Effect of La2O3 on the oxidation resistance of SiC ceramic at 1973 K: Experimental and theoretical study

The effect of La₂O₃ on the oxidation resistance of SiC ceramic at 1973 K was investigated using isothermal oxidation test and first-principles calculations. The SiC ceramic with La₂O₃ shows a better oxidation resistance compared with that without La₂O₃ due to the in situ formed La₂Si₂O₇ in SiO₂ glass layer after oxidation at 1973 K. First-principles calculations based on density functional theory were applied to analyze the solution behaviors of La atom in the surface of SiO₂ and La₂Si₂O₇. The solution energy of La atom in SiO₂ (0 1 1) is −19.05 eV, which is far less than −4.19 eV in La₂Si₂O₇ (2 0 1) with a La vacancy, thus resulting in that La atom in La₂Si₂O₇ (2 0 1) diffuses into SiO₂ (0 1 1). The SiO₂ lattice with an interstitial La atom is more stable than that with a substitutional La atom and the interstitial La breaks the nearest Si–O bond to form La–O and La–Si bonds, which is beneficial to improving the high-temperature stability of SiO₂. Experimental and theoretical results indicate that the formation of refractory La₂Si₂O₇ phase enhances the stability of SiO₂ glass layer, so as to protect SiC ceramic from further oxidation at 1973 K.     

Preparation and characterization of nanocrystalline La-doped ZnO powders through a mechanical milling and their optical properties

Structural and optical properties of mechanically milled La-doped ZnO powders are presented in this paper. The Zn_1−xLa_xO phase formed when x varied in a range of 0.02-0.06 and milled at 400 rpm for 20 h. The secondary La₂O₃ phase occurred with an increase of La content. The crystallite and particle size decreased as a function of La content as x = 0-0.14 due to the effect of Zener pinning and solute drag. The absorption edge shifted to a lower wavelength when La content was increased to x = 0.14 because of the size effect. The energy band gap of Zn_1−xLa_xO powders varied in a range of 2.96-3.12 eV depending on the crystallite size. The broad emission bands in a visible region centered at about 640 nm are attributed to oxygen deficiency.     

The transition from non-ohmic to ohmic characteristics in La2O3 doped ZnO–MgO–TiO2 linear resistance ceramics

La₂O₃ doped ZnO–MgO–TiO₂ based linear resistance ceramics were prepared by the solid phase sintering method. The doping content of La₂O₃ is from 0.0 wt% to 2.5 wt%. The solubility of La₂O₃ in ZnO is less than 0.06 mol% (0.5 wt%), La_0.66TiO_2.993 phases will be formed at grain boundary and change the distribution of spinel phase when La₂O₃ is excessive. For I–V test, undoped sample exhibits typical non-ohmic characteristics, but La-doped samples show excellent ohmic behaviors under low DC and high pulse current (PC). The complex impedance spectrum and the frequency dependent conductivity furtherly demonstrate that La-doped samples possess linear characteristics because there is no grain boundary effect which can affect the electron transmission at grain boundaries. Besides, the decrease of the grain boundary barrier from 0.2135eV for undoped sample to 0.0031eV for 0.5 wt% La doped samples can account for the elimination or reduction of grain boundary effect. In this work, the transition from non-ohmic to ohmic properties by doping La₂O₃ in ZnO–MgO–TiO₂ multiphase ceramics is realized.     

High Conductivity Electrolyte: Zn2GeO4

Zn₂GeO₄ ceramic materials were synthesized by the solid‐state method. Zn₂GeO₄ powders were investigated with X‐ray powder diffraction (XRD) and high‐resolution transmission electron microscopy (HRTEM). Oxygen defects in the Zn₂GeO₄ ceramics were investigated by photoluminescence, Raman, and EDS spectra. Conductivity of Zn₂GeO₄ was 0.18 S/cm at low temperature of 773 K, and its activation energy was 0.49 eV. The results showed that Zn₂GeO₄ was a promising low‐temperature electrolyte with high conductivity.     

