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.     

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.     

Influence of Thermal Annealings in Argon on the Structural and Thermochromic Properties of $$\mathrm{MoO}_{3}$$ Thin Films

The effect of thermal annealing in an inert atmosphere (argon) on the structural and thermochromic properties of \(\hbox {MoO}_{3}\) thin films was investigated. \(\hbox {MoO}_{3}\) thin films were deposited by thermal evaporation in vacuum of \(\hbox {MoO}_{3}\) powders. X-ray diffraction patterns of the films showed the presence of the monoclinic Magneli phase \(\hbox {Mo}_{9}\hbox {O}_{26}\) for annealing temperatures above \(250\,{^{\circ }}\hbox {C}\). Absorbance spectra of the films annealed in argon indicated that their thermochromic response increases with the annealing temperature in the analyzed range (23 \({^{\circ }}\hbox {C}\)–300 \({^{\circ }}\hbox {C}\)), a result opposite to the case of thermal annealings in air, for which case the thermochromic response shows a maximum value around 200 \({^{\circ }}\)C–225 \({^{\circ }}\)C and decreases for higher temperatures. These results are explained in terms of a higher density of oxygen vacancies formed upon thermal treatments in inert atmospheres.     

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.     

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%.     

The Influence of Impurities on the Zinc Fixed Point

Impurities are considered to be the most significant source of uncertainty for the realization of the International Temperature Scale of 1990 by means of metal fixed points. The determination and further reduction in this uncertainty require a traceable chemical analysis of dissolved impurities in the fixed-point metal and accurate knowledge of the specific temperature change caused by impurities (slope of the liquidus line). We determined the slope of the liquidus line for three binary systems and present results and conclusions from the chemical analysis of zinc with a nominal purity of 7N. For the Fe–Zn system, we determined a liquidus slope of (\(-0.91\pm 0.14\)) mK / (\(\upmu \hbox {g}{\cdot }\hbox { g}^{-1}\)) from the evaluation of freezing plateaus and (\(-0.76~\pm 0.20\)) mK / (\(\upmu \hbox {g}{\cdot }\hbox { g}^{-1}\)) from the evaluation of melting plateaus; for the Pb–Zn system, the corresponding results are (\(-0.27~\pm 0.05\)) mK / (\(\upmu \hbox {g}{\cdot }\hbox { g}^{-1}\)) and (\(-0.26~\pm 0.05\)) mK / (\(\upmu \hbox {g}{\cdot }\hbox { g}^{-1}\)). Although for the Sb–Zn system, we determined a liquidus slope of about \(-0.8\) mK / (\(\upmu \hbox {g}{\cdot }\hbox { g}^{-1}\)), our investigations showed that a correction of the influence of antimony is highly questionable because antimony can be found in zinc in a fully dissolved state or precipitated as an insoluble compound. Iron is the only impurity where a correction of the fixed-point temperature was possible. For the realization of the zinc fixed point at PTB, this correction is between 2 \(\upmu \)K and 16 \(\upmu \)K depending on the batch of zinc used. The influence of the sum of all impurities was estimated by means of the OME method. The resulting uncertainty contribution is between 12 \({\upmu }\hbox {K}\) and 48 \({\upmu }\hbox {K}\).     

A comparative study on dielectric behaviours of Au/(Zn-doped PVA)/<Emphasis Type="Italic">n</Emphasis>-4H-SiC (MPS) structures with different interlayer thicknesses using impedance spectroscopy methods

