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.     

Microstructure and Magnetic Properties of Sn<Subscript>1 − <Emphasis Type="Italic">x</Emphasis></Subscript>Ni<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>2</Subscript> Thin Films Prepared by Flash Evaporation Technique

An effort was made to develop semiconductor oxide-based room temperature dilute magnetic semiconductor (DMS) thin films based on wide band gap and transparent host lattice with transition metal substitution. The Sn\(_{\mathrm {1}-x}\)Ni\(_{x}\textit {O}_{\mathrm {2}}\) (\(x\,= \mathrm {0.00, 0.03, 0.05, 0.07, 0.10, and \,0.15}\)) thin film samples were prepared on glass substrates by flash evaporation technique. All the samples were shown single phase crystalline rutile structure of host SnO\(_{\mathrm {2}}\) with dominant (110) orientation. The Ni substitution promotes reduction of average crystallite size in SnO\(_{\mathrm {2}}\) as evidenced from the reduction of crystallite size from 40 (SnO\(_{\mathrm {2}}\)) to 20 nm (Sn\(_{\mathrm {0.85}}\)Ni\(_{\mathrm {0.15}}\textit {O}_{\mathrm {2}}\)). In the energy dispersive spectra as well as X-ray photoelectron spectra of all the samples show, the chemical compositions are close to stoichiometric with noticeable oxygen deficiency. The crystalline films were formed by coalescence of oval-shaped polycrystalline particles of 100 nm size as evidenced from the electron micrographs. The energy band gap of DMS films decreases from 4 (SnO\(_{\mathrm {2}}\)) to 3.8 eV (x \(=\) 0.05) with increase of Ni content. The magnetic hysteresis loops of all the samples at room temperature show soft ferromagnetic nature except for SnO\(_{\mathrm {2}}\) film. The SnO\(_{\mathrm {2}}\) films show diamagnetic nature and it converts into ferromagnetic upon substitution of 3 % Sn\(^{\mathrm {4+}}\) by Ni\(^{\mathrm {2+}}\). The robust intrinsic ferromagnetism (saturation magnetization, 21 emu/cm\(^{\mathrm {3}}\)). Further increase of Ni content weakens ferromagnetic strength due to Ni-O antiferromagnetic interactions among the nearest neighbour Ni ions via O\(^{\mathrm {2-}}\) ions. The observed magnetic properties were best described by bound magnetic polarons model.     

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 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.     

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.     

Bootstrap in semi-functional partial linear regression under dependence

This paper deals with the semi-functional partial linear regression model \(Y={{\varvec{X}}}^\mathrm{T}{\varvec{\beta }}+m({\varvec{\chi }})+\varepsilon \) under \(\alpha \)-mixing conditions. \({\varvec{\beta }} \in \mathbb {R}^{p}\) and \(m(\cdot )\) denote an unknown vector and an unknown smooth real-valued operator, respectively. The covariates \({{\varvec{X}}}\) and \({\varvec{\chi }}\) are valued in \(\mathbb {R}^{p}\) and some infinite-dimensional space, respectively, and the random error \(\varepsilon \) verifies \(\mathbb {E}(\varepsilon |{{\varvec{X}}},{\varvec{\chi }})=0\). Naïve and wild bootstrap procedures are proposed to approximate the distribution of kernel-based estimators of \({\varvec{\beta }}\) and \(m(\chi )\), and their asymptotic validities are obtained. A simulation study shows the behavior (on finite sample sizes) of the proposed bootstrap methodology when applied to construct confidence intervals, while an application to real data concerning electricity market illustrates its usefulness in practice.     

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.     

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%.     