Wavelength Tailorability of Broadband Near‐Infrared Luminescence in Cr4+‐Activated Transparent Glass‐Ceramics

Four Cr⁴⁺‐activated transparent glass‐ceramics containing different species of silicate nano‐crystals (Zn₂SiO₄, Mg₂SiO₄, Li₂ZnSiO₄, and Li₂MgSiO₄) were successfully prepared. Absorption spectra, photoluminescence spectra, lifetime decay curves, and quantum yield of these transparent glass‐ceramics were measured. According to the crystal field strength of Cr⁴⁺‐incorporated tetrahedral sites, the broadband near‐infrared (NIR) luminescence of Cr⁴⁺ can be tailored from 1130 to 1350 nm and the lifetime of Cr⁴⁺ luminescence can be prolonged from 6 to 100 μs. Quantum yield in the transparent glass‐ceramics containing Li₂ZnSiO₄ nano‐crystals reached at 17%, which is the highest value of NIR luminescence in transition‐metal‐activated glass materials.     

Enhanced structural,optical, and photocatalytic activity of novel Cd–Zn co-doped Mg0.25 Fe1.75O4 for degradation of RhB dye under visible light irradiation

Cd_xZn_1-xMg_0.25Fe_1.75O₄ (where x = 0.00, 0.25, 0.50, 0.75, 1.00) have been successfully produced by a facile hydrothermal technique for a thorough comparison of structural, optical, and photocatalytic properties (degradation of Rhodamine B -RhB dye under visible light irradiation). X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) confirmed the formation of cubic spinel structure for all of the samples. Fourier transform infrared (FTIR) spectroscopy verified the presence of metal-oxygen (M–O) bonding in the prepared samples with two frequency bands corresponding to phonon vibrational stretching in both the octahedral and tetrahedral lattice positions. UV–Visible Spectrophotometer and photoluminescence (PL) spectroscopy investigated the bandgap variation (2.7 eV-1.7 eV) and emission spectrum peaks appearing in the range of 405–471 nm region. The comparison in the photo-degradation of Rhodamine B (RhB) revealed the superior performance (98% degradation of RhB dye in 80 min having a K value of 0.04966 with excellent reusability) of Cd_0.50Zn_0.50Mg_0.25Fe_1.75O₄ sample having 50/50 dopant ratio of Cd and Zn in the parent Mg Ferrite, attributed to the lowest bandgap, longer lifetime of charge carriers, active octahedral lattice site, electron/hole pair recombination preventions, and the least value of ohmic impedance at higher frequency.     

Tuning the optical bandgap of multi-walled carbon nanotube-modified zinc silicate glass-ceramic composites

Novel glass-ceramic composites with optical bandgap tunability were synthesised. Zinc silicate powder (ZS) was mixed with multi-walled carbon nanotubes (MWCNTs) at various mass fractions (0, 1, 2, and 3 wt %), followed by argon sintering. X-ray diffraction (XRD) analysis revealed the structural change from an amorphous ZS phase to a crystalline willemite phase (Zn₂SiO₄) by adding MWCNTs, and the largest crystallite size was obtained for ZS with 2.0 wt% MWCNTs. Although the agglomeration of ZS and MWCNTs was observed by field emission scanning electron microscopy (FESEM), there was no chemical interaction between ZS and MWCNTs as confirmed by Fourier transform infrared spectroscopy (FTIR). MWCNTs enhanced the crystallisation, which led to the green emission of Zn₂SiO₄ blue-shifting from 572 nm to 557 nm. The narrowed optical bandgap of Zn₂SiO₄ was attributed to the MWCNT-induced exciton localised between the valence band and conduction band of Zn₂SiO₄. The bandgap tuning effect of MWCNTs potentially paved new ways to mass fabricate zinc silicate-based semiconductors with desirable optical bandgap energy E_g, which significantly benefits the sensor and laser-related industry.     