Three different thicknesses (50, 150 and 500 nm) Zn-doped polyvinyl alcohol (PVA) was deposited on n-4H-SiC wafer as interlayer by electrospinning method and so, Au/(Zn-doped PVA)/n-4H-SiC metal–polymer–semiconductor structures were fabricated. The thickness effect of Zn-doped PVA on the dielectric constant (\(\varepsilon ^{\prime }\)), dielectric loss (\(\varepsilon ^{{\prime }{\prime }}\)), loss-tangent (tan \(\delta \)), real and imaginary parts of electric modulus (\(M^{\prime }\) and \(M^{{\prime }{\prime }})\) and ac electrical conductivity \((\sigma _{\mathrm{ac}})\) of them were analysed and compared using experimental capacitance (C) and conductance (\(G/\omega \)) data in the frequency range of 1–500 kHz at room temperature. According to these results, the values of \(\varepsilon ^{\prime }\) and \(\varepsilon ^{{\prime }{\prime }}\) decrease with increasing frequency almost exponentially, \(\sigma _{\mathrm{ac}}\) increases especially, at high frequencies. The \(M^{\prime }\) and \(M^{{\prime }{\prime }}\) values were obtained from the \(\varepsilon ^{\prime }\) and \(\varepsilon ^{{\prime }{\prime }}\) data and the \(M^{\prime }\) and \(M^{{\prime }{\prime }}\) vs. f plots were drawn for these structures. While the values of \(\varepsilon ^{\prime }\), \(\varepsilon ^{{\prime }{\prime }}\) and tan \(\delta \) increase with increasing interlayer thickness, the values of \(M^{\prime }\) and \(M^{{\prime }{\prime }}\) decrease with increasing interlayer thickness. The double logarithmic \(\sigma _{\mathrm{ac}}\) vs. f plots for each structure have two distinct linear regimes with different slopes, which correspond to low and high frequencies, respectively, and it is prominent that there exist two different conduction mechanisms. Obtained results were found as a strong function of frequency and interlayer thickness.     

Measurement on the Thermal Properties of Graphene Powder

We report on an in-plane thermal diffusivity study of suspended graphene powder (GP) measured by the transient electro-thermal (TET) technique. The GP with a density of 0.24 \(\hbox {g}\,\cdot \,\hbox {cm}^{-3}\) is made up of five–six-layer graphene. And the average size of graphene flakes used in our study is 0.98 \(\upmu \)m. The intrinsic thermal conductivity perpendicular to in-plane of GP is determined at 18.8 \(\hbox {W}\,\cdot \,(\hbox {m}\,\cdot \,\hbox {K})^{-1}\) using the thermal conductivity instrument, and the range of the in-plane thermal diffusivity of GP is identified from \(0.86\times 10^{-5 }\,\hbox {m}^{2 }\,\cdot \,\hbox {s}^{-1}\) to \(1.52\times 10^{-5 }\,\hbox {m}^{2}\,\cdot \,\hbox {s}^{-1}\) measured by the TET technique. Accordingly, the corresponding intrinsic thermal conductivity is 13.5 \(\hbox {W}\,\cdot \,(\hbox {m}\,\cdot \,\hbox {K})^{-1}\)–23.8 \(\hbox {W}\,\cdot \,(\hbox {m}\,\cdot \,\hbox {K})^{-1}\). It is obvious that the two methods used in the experimental research on the intrinsic thermal conductivity of GP in different directions are not only the same order of magnitude but also have a maximum difference of only 5 \(\hbox {W}\,\cdot \,(\hbox {m}\,\cdot \,\hbox {K})^{-1}\). The results of our experiments are about one order of magnitude lower than those reported for four–five-layer graphene. There are various porosities in the whole sample after the compaction steps in the preparation of the samples, which gives rise to a large thermal contact resistance. And widely uneven surface defects observed under an optical microscope for the studied GP lead to substantial phonon scattering. Those factors combine together to give the observed significant reduction in the thermal conductivity.     

Synthesis and luminescence in sol–gel auto-combustion-synthesized $$\hbox {CaSnO}_{3}{:}\hbox {Eu}^{3+}$$ phosphor

Undoped and Eu-doped \(\hbox {CaSnO}_{3}\) nanopowders were prepared by a facile sol–gel auto-combustion method calcined at \(800{^{\circ }}\hbox {C}\) for 1 h. The samples are found to be well-crystallized pure orthorhombic \(\hbox {CaSnO}_{3}\) structure. Photoluminescence (PL) measurements indicated that the undoped sample exhibits a broad blue emission at about 420–440 nm, which can be recognized from an intrinsic centre or centres in \(\hbox {CaSnO}_{3}\). Eu-doped \(\hbox {CaSnO}_{3}\) showed broad blue emission centred about 434 nm, a weak peak at 465 nm and a sharp intense yellow emission line at 592 nm. The emission situated at 592 nm was assigned to the f–f transition of \(^{5}\hbox {D}_{0}\rightarrow ^{7}\hbox {F}_{1}\) in \(\hbox {Eu}^{3+}\) ions. The afterglow emission and PL decay results in Eu-doped \(\hbox {CaSnO}_{3}\) phosphor, which revealed that there are at least two different traps in this phosphor. From the obtained results, \(\hbox {Eu}^{3+}\)-doped \(\hbox {CaSnO}_{3}\) phosphor could be proposed as a potential white luminescent optical material.     

