Measurement of the Water Relaxation Time of $${\upvarepsilon }$$-Polylysine Aqueous Solutions

\({\upvarepsilon }\)-Polylysine is an effective food preservative. In this paper, the \({\upbeta }\)-relaxation time of \({\upvarepsilon }\)-polylysine aqueous solutions, which represents the rotational speed of a single water molecule, was measured by broadband dielectric spectroscopy at various temperatures and concentrations. The broadband dielectric spectrum of each sample containing water ranging from 35 wt% to 75 wt% at temperatures ranging from \(0\,^{\circ }\hbox {C}\) to \(25\,^{\circ }\hbox {C}\) was measured using a co-axial semirigid cable probe. The measured dielectric spectra of the samples were composed of several Debye relaxation peaks, including a shortest single molecular rotational relaxation time of water, the \({\upbeta }\)-relaxation time, longer than that of pure water. This result represents that \({\upvarepsilon }\)-polylysine suppresses the molecular kinetics of water. It is also found that the \({\upbeta }\)-relaxation time of an \({\upvarepsilon }\)-polylysine solution that contained more than 35 wt% water showed a typical Arrhenius plot in the temperature range from \(0\,^{\circ }\hbox {C}\) to \(25\,^{\circ }\hbox {C}\). The activation energy of each sample depends on the water content ratio of the sample. As indicated by its long \({\upbeta }\)-relaxation time, \({\upvarepsilon }\)-polylysine is expected to possess high abilities of suppressing freezing and ice coarsening.     

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.     

The parameters governing the coefficient of dispersion of cubes in rotating cylinders

Axial dispersion of cubic particles in horizontal, rotating cylinders was investigated using discrete element modelling simulations. We found that, similar to the behavior of spheres, the axial dispersion coefficient of cubes depends on (1) the rotational speed of the cylinder \({\omega }\), (2) the acceleration due to gravity g and (3) the particle size d, satisfying the relationship \({D}_\mathrm {ax}\propto {\omega }^{1-2{\lambda }}{g}^{{\lambda }}{d}^{2-{\lambda }}\) with \({\lambda }\approx 0.15\) (\({\lambda }\approx 0.1\) for beds of spheres) (Third et al. in Powder Technol 203:510–517, 2010). This observation suggested that, although particle shape influences significantly the rate of axial dispersion (cubes disperse almost twice as fast as spheres of equal volume), the parameters controlling the coefficient of dispersion are independent of particle shape.     

In situ synthesis and properties of self-reinforced $$\hbox {Si}_{3} \hbox {N}_{4}\textendash \hbox {SiO}_{2}\textendash \hbox {Al}_{2} \hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3} \ (\hbox {La}_{2}\hbox {O}_{3}$$) glass–ceramic composites

In-situ-grown \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\)-reinforced \(\hbox {SiO}_{2}\textendash \hbox {Al}_{2}\hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3}\) \((\hbox {La}_{2}\hbox {O}_{3})\) self-reinforced glass–ceramic composites were obtained without any \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\) seed crystal. These composites with different compositions were prepared in a nitrogen atmosphere for comparison of phase transformation and mechanical properties. The results showed that \(\hbox {SiO}_{2}\textendash \hbox {Al}_{2}\hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3}\) \((\hbox {La}_{2}\hbox {O}_{3})\) glass can effectively promote \(\upalpha \)- to \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\) phase transformation. The crystallized \(\hbox {Y}_{2}\hbox {Si}_{2}\hbox {O}_{7}\textendash \hbox {La}_{4.67}\hbox {Si}_{3}\hbox {O}_{13}\) phases with a high melting point significantly benefited the high-temperature mechanical properties of the composites. The \(\hbox {Si}_{3}\hbox {N}_{4}\textendash \hbox {SiO}_{2}\textendash \hbox {Al}_{2} \hbox {O}_{3}\textendash \hbox {Y}_{2}\hbox {O}_{3}\) \((\hbox {La}_{2}\hbox {O}_{3})\) glass–ceramic composites exhibit excellent mechanical properties compared with unreinforced glass–ceramic matrix, which is undoubtedly attributed to the elongated \(\upbeta \!\hbox {-Si}_{3}\hbox {N}_{4}\) grains. These glass–ceramic \(\hbox {Si}_{3}\hbox {N}_{4}\) composites with excellent comprehensive properties might be a promising material for high-temperature applications.     