Fracture of pre-cracked thin metallic conductors due to electric current induced electromagnetic force

We investigated propagation of a sharp crack in a thin metallic conductor with an edge crack due to electric current induced electromagnetic forces. Finite element method (FEM) simulations showed mode I crack opening in the edge-cracked conductor due to the aforementioned (i.e., self-induced) electromagnetic forces. Mode I stress intensity factor due to the self-induced electromagnetic forces, \(K_{\mathrm{IE},}\) was evaluated numerically as \(K_{\mathrm{IE}}=\upmu l^{2}j^{2}(\uppi a)^{0.5}f(a/w)\), where \(\upmu \) is the magnetic permeability, l is the length of the conductor, a is the crack length, j is the current density, w is the width of the sample and f(a / w) is a geometric factor. Effect of dynamic electric current loading on edge-cracked conductor, incorporating the effects of induced currents, was also studied numerically, and dynamic stress intensity factor, \(K_{\mathrm{IE,d}}\), was observed to vary as \(K_{\mathrm{IE,d}} \sim f_{d}(a/w)j^{2}(\uppi a)^{1.5}\). Consistent with the FEM simulation, experiments conducted using \(12\,\upmu \hbox {m}\) thick Al foil with an edge crack showed propagation of sharp crack due to the self-induced electromagnetic forces at pulsed current densities of \(\ge \) \(1.85\times 10^{9}\,\hbox {A/m}^{2}\) for \(a/w = 0.5\). Further, effects of current density, pulse-width and ambient temperature on the fracture behavior of the Al foil were observed experimentally and corroborated with FEM simulations.     

Experimental Study of the Thermodynamic Properties of Diethyl Ether (DEE) at Saturation

The isochoric heat capacities \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\), saturation densities (\({\rho _{\rm S}^{\prime}}\) and \(({\rho_{\rm S}^{\prime\prime})}\)), vapor pressures (P _S), thermal-pressure coefficients \({\gamma_V=\left({\partial P/\partial T}\right)_V}\), and first temperature derivatives of the vapor pressure γ _S = (dP _S/dT) of diethyl ether (DEE) on the liquid–gas coexistence curve near the critical point have been measured with a high-temperature and high-pressure nearly constant-volume adiabatic piezo-calorimeter. The measurements of \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) were made in the liquid and vapor one- and two-phase regions along the coexistence curve. The calorimeter was additionally supplied with a calibrated extensometer to accurately and simultaneously measure the PVT, C _V VT, and thermal-pressure coefficient, γ _V , along the saturation curve. The measurements were carried out in the temperature range from 416 K to 466.845 K (the critical temperature) for 17 liquid and vapor densities from 212.6 kg · m^?3 to 534.6 kg · m^?3. The quasi-static thermo- (reading of PRT, T ? τ plot) and baro-gram (readings of the tensotransducer, P ? τ plot) techniques were used to accurately measure the phase-transition parameters (P _S ,ρ _S ,T _S) and γ _V . The total experimental uncertainty of density (ρ _S), pressure (P _S), temperature (T _S), isochoric heat capacities \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\), and thermal-pressure coefficient, γ _V , were estimated to be 0.02 % to 0.05 %, 0.05 %, 15 mK, 2 % to 3 %, and 0.12 % to 1.5 %, respectively. The measured values of saturated caloric \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) and saturated thermal (P _S, ρ _S, T _S) properties were used to calculate other derived thermodynamic properties C _P , C _S, W, K _T , P _int, ΔH _vap, and \({\left({\partial V/\partial T}\right)_P^{\prime}}\) of DEE near the critical point. The second temperature derivatives of the vapor pressure, (d² P _S/dT ²), and chemical potential, (d² μ/dT ²), were also calculated directly from the measured one- and two-phase liquid and vapor isochoric heat capacities \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) near the critical point. The derived values of (d² P _S/dT ²) from calorimetric measurements were compared with values calculated from vapor–pressure equations. The measured and derived thermodynamic properties of DEE near the critical point were interpreted in terms of the “complete scaling” theory of critical phenomena. In particular, the effect of a Yang–Yang anomaly of strength R _μ on the coexistence-curve diameter behavior near the critical point was studied. Extended scaling-type equations for the measured properties P _S (T), ρ _S (T), and \({({C_{V1}^{\prime}} ,{C_{V1}^{\prime\prime}},{C_{V2}^{\prime}},{C_{V2}^{\prime\prime}})}\) as a function of temperature were developed.     