Effect of Size-Dependent Thermal Instability on Synthesis of Zn<Subscript>2</Subscript> SiO<Subscript>4</Subscript>-SiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Core–Shell Nanotube Arrays and Their Cathodoluminescence Properties

Vertically aligned Zn₂SiO₄-SiO _x (x < 2) core–shell nanotube arrays consisting of Zn₂SiO₄-nanoparticle chains encapsulated into SiO _x nanotubes and SiO _x -coated Zn₂SiO₄ coaxial nanotubes were synthesized via one-step thermal annealing process using ZnO nanowire (ZNW) arrays as templates. The appearance of different nanotube morphologies was due to size-dependent thermal instability and specific melting of ZNWs. With an increase in ZNW diameter, the formation mechanism changed from decomposition of “etching” to Rayleigh instability and then to Kirkendall effect, consequently resulting in polycrystalline Zn₂SiO₄-SiO _x coaxial nanotubes, single-crystalline Zn₂SiO₄-nanoparticle-chain-embedded SiO _x nanotubes, and single-crystalline Zn₂SiO₄-SiO _x coaxial nanotubes. The difference in spatially resolved optical properties related to a particular morphology was efficiently documented by means of cathodoluminescence (CL) spectroscopy using a middle-ultraviolet emission at 310 nm from the Zn₂SiO₄ phase.     

Spectroscopic Features of Silica Glasses Doped with Tin

The absorption, photoluminescence, and photoluminescence excitation spectra are investigated for tin-doped silica glasses synthesized by different methods. In all the glasses studied, two new centers belonging to the tin dopant in the SiO₂ network are revealed in addition to the well-known oxygen-deficient center with the absorption band at 4.9 eV. One new center is associated with the absorption band at 5.9 eV and the photoluminescence bands at 2.7 and 3.6 eV, whereas the other center is characterized by the absorption band in the range of 4.56 eV and the photoluminescence band at 2.95 eV. Both new centers are identified as oxygen-deficient centers. The latter center is an analog of the centers observed in pure silica glasses synthesized in a nitrogen atmosphere and in germanosilicate glasses prepared by the MCVD and SPCVD methods. It is revealed that the formation of the oxygen-deficient center is one of the main channels of incorporating tin into the SiO₂ network in all tin-containing silica glasses. Consideration is given to the reasons for the lower efficiency of the photodecay of oxygen-deficient centers in the SiO₂ network in tin-containing glasses as compared to that in germanosilicate glasses and for the relatively high efficiency in the formation of the photoinduced refractive index in optical fibers with a core consisting of tin-containing silica glass.     

Low-cost flame synthesized La2/3Cu3Ti4O12 electro-ceramic and extensive investigation on electrical,impedance, modulus,and optical properties

An environmentally-friendly synthesis route and low-cost starting materials are more appropriate for the production of ceramic materials at the industry level. With this concern we prepared the La_2/3Cu₃Ti₄O₁₂(LCTO), which is isostructural of CaCu₃Ti₄O₁₂ (CCTO), using the low-cost TiO₂ instead of a high-cost of titanium source (titanium isopropoxide or titanium chloride) using a low-cost wet-chemical route. Although, there are lots of synthetic methods reported for LCTO fabrication in terms of duration, cheap reagents, energy consumption, feasibility, etc. The present method is far better than the others. The prepared ceramic samples were sintered at 1050 ^°C/12 h and studied their structural, morphology and impedance, and modulus studies for further confirmation. The prepared LCTO ceramic shows the pure phase with the cubic type of morphology. The homogenous distribution of all the elements was observed through dispersive X-ray analysis. X-ray photoelectron spectroscopy studies revels that La is in +3 oxidation state, Cu is in a +2 oxidation state, and Ti is multiple (+3 and + 4) oxidation state. The LCTO ceramic displayed the very high dielectric constant (∼3852) and dielectric loss (0.322), at 1 kHz and at room temperature. Calculated the activation energy using the impedance and modulus data and it shows the superior to that of CCTO ceramic synthesized by the same method. The prepared samples exhibited Debye-type relaxation, which is evoked from the impedance and modulus studies. The calculated optical energy bandgap of LCTO (2.06 eV) is found to be lesser than that of the well-known structure of perovskites (BaTiO₃ (3.28 eV), PbTiO₃ (3.18 eV), LiNbO₃ (3.78 eV) and BiFeO₃ (2.67 eV) as well as structure of spinel CoCr₂O₄ (3.10 eV) and LuFe₂O₄ (2.18 eV)) materials.     