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.     

Novel composites of $$\upbeta $$-SiAlON and radome manufacturing technology developed at ARCI,Hyderabad, for hypervelocity vehicles

Keeping the importance of developing suitable radome (a word derived from radar \(+\) dome) materials and near-net shape consolidation technique for manufacturing radomes suitable for hypersonic (>mach 5) radar-guided missiles in India, the International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Hyderabad, has initiated an in-house R&D programme and successfully developed a complete process know-how for manufacturing defect-free prototype \(\upbeta \)-SiAlON-based radome structures with all the desired properties. As a part of this R&D programme, total six separate sub-projects mentioned below were undertaken and executed: (i) identification of the best composition out of \(\upbeta \)-\(\hbox {Si}_{6-z}\hbox {Al}_{z}\hbox {O}_{z}\hbox {N}_{8-z}\) (0 \(\le z \le \) 4.1) solid solution, which possesses a right combination of properties required for radome applications, (ii) designing of an AlN-free precursor mixture for consolidating \(\upbeta \)-\(\hbox {Si}_{4}\hbox {Al}_{2}\hbox {O}_{2}\hbox {N}_{6}\) ceramics by following aqueous colloidal processing routes, (iii) development of a process for passivating water-sensitive AlN powder against hydrolysis, (iv) development of aqueous gelcasting (GC) and hydrolysis-assisted solidification (HAS) powder processing routes for consolidating dense \(\upbeta \)-SiAlON ceramics using highly solids loaded (>50 vol%) aqueous slurries, (v) development of an hydrolysis-induced aqueous gelcasting (GCHAS) process, a novel near-net-shape consolidation technique, to produce radomes with very high-production yields and (vi) development of an economic route for synthesizing the low-dielectric constant and high strength novel \(\upbeta \)-SiAlON-\(\hbox {SiO}_{2}\) ceramic composites. In this paper, (i) the basis for choosing \(\upbeta \)-SiAlON-based ceramics for hypervelocity radome applications, and (ii) the various bottle-neck problems faced, while executing this entire R&D work and the way they were overcome have been critically analysed and discussed systematically, while citing all the relevant and important references.     

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.     

Calorimetric Observation of Single $$\hbox {He}_2^*$$ Excimers in a 100-mK He Bath

We report the first calorimetric detection of individual \(\hbox {He}_2^*\) excimers within a bath of superfluid \(^4\hbox {He}\). The detector used in this work is a single superconducting titanium transition edge sensor (TES) with an energy resolution of \({\sim }1~\hbox {eV}\), immersed directly in the helium bath. \(\hbox {He}_2^*\) excimers are produced in the surrounding bath using an external gamma-ray source. These excimers exist either as short-lived singlet or long-lived triplet states. We demonstrate detection (and discrimination) of both states: In the singlet case the calorimeter records the absorption of a prompt \({\approx }15~\hbox {eV}\) photon, and in the triplet case the calorimeter records a direct interaction of the molecule with the TES surface, which deposits a distinct fraction of the \({\approx }15~\hbox {eV}\), released upon decay, into the surface. We also briefly discuss the detector fabrication and characterization.     

Ultra-low friction and excellent elastic recovery of fullerene-like hydrogenated carbon film based on multilayer design

Multilayer fullerene-like hydrogenated carbon (FL-C:H) films were synthesized by using the chemical vapour deposition technique with a different flow rate of methane. The typical fullerene-like structure of as-prepared films was investigated by using transmission electron microscopy and Raman spectra. The prepared multilayered FL-C:H films showed a high elastic recovery (\({\sim }\)90\(\%\)), ultra-low friction coefficient (\({\sim }\)0.019) and low wear rate \(({\sim }3.0\times 10^{-9}\,\hbox {mm}^{3}\,\hbox {Nm}^{-1})\) in humid air.     