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.     

The Effect of Inhomogeneous Phase on the Critical Temperature of Smart Meta-superconductor MgB<Subscript>2</Subscript>

The critical temperature (T_C) of MgB₂, one of the key factors limiting its application, is highly desired to be improved. On the basis of the meta-material structure, we prepared a smart meta-superconductor structure consisting of MgB₂ micro-particles and inhomogeneous phases by an ex situ process. The effect of inhomogeneous phase on the T_C of smart meta-superconductor MgB₂ was investigated. Results showed that the onset temperature (\(T_{\mathrm {C}}^{\text {on}}\)) of doping samples was lower than those of pure MgB₂. However, the offset temperature (\({T}_{\mathrm {C}}^{\text {off}}\)) of the sample doped with Y₂O₃:Eu³⁺ nanosheets with a thickness of 2 ～ 3 nm which is much less than the coherence length of MgB₂ is 1.2 K higher than that of pure MgB₂. The effect of the applied electric field on the T_C of the sample was also studied. Results indicated that with the increase of current, \({T}_{\mathrm {C}}^{\text {on}}\) is slightly increased in the samples doping with different inhomogeneous phases. With increasing current, the \({T}_{\mathrm {C}}^{\text {off}}\) of the samples doped with nonluminous inhomogeneous phases was decreased. However, the \({T}_{\mathrm {C}}^{\text {off}}\) of the luminescent inhomogeneous phase doping samples increased and then decreased with increasing current.     

Network structure dependence on unconstrained isothermal-recovery processes for shape-memory thiol-epoxy “click” systems

The shape-memory response (SMR) of “click” thiol-epoxy polymers produced using latent catalysts, with different network structure and thermo-mechanical properties, was tested on unconstrained shape-recovery processes under isothermal conditions. Experiments at several programming temperatures (\(T_{\mathrm{prog}}\)) and isothermal-recovery temperatures (\(T_{\mathrm{iso}}\)) were carried out, and the shape-memory stability was analyzed through various consecutive shape-memory cycles. The temperature profile during the isothermal-recovery experiments was monitored, and it showed that the shape-recovery process takes place while the sample is becoming thermally stable and before stable isothermal temperature conditions are eventually reached. The shape-recovery process takes place in two different stages regardless of \(T_{\mathrm{iso}}\): a slow initial stage until the process is triggered at a temperature strongly related with the beginning of network relaxation, followed by the typical exponential decay of the relaxation processes until completion at a temperature below or very close to \(T_{\mathrm{g}}\). The shape-recovery process is slower in materials with more densely crosslinked and hindered network structures. The shape-recovery time (\(t_{\mathrm{sr}}\)) is significantly reduced when the isothermal-recovery temperature \(T_{\mathrm{iso}}\) increases from below to above \(T_{\mathrm{g}}\) because the network relaxation dynamics accelerates. However, the temperature range from the beginning to the end of the recovery process is hardly affected by \(T_{\mathrm{iso}}\); at higher \(T_{\mathrm{iso}}\) it is only slightly shifted to higher temperatures. These results suggest that the shape-recovery process can be controlled by changing the network structure and working at \(T_{\mathrm{iso}} < T_{\mathrm{g}}\) to maximize the effect of the structure and/or by increasing \(T_{\mathrm{iso}}\) to minimize the effect but increasing the shape-recovery rate.     

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 \(\hbox {BiO}_{0.75}\hbox {F}_{0.25}\hbox {BiS}_{2}\).     

