiO}_{4}\) electrode compound. It was observed that Li–\(\hbox {Li}_{2}\hbox {Ni}_{0.4}\hbox {Fe}_{0.6}\hbox {SiO}_{4}\) battery has initial discharge capacity of 164 mAh \(\hbox {g}^{-1}\) at 0.1C rate. The cycle life performance of all \(\hbox {Li}_{2}\hbox {Ni}_{x}\hbox {Fe}_{1-x}\hbox {SiO}_{4}\) batteries ranged between 100 and 156 mAh \(\hbox {g}^{-1}\) with coulombic efficiency range between 70.9 and 93.9%.