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 \({\upmu }\hbox {K}\).     

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.     

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.     

Effect of Pressure on Deep-Ocean Thermometers

A laboratory experiment was devised and performed to investigate the pressure dependence of Sea-Bird Electronics SBE35 and SBE3 deep-ocean thermometers. The thermometers were mounted in a massive brass comparator together with a calibrated standard platinum resistance thermometer. The measurements were performed in a pressure chamber in the pressure range 0.1 MPa to 60 MPa. The results showed that both the investigated SBE35 and SBE3 thermometers are pressure dependent, with a pressure sensitivity of +41 \(\upmu \)K\(\cdot \)MPa\(^{-1}\) and \(-77\) \(\upmu \)K\(\cdot \)MPa\(^{-1}\), respectively. Nevertheless, the results obtained in only one individual device per model (one SBE35 and one SBE3) cannot be generalized and further investigations of a larger number of devices per model are needed.     

Crystal structure,thermal behaviour,vibrational spectroscopy and optical properties of new compounds K$$_{}$$Ca(HAsO$$_{4}$$4)$$_{}\cdot $$·H$$_{}$$O with kröhnkite-type chain

The new kröhnkite compound called potassium calcium-bis-hydrogen arsenate dihydrate K\(_{2}\)Ca(HAsO\(_{4})_{2}\cdot \)2H\(_{2}\)O was obtained by hydrothermal method and characterized by X-ray diffraction, infrared spectroscopy, Raman scattering, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) analysis and optical (photoluminescence and absorption) properties. It crystallizes in the triclinic space group P\(\bar{1}\) and unit cell parameters \(a = 5.971(3)\) Å, \(b =6.634(3)\) Å, \(c = 7.856(4)\) Å, \(\alpha =104.532(9)\) \(^{\circ }\), \(\beta = 105.464(9)\) \(^{\circ }\) and \(\gamma = 109.698(9)\) \(^{\circ }\). The structure of K\(_{2}\)Ca(HAsO\(_{4})_{2}\cdot \)2H\(_{2}\)O built up from this infinite, (Ca(HAsO\(_{4})_{2}\)(H\(_{2}\)O)\(_{2})^{2+}\), was oriented along an axis resulting from the association of CaO\(_{6}\) octahedra alternating with each two HAsO\(_{4}\) tetrahedra by sharing corners. Each potassium atom links two adjacent chains by three oxygen atoms of HAsO\(_{4}\) tetrahedra. TGA and DSC have shown the absence of phase transition. The existence of vibrational modes corresponding to the kröhnkite is identified by the IR and Raman spectroscopies in the frequency ranges of 400–4000 and 20–4000 cm\(^{-1}\), respectively. The photoluminescence measurement show one peak at 507 nm, which is attributed to band–band (free electron–hole transitions) and (bound electron–hole transitions) emissions within the AsO\(_{4}\) inorganic part.     

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 \(K_{\mathrm{p}} = 27\%\).     

Study of Lanthanide Complexes with BTFA in Silica Gels by Photoacoustic Spectroscopy

In this work, lanthanide \(\beta \)-diketonate complexes Ln(btfa)\({}_{3} \cdot 2\hbox {H}_{2}\)O (Ln\(^{3+}\): Eu\(^{3+}\), Sm\(^{3+ }\), and Tb\(^{3+}\); btfa: 4,4,4-trifluoro-l-phenyl-1,3-butanedione) were incorporated into silica gels by a sol–gel method. Photoacoustic (PA) spectra of these complex-doped silica samples were measured and studied. The PA intensity of the \(\beta \)-diketonate ligand is nearly the same for lanthanide complexes in wet gels. After heat treatment at 150 \(^{\circ }\)C, however, the PA intensity of the ligand increases for Eu\(^{3+}\), Sm\(^{3+}\), and Tb\(^{3+}\) complexes in silica gels, respectively. Different PA intensities of the samples are interpreted by comparison with their luminescence spectra. The luminescence result is consistent with the PA spectra. The result indicates that lanthanide \(\beta \)-diketonate complexes cannot be formed in silica gels without a suitable heat treatment. Moreover, the relaxation process model is proposed based on the PA and luminescence results.     