Magnetism in Solid Oxygen Studied by High-Pressure Neutron Diffraction

A systematic modification of the entropy trajectory (\(S_\mathrm{m}(T)\)) is observed at very low temperature in magnetically frustrated systems as a consequence of the constraint (\(S_\mathrm{m}\ge 0\)) imposed by the Nernst postulate. The lack of magnetic order allows to explore and compare new thermodynamic properties by tracing the specific heat (\(C_\mathrm{m}\)) behavior down to the sub-Kelvin range. Some of the most relevant findings are: (i) a common \(C_\mathrm{m}/T|_{T\rightarrow 0} \approx 7\) J/mol K\(^2\) ‘plateau’ in at least five Yb-based very-heavy-fermions (VHF) compounds; (ii) quantitative and qualitative differences between VHF and standard non-Fermi-liquids; (iii) entropy bottlenecks governing the change of \(S_\mathrm{m}(T)\) trajectories in a continuous transition into alternative ground states. A comparative analysis of \(S_\mathrm{m}(T\rightarrow 0)\) dependencies is performed in compounds suitable for adiabatic demagnetization processes according to their \(\partial ^2 S_\mathrm{m}/\partial T^2\) derivatives.     

Physical,optical and structural studies of copper-doped lead oxychloro borate glasses

Bluish coloured glasses are obtained from the composition PbCl\(_{2}\)–PbO–B\(_{2}\)O\(_{3}\) doped with Cu\(^{2+}\) ions. Basic physical properties and spectroscopic studies (optical absorption, electron paramagnetic resonance, Fourier transform infrared and Raman spectroscopies) were carried out on these samples. The increase in PbCl\(_{2}\) content resulted in the decrease in density and increase in molar volume. At optical frequencies, band gaps and Urbach energies were evaluated and their variation is explained. Spin-Hamiltonian parameters (SHP) obtained from the EPR spectra suggest that the ligand environment around Cu\(^{2+}\) is tetragonally distorted octahedral sites and the orbital \(d_{x^{2}-{y}^{2}} \) is the ground state. The characteristics broad bands in the optical absorption spectra are assigned to the \(^{2}\)B\(_{\mathrm{1g}}\,\rightarrow \, {}^{2}\)B\(_{\mathrm{2g}}\) transition. The bonding coefficient values were evaluated using optical data and SHP. FTIR studies suggested that the glass structure is built up of BO\(_{3}\) and BO\(_{4}\) units. The presence of diborate, pyroborate, pentaborate groups, etc. in the glass network was confirmed from Raman spectra.     

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 \(24\hbox { ppm }^{\circ }\hbox {C}^{-1}\).     

Cooling of High-Power LED Lamp Using a Commercial Paraffin Wax

Commercial paraffin wax used by Bolsius Nederland B.V. for manufacturing various kinds of candles was applied as a phase-change material (PCM) for cooling a 28 W high-power light emitting diode (LED) panel during its operation. The main problem arising during operation of an LED is thermal management. According to the manufacturer’s datasheet specifications (BioSolution Ltd. www.biosolution.pl), the operating temperature range for the LED street lamp UL28W is \((-30~{^{\circ }}\hbox {C})\) to \((+40~{^{\circ }}\hbox {C})\). The object of the present study was an LED panel containing 28 pieces of high-power 1W LEDs connected in series (4 LEDs in each of the 7 rows) mounted on an aluminum plate of dimensions 80 mm by 135 mm. The tested aluminum plate was placed in a block made of aluminum with a hollow compartment containing Bolsius paraffin wax of density \(914~\hbox {kg}\cdot \hbox {m}^{-3}\) at room temperature. Temperatures were recorded using K-type thermocouples at selected locations of the tested LED panel for several values of the power supplied to it, while utilizing PCM and without it. As the manufacturer of Bolsius wax candles does not provide any data on the thermal properties of the material used, it was necessary to carry out micro-calorimetric research. Thermophysical properties of the paraffin wax such as the apparent specific heat, enthalpy of phase transition and temperature of phase change transition during heating and cooling were determined using the Netzsch DSC 214 Polyma. The Netzsch TG 209F3 Tarsus was used for TG/DTG measurements. DSC investigations revealed the following thermal transitions taking place during the first heating: solid–solid transition (onset \(30.4~{^{\circ }}\hbox {C}\), peak at \(40.9~{^{\circ }}\hbox {C}\)), solid–liquid transition (onset \(47.7~{^{\circ }}\hbox {C}\), peak at \(54.9~{^{\circ }}\hbox {C}\), end at \(58.3~{^{\circ }}\hbox {C}\)), latent heat of energy storage \(201~\hbox {J}\cdot \hbox {g}^{-1}\), apparent specific heat corresponding to peak at \(41.5~{^{\circ }}\hbox {C}\) \((5.498~\hbox {J}\cdot \hbox {g}^{-1}\cdot \hbox {K}^{-1})\). DTG investigations revealed that the decomposition of paraffin wax is a two-step process. At \(283~{^{\circ }}\hbox {C}\) there was observed a slightly slower decomposition \((9.43\,\%\cdot \hbox {min}^{-1})\) than that at \(323~{^{\circ }}\hbox {C} (12.5\,\%\cdot \hbox {min}^{-1})\). The experimental results obtained upon cooling the high-power LED lamp during its operation can be applied to verify results of numerical modeling of the heat transfer problems with phase-change transitions. An attempt at modeling such a problem based on 1D fixed grid with variable time step approach was undertaken in this work.     

