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.     

Thermodynamic Properties at Saturation Derived from Experimental Two-Phase Isochoric Heat Capacity of 1-Hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide

New measurements are reported for the isochoric heat capacity of the ionic liquid substance 1-hexyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ([C6mim][NTf2]). These measurements extend the ranges of our earlier study (Polikhronidi et al. in Phys Chem Liq 52:657, 2014) by 5 % of the compressed liquid density and by 75 K. An adiabatic calorimeter was used to measure one-phase \((C_{\mathrm{V1}})\) liquid and two-phase \((C_{\mathrm{V2}})\) liquid + vapor isochoric heat capacities, densities \((\rho _s)\), and phase-transition temperatures \((T_s)\) of the ionic liquid (IL) substance. The combined expanded uncertainty of the density \(\rho \) and isochoric heat capacity \(C_\mathrm{V}\) measurements at the 95 % confidence level with a coverage factor of \(k = 2\) is estimated to be 0.15 % and 3 %, respectively. Measurements are concentrated in the immediate vicinity of the liquid + vapor phase-transition curve, in order to closely observe phase transitions. The present measurements and those of our earlier study are analyzed together and are presented in terms of thermodynamic properties \((T_s\), \(\rho _s\), \(C_{\mathrm{V1}}\) and \(C_{\mathrm{V2}})\) evaluated at saturation and in terms of key-derived thermodynamic properties \(C_\mathrm{P}\), \(C_\mathrm{S}\), \(W_\mathrm{S}^{{\prime }}\), \(K_{\mathrm{TS}}^{{\prime }}\), \(\left( {\partial P/\partial T} \right) _{\mathrm{V}}^{\prime }\), and \(\left( {\partial V/\partial T} \right) _\mathbf{P}^{\prime })\) on the liquid + vapor phase-transition curve. A thermodynamic relation by Yang and Yang is used to confirm the internal consistency of measured two-phase heat capacities \(C_{\mathrm{V2}} \), which are observed to fall perfectly on a line as a function of specific volume at a constant temperature. The observed linear behavior is exploited to evaluate contributions to the quantity \(C_{\mathrm{V2}} = f(V, T)\) from chemical potential \(C_{{\mathrm{V}\upmu }} =-T\frac{\mathrm{d}^{{2}}\mu }{\mathrm{d}T^{2}}\) and from vapor pressure \(C_{\mathrm{VP}} =VT\frac{\mathrm{d}^{2}P_{\mathrm{S}} }{\mathrm{d}T^{2}}\). The physical nature and specific details of the temperature and specific volume dependence of the two-phase isochoric heat capacity and some features of the other derived thermodynamic properties of IL at liquid saturation curve are considered in detail.     

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.     

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.     

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.     

Study of optical properties of potassium permanganate ($$\hbox {KMnO}_{4}$$) doped poly(methylmethacrylate) (PMMA) composite films

We have developed films of pure polymethylmethacrylate (PMMA) (0.5, 1, 2 and 5%) and potassium permanganate \((\hbox {KMnO}_{4})\)-doped PMMA composite films of thickness (\(\sim 100\, \upmu \hbox {m}\)) using the solution-cast technique. To identify the possible change that happen to the PMMA films due to doping, the optical properties were investigated for different concentrations of \(\hbox {KMnO}_{4}\) by recording the absorbance (A) and transmittance (\(T\%\)) spectra of these films using UV–Vis spectrophotometer in the wavelength range of 300–1100 nm. From the data obtained from the optical parameters viz. absorption coefficient (\(\alpha \)), extinction coefficient (\(\kappa \)), finesse coefficient (F), refractive index (\(\eta \)), real and imaginary parts of dielectric constant (\(\varepsilon _{\mathrm{r}}\) and \(\varepsilon _{\mathrm{i}})\) and optical conductivity (\(\sigma \)) were calculated for the prepared films. The indirect optical band gap for the pure and the doped-PMMA films were also estimated.     

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.     

Structural,magnetic and photocatalytic characterization of Bi<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>La<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>FeO<Subscript>3</Subscript> nanoparticles synthesized by thermal decomposition method

Single-phase La-substituted bismuth ferrite (Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\)) nanoparticles have been synthesized by thermal decomposition of a glyoxylate precursor. The crystal structure transition of BiFeO\(_{\mathbf {3}}\) from the rhombohedral (R3c) to the cubic \(\boldsymbol {Pm}\bar {\mathbf {3}}\boldsymbol {m}\) structure by La addition was confirmed by X-ray diffraction and infrared spectrometry methods. Furthermore, the Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\) nanoparticles showed a weak ferrimagnetism behaviour, while the magnetization increased from 0.18 to 0.48 emu g\(^{\mathbf {-1}}\) with La substitution. The Bi\(_{\boldsymbol {1-x}}\)La\(_{\boldsymbol {x}}\)FeO\(_{\mathbf {3}}\) nanoparticles exhibited strong absorption in the visible region with the optical band gap calculated from Tauc’s plot in the range of 2.19–2.15 eV. Furthermore, the effects of La substitution on the photodegradation of the methylene blue (MB) under visible light were also studied. The photodegradation of MB dye was enhanced from 64 to \(\sim \)99% with increasing La substitution from \(\boldsymbol {x =}\) 0 to 0.1 and then decreased to 8% for \(\boldsymbol {x =}\) 0.15.     

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%.     

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.     

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.     

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.     

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 \(K_{\mathrm{p}} = 27\%\).     

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

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.     

An illumination problem with tradeoff between coverage of a dataset and aperture angle of a conic light beam

Let \(\{a_i:i\in I\}\) be a finite set in \({\mathbb{R}}^n\). The illumination problem addressed in this work concerns the optimal location and orientation of a conic light beam

$$ R\big (z,y,s\big )= \left\{ x \in {\mathbb{R}}^n : s\,\Vert x-z\Vert - \langle y, x-z\rangle \le 0\right\} .$$

The aperture angle \(\vartheta = 2\arccos s\) of the conic light beam is a decreasing function of the sharpness coefficient \( s\in [0,1]\). The problem at hand is to select an apex z in a prescribed compact region \(Z\subseteq {\mathbb{R}}^n\) and a unit vector \(y\in {\mathbb{R}}^n\) so that the conic light beam R(z, y, s) fulfils two conflicting requirements: it captures as many points \(a_i\) as possible and, at the same time, it has a sharpness coefficient s as large as possible.

     

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.     

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 \({\upmu }\hbox {K}\).