Temperature and Heat Flow Rate Calibration of a Calvet Calorimeter from $$0\,{^{\circ }}\hbox {C}$$ to $$190 \,{^{\circ }}\hbox {C}$$19

This study describes the temperature and heat flow rate calibrations of a Calvet calorimeter (SETARAM, BT2.15) in the temperature range of 0–190 \({^{\circ }}\hbox {C}\). Temperature calibration is carried out using three reference materials, namely water, gallium, and indium, as specified in the International Temperature Scale of 1990 (ITS-90). The sample temperature of the Calvet calorimeter is corrected by the obtained mean value, \(-0.489 \,{^{\circ }}\hbox {C}\), of the measured extrapolated peak onset temperature (\(T_{e})\) when the heating rate (\(\upbeta )\) is zero (\(\Delta T_\mathrm{corr }(\upbeta ~=~0\))). The heat flow rate is calibrated using a reference material with a known heat capacity, namely SRM 720 \(\alpha \)-\(\hbox {Al}_{2}\hbox {O}_{3}\) (synthetic sapphire), which is traceable to the National Institute of Standards and Technology. From the heat flow rate measurements of the blank baseline and SRM 720, the proportional calibration factor, \(\hbox {K}_{\Phi }\), in the 0–190\( \,{^{\circ }}\hbox {C}\) temperature range was determined. The specific heat capacity of copper was measured with the obtained calibration values, and the measured data show consistency with the reference value.     

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.     

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.     

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.     

Critical Parameters and Critical-Region ($$p,\rho,T)$$ Data of trans-1,1,1,3-Tetrafluorobut-2-ene [HFO-1354mzy(E)]

This study presents the experimental measurement of the \(p\rho T\) properties and critical parameters of a low GWP type refrigerant, trans-1,1,1,3-Tetrafluorobut-2-ene (HFO-1354mzy(E)). The sample purity of the substance was 99 area %. \(p \rho T\) property measurements and visual observations of the meniscus of HFO-1354mzy(E) were carried out using a metal-bellows volumometer with an optical cell. The critical temperature was determined by observation of the critical opalescence. The critical pressure and critical density were determined as the inflection point of the isothermal \(p \rho T\) property data at the critical temperature. For more precise clarification of the thermodynamic surface in the vicinity of the critical point, additional \(p \rho T\) property measurements were carried out on three isotherms in the supercritical region. The expanded uncertainties (\(k = 2\)) in the temperature, pressure, and density measurements were estimated to be less than 3 mK, 1.2 kPa, and 0.32 \(\hbox {kg} \cdot \hbox {m}^{-3}\), respectively. The expanded uncertainties of the critical parameters were estimated to be less than 13 mK, 1.4 kPa, and 2.3 \(\hbox {kg} \cdot \hbox {m}^{-3}\), respectively. These values are the first reported for HFO-1354mzy(E) and are necessary for the development of its equation of state in the near future.     

Further Estimates of $$(T-T_{90})$$ Close to the Triple Point of Water

Recent advances in primary acoustic gas thermometry (AGT) have revealed significant differences between temperature measurements using the International Temperature Scale of 1990, \(T_{90}\), and thermodynamic temperature, T. In 2015, we published estimates of the differences \((T-T_{90})\) from 118 K to 303 K, which showed interesting behavior in the region around the triple point of water, \(T_\mathrm{TPW}=273.16\) K. In that work, the \(T_{90}\) measurements below \(T_\mathrm{TPW}\) used a different ensemble of capsule standard platinum resistance thermometers (SPRTs) than the \(T_{90}\) measurements above \(T_\mathrm{TPW}\). In this work, we extend our earlier measurements using the same ensemble of SPRTs above and below \(T_\mathrm{TPW}\), enabling a deeper analysis of the slope \(\mathrm{d}(T-T_{90})/\mathrm{d}T\) around \(T_\mathrm{TPW}\). In this article, we present the results of seven AGT isotherms in the temperature range 258 K to 323 K. The derived values of \((T-T_{90})\) have exceptionally low uncertainties and are in good agreement with our previous data and other AGT results. We present the values \((T-T_{90})\) alongside our previous estimates, with the resistance ratios W(T) from two SPRTs which have been used across the full range 118 K to 323 K. Additionally, our measurements show discontinuities in \(\mathrm{d}(T-T_{90})/\mathrm{d}T\) at \(T_\mathrm{TPW}\) which are consistent with the slope discontinuity in the SPRT deviation functions. Since this discontinuity is by definition non-unique, and can take a range of values including zero, we suggest that mathematical representations of \((T-T_{90})\), such as those in the mise en pratique for the kelvin (Fellmuth et al. in Philos Trans R Soc A 374:20150037, 2016. doi: 10.1098/rsta.2015.0037), should have continuity of \(\mathrm{d}(T-T_{90})/\mathrm{d}T\) at \(T_\mathrm{TPW}\).     