Enhancement in energy storage performance of La-modified bismuth-ferrite-based relaxor ferroelectric ceramics by defect compensation and process optimization

In this investigation, La₂O₃ was doped into 0.85(0.65BF-0.35BT)-0.15Sr_0.7Bi_0.2TiO₃ (BF-BT-SBT) to form a solid solution with relaxation ferroelectric properties. The dielectric breakdown strength (BDS) of 1% mole of La doping was 220 kV/cm, the maximum recoverable energy storage (W_rec) was 2.35 J/cm³, and the energy storage efficiency (η) was 71%. The relationship between ceramic properties and microstructure was investigated in detail. Doping with La has the following main features: (1) The dissolution of La³⁺ ions in the A position of the original perovskite structure reduced the concentration of oxygen vacancies in the lattice and played a role of compensating the defects. (2) The dielectric loss of ceramics was reduced, the impedance was greatly increased, and the specimen exhibited a high-temperature stability: a maximum W_rec of 4.04 ± 1.7% J/cm³ in 30–130 °C. (3) The core–shell–like with single phase structure in La-doped ceramics had been successfully observed, which may become a strategy for preparing high-performance ceramics. Higher BDS and denser structures were obtained in 0.01 La ceramics by further optimizing the preparation of the above compositions by the viscous polymer process (VPP). The BDS of 0.01La ceramics prepared by VPP reached 480 kV/cm, the effective energy storage density reached 6.15 J/cm³, and the η was about 81%. This made La-doped 15SBT (chemical composition of BF-BT-SBT + La₂O₃) ceramics become a potential candidate material for energy storage devices.     

Sintering mechanism and properties of ZnVMnNbO varistor ceramic and their evolutions by Ce–La doping

This paper studies the sintering mechanism and property of ZnO–V₂O₅–MnCO₃–Nb₂O₅ (ZnVMnNbO) varistor ceramic and their evolution by Ce–La dopant. The XRD, SEM, EBSD and TEM results show MnZn₂Nb₂O₈ has a similar effect as ZnV₂O₄ and Zn₃(VO₄)₂ on contributing to the formation of Vanadium (V)-rich liquid phase and promoting the sintering of ZnVMnNbO ceramic. Oppositely, ZnMn₂O₄ particle phase can only postpone sintering by pinning the growth of ZnO grains. Adding Ce–La dopant leads to forming Ce(La)VO₄ intergranular particle phase that further hinders the sintering of the ceramic. This conclusion agrees with the result of the following kinetics study that shows the grain-growth exponent and apparent activation energy of ZnVMnNbO ceramic increasing from 2.39 and 186 KJ mol-1 to 2.95 and 263 KJ mol-1 with the addition of Ce–La dopant. Meanwhile, the electrical properties of the Ce–La doped ZnVMnNbO varistor ceramics are generally better than its Rare Earth (RE)-free counterparts. Sintering at 875 °C for 3 h can increase the nonlinear coefficient of Ce–La doped ZnVMnNbO varistor ceramic to its highest value of 48.4, therefore, is proposed as the optimum fabricating procedure.     