Dry Block Calibrator with Improved Temperature Field and Integrated Fixed-Point Cells

To reduce uncertainty of calibrations of contact thermometers using dry block calibrators, a concept was developed at Institute for Process Measurement and Sensor Technology of Technische Universität Ilmenau. This concept uses a multi-zone heating, heat flux sensors and a multiple fixed-point cell. The paper shows the concept and its validation on the basis of a dry block calibrator with a working temperature range of \(70\,^{\circ }\hbox {C}\) to \(430\,^{\circ }\hbox {C}\). The experimental results show a stability of \({\pm } 4\,\hbox {mK}\) for the reference temperature and axial temperature differences in the normalization block less than \({\pm }55\,\hbox {mK}\).     

Synthesis,characterization and catalytic application of Ni catalysts supported on alumina–zirconia mixed oxides

Alumina and alumina–zirconia mixed oxides were compared as supports to prepare nickel catalysts. The oxides were prepared by the sol–gel method using aluminum tri-sec-butoxide and zirconium (IV) propoxide as precursors, and its physicochemical properties were determined by BET, TGA, DTA, XRD, SEM and TEM. The catalysts of nickel were obtained by the impregnation of the supports with nickel nitrate (10 wt%) and were heat-treated at \(700{^{\circ }}\hbox {C}\). The specific area of the supports and catalysts decreased with the increase in the zirconia content in agreement with the crystalline phase formed. TEM micrographs of nickel catalysts revealed particles in the size range of 10–30 nm. The \(\hbox {Ni/Al}_{2}\hbox {O}_{3}\)–\(\hbox {ZrO}_{2}\) catalysts were tested in the steam reforming reaction of ethanol (SRE) at \(500{^{\circ }}\hbox {C}\), and the obtained results suggest that the differences in catalytic activities depended on the content of \(\hbox {ZrO}_{2}\). The selectivity towards \(\hbox {H}_{2}\) was \({\sim }56\%\) for the named catalyst Ni–Al–0.25Zr.     

Measurement of Out-of-Plane Thermal Conductivity of Epitaxial $$\hbox {YBa}_{2}\hbox {Cu}_{3}\hbox {O}_{7-{\delta }}$$ Thin Films in the Temperature Range from 10 K to 300 K by Photothermal Reflectance

We measured the out-of-plane (c-axis) thermal conductivity of epitaxially grown \(\hbox {YBa}_{2}\hbox {Cu}_{3}\hbox {O}_{7-{\delta }}\) (YBCO) thin films (250 nm, 500 nm and 1000 nm) in the temperature range from 10 K to 300 K using the photothermal reflectance technique. The technique enables us to determine the thermal conductivity perpendicular to a thin film on a substrate by curve fitting analysis of the phase lag between the thermoreflectance signal and modulated heating laser beam in the frequency range from \(10^{2}\,\hbox {Hz}\) to \(10^{6}\,\hbox {Hz}\). The uncertainties of measured thermal conductivity of all samples were estimated to be within \({\pm }9\,\%\) at 300 K, \({\pm }12\,\%\) at 180 K, \({\pm }16\,\%\) at 90 K and \({\pm }20\,\%\) below 50 K. The experimental results show that the thermal conductivity is dependent on the thickness of the thin films across the entire temperature range. We also observed that the thermal conductivity of the present YBCO thin films showed \(T^{1.4}\) to \(T^{1.6}\) glass-like dependence below 50 K, even though the films are crystalline solids. In order to explain the reason for this temperature dependence, we attempted to analyze our results using phonon relaxation times for possible phonon scattering models, including stacking faults, grain boundary and tunneling states scattering models.     