Macroscopic Thermal Rectification Device Using Vanadium Dioxide Thin Film

A thermal rectifier is a device in which heat flows in the forward direction but very little can flow in the opposite direction. Because the heat current can be controlled, the device is promising for future practical applications. In this study, the experiments were performed to investigate temperature-gated thermal rectification using macroscopic vanadium dioxide \((\hbox {VO}_{2})\) thin films deposited on an asymmetric substrate. The \(\hbox {VO}_{2}\) phase transition, occurred near 340 K, changed both the electrical and thermal properties. Therefore, we used these properties to investigate the thermal rectification. The \(\hbox {VO}_{2}\) thin films were prepared on cover glass substrates by RF sputtering with a \(\hbox {VO}_{2}\) disk target at \(500~{^{\circ }}\hbox {C}\). The morphology of the thin films was investigated. Silver paste and a copper band were used to connect the films with a heater and temperature controller. We observed thermal rectification in the temperature range of T = 310 K–370 K in several film samples obtained with different degrees of asymmetry, deposition times, and post-annealing times. It is found that \(60{^{\circ }}\) triangular-shaped samples have a rectification coefficient of 1.14, and the rectification coefficient is increased with the increasing of the angle. In addition, the two rectangular-shaped samples have the coefficient of 1.06, which could also be enhanced by increasing the ratio of width.     

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.     

Thermal Decomposition Study on CuInSe$$_{}$$ Single Crystals

The thermal analysis of the chemical vapor transport (CVT)-grown \(\hbox {CuInSe}_{2}\) single crystals was carried out by recording the thermogravimetric, differential thermogravimetric and differential thermal analysis curves. All the three thermo-curves were recorded simultaneously by thermal analyzer in the temperature range of ambient to 1080 K in inert nitrogen atmosphere. The thermo-curves were recorded for four heating rates of 5 K \(\cdot \,\hbox {min}^{-1}\), 10 K \(\cdot \,\hbox {min}^{-1}\), 15 K \(\cdot \,\hbox {min}^{-1}\) and 20 K \(\cdot \,\hbox {min}^{-1}\). The TG curve analysis showed negligible mass loss in the temperature range of ambient to 600 K, stating the sample material to be thermally stable in this temperature range. Above 601 K to the temperature of 1080 K, the sample showed continuous mass loss. The DTG curves showed two peaks in the temperature range of 601 K to 1080 K. The corresponding DTA showed initial minor exothermic nature followed by endothermic nature up to nearly 750 K and above it showed exothermic nature. The initial exothermic nature is due to absorbed water converting to water vapor, whereas the endothermic nature states the absorption of heat by the sample up to nearly 950 K. Above nearly 950 K the exothermic nature is due to the decomposition of sample material. The absorption of heat in the endothermic region is substantiated by corresponding weight loss in TG. The thermal kinetic parameters of the CVT-grown \(\hbox {CuInSe}_{2}\) single crystals were determined employing the non-mechanistic Kissinger relation. The determined kinetic parameters support the observations of the thermo-curves.     

Preparation,characterization of chitosan/bamboo charcoal/poly(methacrylate) composite beads

Preparation and characterization of a low-cost, novel steam-activated bamboo charcoal (BC) and poly(methacrylate) (PMAA) bound with chitosan (CTS) to form chitosan/bamboo charcoal/poly(methacrylate) (CTS/BC/PMAA) composite beads is reported for the first time in this paper. The characteristics are revealed by techniques such as X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC), scanning electron microscopy (SEM), Brunauer Emmett Teller (BET), solution pH and pH at point of zero charge \((\hbox {pH}_{\mathrm {pzc}})\). The composite beads possessed a dominant acidic surface group of 0.663 mmol \(\hbox {g}^{\mathrm {-1}}\), as revealed by Boehm titration method. This acidity was confirmed by its solution pH of 6.46; \(\hbox {pH}_{\mathrm {pzc}}\) of 6.70 and increase in oxygen surface via XPS analysis. \(\hbox {N}_{\mathrm {2}}\) adsorption–desorption isotherms at 77 K of the beads revealed high BET surface area (SA) of 681.15 \(\hbox {m}^{\mathrm {2}}\hbox {g}^{\mathrm {-1}}\). Langmuir model affords a SA of 773.34 \(\hbox {m}^{\mathrm {2}}\hbox {g}^{\mathrm {-1}}\). SEM showed the microporous nature of the composite beads. The properties of CTS/BC/PMAA composite beads were compared to CTS/BC and neat BC. Thermal stability and successful coating of 5.1 wt% of PMAA and 6.8 wt% of CTS to CTS/BC/PMAA beads were shown by DSC and TGA analyses. The composite beads showed low carbon particle released at pH 7.4 and 6.8. Furthermore, dynamic adsorption revealed that CTS/BC/PMAA composite beads can be used to capture a polar substance, such as creatinine.     