Optimization of Opto-Electrical and Photocatalytic Properties of SnO<Subscript>2</Subscript> Thin Films Using Zn<Superscript>2+</Superscript> and W<Superscript>6+</Superscript> Dopant Ions

Abstract  

A series of Zn²⁺ and W⁶⁺ doped tin oxide (SnO₂) thin films with various dopant concentrations were prepared by spray pyrolysis deposition, and were characterized by X-ray diffraction, atomic force microscopy, contact angle, absorbance, current density–voltage (J–V) and photocurrent measurements. The results showed that W⁶⁺ doping can prevent the growth of nanosized SnO₂ crystallites. When Zn²⁺ ions were used, the crystallite sizes were proved to be similar with the undoped sample due to the similar ionic radius between Zn²⁺ and Sn⁴⁺. Regardless of the dopant ions’ type or concentration, the surface energy has a predominant dispersive component. By using Zn²⁺ dopant ions it is possible to decrease the band gap value (3.35 eV) and to increase the electrical conductivity. Photocatalytic experiments with methylene blue demonstrated that with zinc doped SnO₂ films photodegradation efficiencies close to 30% can be reached.     

Rare earth titano-silicates for high k gate dielectric applications

The present paper explores the properties of rare earth titano-silicates compounds for high k applications. RE₂Ti₂SiO₉ (RE=La, Pr and Nd) ceramic compounds were prepared using conventional solid state reaction route. Its structural, dielectric, optical and thermal properties were investigated. It was found that these materials possess a high dielectric constant in the range of 20–34 at room temperature, which is greater than that of HfO₂. The UV Visible absorption spectra indicates reasonably large band gap of above 5 eV. Further these compounds also have low coefficient of thermal expansion of less than 9 ppm/°C.     

Dielectric properties of conventional and microwave sintered Lanthanum doped CaCu3Ti4O12 ceramics for high-frequency applications

The colossal dielectric response of La-doped CaCu₃Ti₄O₁₂ ceramics has been probed at room temperature for a frequency of 1Hz–20 MHz. In this work, the La-doped (CaCu₃Ti₄O₁₂)_x samples for x = 0.1, 0.2, and 0.3 have been sintered at 1100 °C using two different heating modes. SEM and EDS analysis investigated the microstructural chrysalis, grain size distribution, and the inhibitions of Cu-rich phase segregation into grain boundaries by the effect of La³⁺. The presence of main cubic single-phase of CCTO and the diminutive Bragg peak shift due to ion size effect of La³⁺ and Ca²⁺ have been identified by XRD for both conventional (CS) and microwave sintered (MWS) samples. XPS study revealed the effect of La³⁺ on the binding energies of Cu and Ti in CCTO. The dielectric properties namely dielectric constant (?), tan δ, and dielectric relaxation peaks were measured using BDS in which CS and MWS La-doped samples demonstrated (?) ～ >10⁴ and ～ >10³ along with low tan δ for x ≥ 0.1 at medium and high frequency (10⁴–10⁷Hz) than pure CCTO.     

Phase evolution and microwave dielectric properties of SrTiO3 added ZnAl2O4–Zn2SiO4–SiO2 ceramics

Phase evolution and microwave dielectric properties of SrTiO₃ added ZnAl₂O₄–3Zn₂SiO₄–2SiO₂ ceramics system were investigated. With the addition of SrTiO₃, the sintering temperature for dense ceramic is reduced from 1320 °C to 1180–1200 °C. According to the nominal composition ZnAl₂O₄–3Zn₂SiO₄–2SiO₂-ySrTiO₃, phase evolution is revealed by XRD patterns and Back Scattering Electron images: Zn₂SiO₄, ZnAl₂O₄ and SiO₂ phases coexist at y = 0; SrTiO₃ reacts with ZnAl₂O₄ and SiO₂ to form SrAl₂Si₂O₈, TiO₂ and Zn₂SiO₄ at y = 0.2 to 0.8, and SiO₂ phase disappears at y = 0.8; new phase of Zn₂TiO₄ is obtained at y = 1. The existence of TiO₂ has important effect on the dielectric properties. The optimized microwave dielectric properties are obtained at y = 0.6 and the ceramics show low dielectric constant (7.16), high-quality factor (57, 837 GHz), and low temperature coefficient of resonant frequency (−30 ppm °C⁻¹).     