Influences of Detection Pinhole and Sample Flow on Thermal Lens Detection in Microfluidic Systems

Thermal lens microscopy (TLM), due to its high temporal (\({\sim }\mathrm{ms}\)) and spatial resolution (\({\sim }\upmu \mathrm{m}\)), has been coupled to lab-on-chip chemistry for detection of a variety of compounds in chemical or biological fields. Due to the very short optical path length (usually below 100 \(\upmu \mathrm{m}\)) in a microchip, the sensitivity of TLM is unfortunately still 10 to 100 times lower than conventional TLS with 1 cm sample length. Optimization of the TLM optical configuration was made with respect to different pinhole aperture-to-beam size ratios for the best signal-to-noise ratio. In the static mode, the instrumental noise comes mainly from the shot noise of the probe beam when the chopper frequency is over 1 kHz or from the flicker noise of the probe beam at low frequencies. In the flowing mode, the flow-induced noise becomes dominant when the flow rate is high. At a given flow rate, fluids with a higher density and/or a higher viscosity will cause larger flow-induced noise. As an application, a combined microfluidic flow injection analysis (\(\upmu \mathrm{FIA}\))–TLM device was developed for rapid determination of pollutants by colorimetric reactions. Hexavalent chromium [Cr(VI)] was measured as a model analyte. Analytical signals for 12 sample injections in 1 min have been recorded by the \({\upmu }\)FIA–TLM. For injections of sub-\(\upmu \)L samples into the microfluidic stream in a \(50\,\upmu \mathrm{m}\) deep microchannel, a limit of detection of \(4\,\mathrm{ng}{\cdot }\mathrm{mL}^{-1}\) was achieved for Cr(VI) in water at 60 mW excitation power.     

Enhanced infrared transmission characteristics of microwave-sintered $$\hbox {Y}_{2}\hbox {O}_{3}$$–$$\hbox {MgO}$$MgO nanocomposite

Infrared (IR) transparent ceramics are found to have applications in demanding defence and space missions. In this work, \(\hbox {Y}_{2}\hbox {O}_{3}\)–\(\hbox {MgO}\) nanocomposites were synthesised by a modified single-step combustion technique. The characterisation of the as-prepared powder by X-ray diffraction and transmission electron microscopy revealed the presence of cubic phases of ultra-fine nanostructured \(\hbox {Y}_{2}\hbox {O}_{3 }\) and MgO, with an average crystallite size of \({\sim }19 \hbox { nm}\). For the first time the resistive and microwave heatings were effectively coupled for sintering the sample, and it was found that the sintering temperature and soaking time were reduced considerably. The pellets were sintered to 99.2% of the theoretical density at \(1430{^{\circ }}\hbox {C}\) for a soaking duration of 20 min. The well-sintered pellets with an average grain size of \({\sim }200 \hbox { nm}\) showed better transmittance properties relative to pure yttria. The promising percentage transmission of 80% in the UV–visible region and 82% in the mid-IR region shown by \(\hbox {Y}_{2}\hbox {O}_{3}\)–\(\hbox {MgO}\) nanocomposites can be tailored and made cost-effective to fabricate high-quality IR windows for strategic defence and space missions.     

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 \({\upmu }\hbox {K}\).     

Emission of Gas and $$\hbox {Al}_{2}\hbox {O}_{3}$$ Smoke in Gas–Al Particle Deflagration: Experiments and Emission Modeling for Explosive Fireballs