Solubility of Nitrogen Gas in Aqueous Solution of Tetra-<Emphasis Type="Italic">n</Emphasis>-Butylammonium Bromide

Semiclathrate hydrates are water-based host-guest compounds formed from aqueous solutions of ionic guest substances. These materials can greatly moderate formation pressures and temperatures from canonical gas hydrates. This is a significant advantage for industrial applications such as gas separation and storage. \(\hbox {N}_{2}\) gas is a major component contained in various flue gases and is usually mixed with \(\hbox {CO}_{2}\). Semiclathrate hydrates can separate these gases under moderate thermodynamic conditions. Tetra-n-butylammonium bromide (TBAB) is a widely used ionic guest substance. To develop the application technologies and their theoretical models, solubility data of \(\hbox {N}_{2}\) gas in TBAB aqueous solutions are required. In this study, we report \(\hbox {N}_{2}\) gas solubility measured by an absolute gravimetric method for the semiclathrate hydrate formation system of \(\hbox {TBAB} + \hbox {H}_{2}\hbox {O} + \hbox {N}_{2}\). The measurement pressures, temperatures and TBAB mass fractions were 3 MPa, 5 MPa and 7 MPa, 292.15 K, 302.15 K and 307.15 K, and 0 (pure water), 0.10, 0.20, 0.32 and 0.40, respectively. The uncertainties were 0.056 MPa, 0.44 K and 0.00012 in mole fraction. Although the technical difficulty lays on measurements of small \(\hbox {N}_{2}\) gas solubility by the absolute gravimetric method, our data implied the unique gas dissolution property of aqueous TBAB solution depending on the TBAB concentration. The aqueous TBAB solutions with mass fractions of 0.10 and 0.20 had similar \(\hbox {N}_{2}\) gas solubility as that in pure water. With higher mass fractions, 0.32 and 0.40, the \(\hbox {N}_{2}\) gas solubility slightly increased from that in pure water, which implies the salting-in effect of TBAB.     

Electrochemical impedance studies of capacity fading of electrodeposited ZnO conversion anodes in Li-ion battery

Electrodeposited ZnO coatings suffer severe capacity fading when used as conversion anodes in sealed Li cells. Capacity fading is attributed to (i) the large charge transfer resistance, \(R_{\mathrm{ct}}\) (300–700 \(\Omega \)) and (ii) the low \(\hbox {Li}^{+}\) ion diffusion coefficient, \(D_{\mathrm{Li}}^{+}\ (10^{-15}\) to \(10^{-13}\hbox { cm}^{2}\hbox { s}^{-1})\). The measured value of \(R_{\mathrm{ct}}\) is nearly 10 times higher and \(D_{\mathrm{Li}}^{+}\) 10–100 times lower than the corresponding values for \(\hbox {Cu}_{2}\hbox {O}\), which delivers a stable reversible capacity.     

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.     

Microwave hydrothermal synthesis and upconversion luminescence properties of $$\hbox {Yb}^{3+}$$/$$\hbox {Tm}^{3+}$$Tm3+ co-doped $$\hbox {NaY}(\hbox {MoO}_{4})_{2}$$NaY(MoO4)2 phosphor