Structural,optical, electrical,dielectric, molecular vibrational and magnetic properties of La3+ doped Mg–Cd–Cu ferrites prepared by Co-precipitation technique

Ferrites are among the most frequently investigated materials mainly due to interesting and practically different properties. Therefore, easily and cost-effective lanthanum doped Mg_0.5Cd_0.25Cu_0.25Fe_2-xLa_xO₄ (x = 0.0, 0.0125, 0.025, 0.0375 and 0.05) ferrites were synthesized by a co-precipitation route, a comprehensive characterisation of their structural, optical, electric, dielectric, molecular vibrational, and magnetic properties were carried out. X-ray diffraction analysis confirmed the formation of a cubic spinel structure. Variations in frequency bands were also observed with amplification in optical band gap energy (2.95 – 3.38 eV) due to La³⁺ ions insertion. The electric resistivity had opposite trends at low and high temperatures with increasing La³⁺ content. The Curie temperature, activation energy, and drift mobility were also determined to have values consistent with the semiconducting behavior of the soft ferrites. The saturation magnetization (M_S) has a maximum value 49.385 emu/g with remanent magnetization (M_r) was 34.928 emu/g and coercivity 661.4 Oe for La³⁺ concentration x = 0.05. The minimum dielectric loss was observed for La³⁺ concentration x = 0.025. Moreover, the resistivity (ρ) has a maximum value of 7.95 × 10⁴ Ω cm for La³⁺ concentration x = 0.025. The calculated frequency range of La³⁺ doped Mg–Cd–Cu ferrites was detected in the microwave range (3.36 – 10.80 GHz), suggesting the potential application of the materials in longitudinal recording media and microwave absorbance.     

Design of TiO2 nanorods and nanotubes doped with lanthanum and comparative kinetic study in the photodegradation of formic acid

Lanthanum doped 1D-TiO₂ nanomaterials (nanorods and nanotubes) with tuned structural and textural properties have been evaluated in the photocatalytic degradation of formic acid (FA) under UV conditions. La-doped nanorods and nanotubes calcined at 973 K show interesting photocatalytic properties with respect to La-free nanomaterials. The presence of La inhibits TiO₂ crystallite growth and increases the lifetime of photo-generated electron–hole pairs.     

Enhanced sunlight driven photocatalytic activity and electrochemical sensing properties of Ce-doped MnFe2O4 nano magnetic ferrites

This research deals with the facile combustion synthesis of manganese ferrite (MFO) nanoparticle with different cerium concentration and their potential application as an efficient photocatalyst and chemical sensor. The concentration of introduced cerium affects the size, structure, compositional, morphological, optical, photoluminescence and magnetic properties of the ferrite nanoparticle. The X-ray diffraction pattern affirmed the arrangement of cubic spinel structure with the formation of secondary phase CeO₂ as the cerium concentration exceed 3 mol%. SEM micrographs revealed irregular morphology with more number of pores and voids. HRTEM along with SAED pattern revealed the crystalline cubic nature. The optical band gap deduced from UV–Vis-DRS spectra was observed to be in the range 2.3–2.8 eV. PL studies indicated a significant minimization in combination of electrons & holes in MnFe₂O₄ on addition of Ce dopant. VSM investigation demonstrated the soft magnetic nature of the prepared sample with moderate magnetization value. An excellent photocatalytic performance of Cerium doped MFO (3 mol%) towards MB and AR dye degradation was found to be 1.5 and 1.67 times more compared to host matrix under Sunlight irradiation that correlated to reduced band gap, Ce dopant and efficient separation of charge carriers. Cerium doped MFO (3 mol%) have high specific capacitance value of 471.7 and 1546.8 Fg^-1 for NaNO₃ and HCl electrolytes respectively, indicating the pseudo capacitance nature due to which it can be used as a supercapacitor. The synthesized nanoparticles can sense d-Glucose and Paracetamol even at a lower concentration varying from 1 to 10 mM. The synthesized Ce-doped MnFe₂O₄ nanomaterials have great potential to be used in the future production of promising active photocatalysts and sensitive chemical sensors for the identification and degradation of toxic industrial dyes for improved safety in the fields of environment and health care.