Emission of gas and \(\hbox {Al}_{2}\hbox {O}_{3}\) smoke within the deflagration of \(\hbox {H}_{2}{-}\hbox {O}_{2}\)–{\(\hbox {N}_{2}{-}\hbox {CO}_{2}\)}–Al particles has been studied in a closed combustion chamber at pressures of up to 18 bar and at gas temperatures of up to 3700 K. Measurements of radiance intensity were taken using a five wavelength pyrometer (0.660 \(\upmu \hbox {m}\), 0.850 \(\upmu \hbox {m}\), 1.083 \(\upmu \hbox {m}\), 1.260 \(\upmu \hbox {m}\), 1.481 \(\upmu \hbox {m}\)) and a grating spectrometer in the range (4.10 \(\upmu \hbox {m}\) to 4.30 \(\upmu \hbox {m}\)). In order to characterize the aluminum oxide smoke size and temperature, an inversion method has been developed based on the radiation transfer equation and using pyrometer measurements and thermochemical calculations of \(\hbox {Al}_{2}\hbox {O}_{3}\) smoke volume fractions. Temperatures in combustion gas have been determined using a method based on the assumed blackbody head of the 4.26 \(\upmu \hbox {m}\) \(\hbox {CO}_{2}\) emission line and on its spectral shift with pressure and temperature. For validation purpose, this method has been applied to measurements obtained when calibrated alumina particles are injected in a combustion chamber prior to gaseous deflagrations. This mathematical inversion method was developed to investigate explosive fireballs.     

Mechanical and Thermophysical Properties of Cerium Monopnictides

The ultrasonic attenuation due to phonon–phonon interaction, thermoelastic relaxation and dislocation damping mechanisms has been investigated in cerium monopnictides CeX (X: N, P, As, Sb and Bi) for longitudinal and shear waves along \({\langle }100{\rangle }\), \({\langle }110{\rangle }\) and \({\langle }111{\rangle }\) directions. The second- and third-order elastic constants of CeX have also been computed in the temperature range 0 K to 500 K using Coulomb and Born–Mayer potential upto second nearest neighbours. The computed values of these elastic constants have been applied to find out Young’s moduli, bulk moduli, Breazeale’s non-linearity parameters, Zener anisotropy, ultrasonic velocity, ultrasonic Grüneisen parameter, thermal relaxation time, acoustic coupling constants and ultrasonic attenuation. The fracture/toughness ratio is less than 1.75, which shows that the chosen materials are brittle in nature as found for other monopnictides. The drag coefficient acting on the motion of screw and edge dislocations due to shear and compressional phonon viscosities of the lattice have also been evaluated for both the longitudinal and shear waves. The thermoelastic loss and dislocation damping loss are negligible in comparison to loss due to Akhieser damping (phonon–phonon interaction). The obtained results for CeX are in qualitative agreement with other semi-metallic monopnictides.     

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.     

Influence of $$\hbox {TiO}_{2}$$ particle size and conductivity of the CuCrO$$_{2}$$2 nanoparticles on the performance of solid-state dye-sensitized solar cells

Solid-state dye-sensitized solar cells have been fabricated with mesoporous \(\hbox {TiO}_{2 }\) photoanode and N719 dye as photosensitizer. First, \(\hbox {TiO}_{2}\) and non-doped, Zn- and Mg-doped CuCrO\(_{2}\) nanoparticles have been synthesized by sol–gel method. In addition, the \(\hbox {TiO}_{2}\) pastes have been prepared through Pechini-type sol–gel method. The effect of \(\hbox {TiO}_{2}\) particle size, mesoporous \(\hbox {TiO}_{2}\) photoanode thickness and solid-state electrolyte thickness on the efficiency of the fabricated devices has been investigated. Our results show that in spite of the low amount of dye loading for photoanode with large \(\hbox {TiO}_{2}\) nanoparticles (80–180 nm), the dye-sensitized solar cell made from it has higher efficiency than that constructed from the photoanode comprising of small particles about 10–15 nm in size. The higher efficiency is attributed to the longer diffusion length of electrons because of a better electron transport and penetration of a large amount of \(\hbox {CuCrO}_{2 }\) nanoparticles in the porous structure of \(\hbox {TiO}_{2}\) photoanode. By using the doped \(\hbox {CuCrO}_{2}\) nanoparticles, the efficiency has been increased from 0.027% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\) to 0.033% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\):Zn and further increased to 0.042% for \(\hbox {TiO}_{2}\)/N719 dye/CuCrO\(_{2}\):Mg. The efficiency enhancement by doping is ascribed to the conductivity improvement due to the presence of impurity atoms.