Tetragonal \(\text {NaY}(\text {MoO}_{4})_{2}\) (NYM) phosphors co-doped with \(\hbox {Yb}^{3+}\) and \(\hbox {Tm}^{3+}\) ions were synthesized through microwave hydrothermal method followed by calcining treatment. Powder X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy and photoluminescence spectra were used to characterize the properties of as-prepared samples. The results show that \(\hbox {Yb}^{3+}\)/\(\hbox {Tm}^{3+}\) co-doped NYM displayed bright blue emission near 472 and 476 nm (\(^{1}\hbox {G}_{4}\rightarrow {}^{3}\hbox {H}_{6}\) transition), strong near-infrared upconversion (UC) emission around 795 nm (\(^{3}\hbox {H}_{4}\rightarrow {}^{3}\hbox {H}_{6}\) transition). The optimum doping concentrations of \(\hbox {Yb}^{3+}\) and \(\hbox {Tm}^{3+}\) for the most intense UC luminescence were obtained, and the related UC mechanism of \(\hbox {Yb}^{3+}\)/\(\hbox {Tm}^{3+}\) co-doped NYM depending on pump power was studied in detail.     

Fabrication and enhanced photoluminescence properties of $$\hbox {NaLa}(\hbox {MoO}_{4})_{2}$$: $$\hbox {Sm}^{3+}$$Sm3+, $$\hbox {Bi}^{3+}$$Bi3+ phosphors with high efficiency white-light-emitting

The tetragonal scheelite-type \(\hbox {Sm}^{3+}\hbox {/Bi}^{3+}\) ions co-doped with \(\hbox {NaLa}(\hbox {MoO}_{4})_{2}\) phosphors were synthesized by a facile sol–gel and combustion process using citric acid as complexing agent. The crystal structure and morphology of these as-prepared samples were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Furthermore, UV-absorption and the photoluminescence (PL) properties of these phosphors were systematically investigated and the PL of the phosphors shows strong white light emissions. Efficient energy transfer from the \(\hbox {MoO}_{4}^{2-}\) group or \(\hbox {Bi}^{3+}\) ions to \(\hbox {Sm}^{3+}\) ions was established by PL investigation excited at 405 nm. The PL intensity of the studied materials was investigated as a function of different \(\hbox {Sm}^{3+}\) and \(\hbox {Bi}^{3+}\) concentrations. The PL investigations revealed that the phosphors exhibit apparent characteristic emissions, which is ascribed to the transition from the ground state energy level \(^{4}\hbox {G}_{5/2}\) to excited state energy levels \(^{6}\hbox {H}_{\mathrm{J}}\) (\(J= 5/2, 7/2, 9/2\)) and the \(\hbox {NaLa}(\hbox {MoO}_{4})_{2}\): 4 mol% \(\hbox {Sm}^{3+}\) and \(\hbox {NaLa}(\hbox {MoO}_{4})_{2}\): 4 mol% \(\hbox {Sm}^{3+}\), 8 mol% \(\hbox {Bi}^{3+}\) present white emissions with the CIE coordinates of (0.350, 0.285) and (0.285, 0.229), respectively. The absolute quantum efficiencies of the phosphors are 40% (\(\hbox {NaLa}(\hbox {MoO}_{4})_{2}\): 4 mol% \(\hbox {Sm}^{3+}\)) and 52% (\(\hbox {NaLa}(\hbox {MoO}_{4})_{2}\): 4 mol% \(\hbox {Sm}^{3+}\), 8 mol% \(\hbox {Bi}^{3+}\)), 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.     

Ionic conductivity and diffusion coefficient of barium-chloride-based polymer electrolyte with poly(vinyl alcohol)–poly(4-styrenesulphonic acid) polymer complex

A composite polymer electrolyte comprising poly(vinyl alcohol)–poly(4-styrenesulphonic acid) with barium chloride dihydrate (\(\hbox {BaCl}_{2}{\cdot } 2\hbox {H}_{2}\hbox {O}\)) salt complex has been synthesized following the usual solution casting. The ionic conductivity of polymer electrolyte was analysed by impedance spectroscopy. The highest room temperature (at 30\({^{\circ }}\)C) conductivity evaluated was 9.38 \(\times \) 10\(^{-6}\) S cm\(^{-1}\) for 20 wt% loading of \(\hbox {BaCl}_{2}\) in the polymer electrolyte. This has been referred to as the optimum conducting composition. The temperature-dependent ionic conductivity of the polymer electrolyte exhibits the Arrhenius relationship, which represents the hopping of ions in polymer composites. Cation and anion diffusion coefficients are evaluated using the Trukhan model. The transference number and enhanced conductivity imply that the charge transportation is due to ions. Therefore this polymer electrolyte can be further studied for the development of electrochemical device applications.