Study of $$\upbeta $$-phase development in spin-coated PVDF thick films

A study was conducted to ascertain the effect of variation in spin speed and baking temperature on \(\upbeta \)-phase content in the spin-coated poly(vinylidene fluoride) (PVDF) thick films (\({\sim }4{-}25\,\upmu \hbox {m}\)). Development of \(\upbeta \)-phase is dependent on film stretching and crystallization temperature. Therefore, to study the development of \(\upbeta \)-phase in films, stretching is achieved by spinning and crystallization temperature is adjusted by means of baking. PVDF films are characterized using Fourier transform infrared spectroscopy, X-ray diffraction, differential scanning calorimetry, and scanning electron microscopy. It is observed that crystallization temperature lower than \(60^{\circ }\hbox {C}\) and increase in spin speed increases the \(\upbeta \)-phase content in PVDF films. Crystallization temperature above \(60^{\circ }\hbox {C}\) reduces \(\upbeta \)-phase content and increases \(\upalpha \)-phase content. It was also observed that viscosity of the PVDF solution affects the \(\upbeta \)-phase development in films at a particular spin speed.     

Microwave-hydrothermal synthesis of mesoporous $$\upgamma $$-$$\hbox {Al}_{2}\hbox {O}_{3}$$Al2O3 and its impregnation with AgNPs for excellent catalytic oxidation of CO

Mesoporous \(\upgamma \)-alumina was synthesized by the microwave-hydrothermal process with a shorter duration time at 150\({^{\circ }}\)C/2 h followed by calcination at 550\({^{\circ }}\)C/1 h. Ag nanoparticles (AgNPs) were impregnated into \(\upgamma \)-alumina under a reducing atmosphere at 450\({^{\circ }}\)C. The synthesized product was characterized by X-ray diffraction (XRD), thermogravimetric (TG)/differential thermal analysis (DTA), X-ray photoelectron spectroscopy (XPS), \(\hbox {N}_{2}\) adsorption–desorption study, field-emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM). The BET surface area values of \(\upgamma \)-alumina and Ag-impregnated \(\upgamma \)-alumina were found to be 258 and 230 m\(^{2}\) g\(^{-1}\), respectively. FESEM images showed the formation of grain-like particles of 50–70 nm in size with a flake-like microstructure. The XRD, XPS and TEM studies confirmed the presence of Ag in the synthesized product. Catalytic properties of the product for CO oxidation was studied with the \(T_{50}\) (50% conversion) and \(T_{100}\) (100% conversion) values of 118 and 135\({^{\circ }}\)C, respectively; the enhanced values were compared with the literature reported values.     

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.     

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.     

Synthesis,structure and thermoelectric properties of $$\mathrm{La}_{1-x}\mathrm{Na}_{x}\mathrm{CoO}_{3 }$$ perovskite oxides

Monovalent ion doped lanthanum cobaltate \(\hbox {La}_{1-x}\hbox {Na}_{x}\hbox {CoO}_{3 }\) (\(0 \le x \le 0.25\)) compositions were synthesized by the nitrate–citrate gel combustion method. All the heat treatments were limited to below 1123 K, in order to retain the Na stoichiometry. Structural parameters for all the compounds were confirmed by the Rietveld refinement method using powder X-ray diffraction (XRD) data and exhibit the rhombhohedral crystal structure with space group R-3c (No. 167). The scanning electron microscopy study reveals that the particles are spherical in shape and sizes, in the range of 0.2–0.5 \(\upmu \)m. High temperature electrical resistivity, Seebeck coefficient and thermal conductivity measurements were performed on the high density hot pressed pellets in the temperature range of 300–800 K, which exhibit p-type conductivity of pristine and doped compositions. The X-ray photoelectron spectroscopy (XPS) studies confirm the monotonous increase in \(\hbox {Co}^{4+}\) with doping concentration up to \(x = 0.15\), which is correlated with the electrical resistivity and Seebeck coefficient values of the samples. The highest power factor of \(10~\upmu \hbox {W~mK}^{-2 }\) is achieved for 10 at% Na content at 600 K. Thermoelectric figure of merit is estimated to be \({\sim }1 \times 10^{-2}\) at 780 K for 15 at% Na-doped samples.     

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.     

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.