Measurement Uncertainty Budget of the PMV Thermal Comfort Equation

Fanger’s predicted mean vote (PMV) equation is the result of the combined quantitative effects of the air temperature, mean radiant temperature, air velocity, humidity activity level and clothing thermal resistance. PMV is a mathematical model of thermal comfort which was developed by Fanger. The uncertainty budget of the PMV equation was developed according to GUM in this study. An example is given for the uncertainty model of PMV in the exemplification section of the study. Sensitivity coefficients were derived from the PMV equation. Uncertainty budgets can be seen in the tables. A mathematical model of the sensitivity coefficients of \(T_{\mathrm{a}}\), \(h_{\mathrm{c}}\), \(T_{\mathrm{mrt}}\), \(T_{\mathrm{cl}}\), and \(P_{\mathrm{a}}\) is given in this study. And the uncertainty budgets for \(h_{\mathrm{c}}\), \(T_{\mathrm{cl}}\), and \(P_{\mathrm{a}}\) are given in this study.     

A Challenge to Improve High-Temperature Platinum Resistance Thermometer

High-temperature standard platinum resistance thermometers (HTSPRTs) are used to interpolate the international temperature scale of 1990 (ITS-90), especially for temperatures between the aluminum and the silver points. For this, long-term stability of the HTSPRT is essential. CHINO R800-3L type SPRT, which has a nominal resistance at the triple point of water (TPW) around 0.25 \(\Omega \), is the one developed earlier for the interpolation of the ITS-90 at this temperature range. Further development to this previous model has been carried out for the purpose of improving the thermal stability. The improvement was focused on reducing the effect coming from the difference in thermal expansion between platinum wire and the quartz frame on which the platinum wire is installed. New HTSPRTs were made by CHINO Corporation. Some series of tests were carried out at CHINO and at NMIJ. Initial tests after the HTSPRT fabrication were done at CHINO, where thermal cycles between \(500\,{^{\circ }}\hbox {C}\) and \(980\,{ ^{\circ }}\hbox {C}\) were applied to the HTSPRTs to see change in the resistances at the TPW \((R_{\mathrm{TPW}})\) and at the gallium point \((R_{\mathrm{Ga}})\). Repeated resistance measurements at the silver point \((R_{\mathrm{Ag}})\) were performed after completing the thermal cycling test. Before and after every measurement at silver point, \(R_{\mathrm{TPW}}\) was measured, while before and after every two silver point realization \(R_{\mathrm{Ga}}\) were measured. After completing this test, the HTSPRTs were transported to NMIJ, where the same repeated measurements at the silver point were done at NMIJ. These were then repeated at CHINO and at NMIJ upon repeated transportation among the institutes, to evaluate some effect due to transportation. This paper reports the details of the above-mentioned tests, the results and the analysis.