Anharmonic lattice dynamics and thermal transport in type-I inorganic clathrates

The anharmonic phonon properties of type-I filled inorganic clathrates Ba8Ga16Ge30 and Sr8Ga16Ge30 are obtained from the first-principles calculations by considering the temperature-dependent sampling of the potential energy surface and quartic phonon renormalization. Owing to the weak binding of guest atoms with the host lattice, the obtained guest modes undergo strong renormalization with temperature and become stiffer by up to 50% at room temperature in Sr8Ga16Ge30. The calculated phonon frequencies and associated thermal mean squared displace- ments are comparable with experiments despite the on-centering of guest atoms at cage centers in both clathrates. Lattice thermal conductivities are obtained in the temperature range of 50- 300 K accounting for three-phonon scattering processes and multi-channel thermal transport. The contribution of coherent transport channel is significant at room temperature (13% and 22% in Ba8Ga16Ge30 and Sr8Ga16Ge30) but is insufficient to explain the experimentally observed glass-like thermal transport in Sr8Ga16Ge30.

First-principles calculations to identify key native point defects in Sr4Al14O25

This article reports for the first time an in-depth ab initio computational study on intrinsic point defects in Sr4Al14O25 that serves as host lattice for numerous phosphors. Defect Formation Enthalpies...

Environmentally benign rare earth pigments: effect of calcium dopant and tuning of bandgaps for different color hues

Purpose As there is a strong inducement to develop new colored inorganic materials to substitute the current industrial pigments that are based on toxic metals hazardous to health and the environment, the purpose of this paper is to invent environmentally benign rare earth-based colorants as viable alternatives to the traditional toxic pigment formulations. Herein, the authors developed a series of rare earth pigments having the general formula Ca0.1 Ln0.9 PO4 ( Ln = Y , Pr , mixed rare earth oxides, RE and Di). After studying all the optical properties, the authors have gone for some coloring application in plastic like PMMA. Design/methodology/approach The designed pigments were synthesized by traditional solid-state method. Stoichiometric amounts of each reagent were mixed in an agate mortar and the mixtures were calcined at optimized temperature 1000 °C for 4 h in electric furnace followed by auto–cooling. The samples were characterized by X-ray diffraction diffraction, UV–vis spectroscopy, scanning electron microscope (SEM), particle size distribution, color coordinates determination, acid/alkali test, thermo gravimetric (TG) analysis and CIE–1976 L*a*b* color scales. Among the various lanthanide ions and calcium ion as dopant, the pigment composition shows various hues ranges from green to yellow. The designed pigments consist of non–toxic elements and were further found to possess high thermal and chemical stability. The pigments were also found to be appropriate candidates for the coloration of polymer substrates like PMMA. Findings The present investigations establish that various color hues can be achieved by the incorporation of suitable chromophore metal ions like calcium in various rare earth host lattice by tuning of the band gaps. The coloring mechanism is based on the strong absorption of the pigments in the blue and red regions due to electronic transitions of the micro states of rare earth ion. The pigment composition shows various hues ranges from green to yellow. The coloring mechanism is based on the tuning of band gap by the dopant like calcium in various rare earth host lattice. In addition, this pigment was chemically and thermally stable. Finally, it has applied in plastics like PMMA. Research limitations/implications Mechanism of the color appearance using band calculations and on possible applications of rare earth phosphate powders as pigments in plastics and paints have not been explored much. However, the properties of the Ca-doped rare earth phosphate implies that this material has a potential to be applied as a satisfactory pigment for coating or coloring except for glaze, which may cause a side reaction at high temperatures, especially taking into consideration the economics and ecologies. The possibility of Ca2+ incorporation in CePO4 with monazite structure-type has been established. Practical implications The designed pigments consist of non-toxic elements and were further found to possess high thermal and chemical stability. The pigments were also found to be appropriate candidates for the coloration of polymer substrates. Thus, the present environmental friendly pigment powders may find potential alternative to the classical toxic inorganic pigments for various applications. Social implications There is a strong incentive to design new colorants based on inorganic materials to substitute for industrial pigments that are based on heavy elements hazardous to health and the environment. However, several industrial yellow pigments such as cadmium yellow (CdS), chrome yellow (PbCrO4) and nickel titanium yellow (TiO2-NiO-Sb2O3) contain the harmful elements (e.g. Cd, Pb, Cr and Sb) for the human body as well as the environment. The designed pigments consist of non-toxic elements and were further found to possess high thermal and chemical stability. The pigments were also found to be appropriate candidates for the coloration of polymer substrates. Thus, the present environmental friendly pigment powders may find potential alternative to the classical toxic inorganic pigments for various applications. Originality/value There is a strong incentive to design new colorants based on inorganic materials to substitute for industrial pigments that are based on heavy elements hazardous to health and the environment. However, several industrial yellow pigments such as cadmium yellow (CdS), chrome yellow (PbCrO4) and nickel titanium yellow (TiO2-NiO-Sb2O3) contain the harmful elements (e.g. Cd, Pb, Cr and Sb) for the human body as well as the environment. So, the authors have developed new class of inorganic pigments that are both non-toxic and environmentally unimpeachable, while preserving or even exceeding the optical, thermal and chemical characteristics of the existing commercial pigments. The developed colorants find practical applications in polymer matrix like PMMA.

Synthesis, characterization and effect of dopant on magnetic hyperthermic efficacy of Gd2O3 nanoparticles

Rare-earth oxides are paramagnetic materials and their high magnetic susceptibility in the bulk makes them potentially promising materials, but the magnetic properties of their nanoparticles remain incompletely characterized. We explore the effect of dopant (Tb3+ and Eu3+) in Gd2O3 host lattice as a heating agent for magnetic hyperthermia application. The structural, optical, and magnetic properties of the pristine, Gd2O3:Tb3+ and Gd2O3:Eu3+ nanocrystals were studied by XRD, HR-TEM, FTIR, and VSM. XRD analysis revealed the presence of mixed phase (cubic and monoclinic) in pristine, and doped Gd2O3 nanoparticles. The morphological information has been observed with the help of HRTEM and the calculated inter-planar spacing is in well agreement with JCPDS data. Particles are nearly spherical and diameter ~15nm, estimated from HRTEM image. FTIR spectroscopic analysis confirms the presence of Gd-O-Gd stretching at 583cm-1 . We confirmed the paramagnetic nature for all samples using VSM analysis. The self-heating capability of prepared samples are investigated by performing the induction heating experiment and it is assessed through calculated SAR and ILP values with help of Box-Lucas fitting model where 10% Tb3+ doped Gd2O3 has maximum values.

Mn4+ Activated Deep Red Emitting Perovskite Type Phosphors for Horticulture Lighting

Red emitting Mn4+ doped oxides are a promising class of materials to improve the colour rendering and luminous efficacy of phosphor-converted light-emitting diodes (pcLEDs). For pcLEDs, the optical properties are crucial w.r.t commercial acceptance. In this work, luminescence spectra and decay curves of Sr2YNbO6, Sr2YTaO6 and Sr2LaNbO6 have been recorded, other Mn4+ doped phosphors show that quenching occurs through thermally activated crossover between the 4T2 excited state and 4A2 ground state. The quenching temperature can be optimized by designing the host lattice in which Mn4+ has a high 4T2 state energy. The main target is to study the influence of the above-mentioned host materials on the emission spectra, PL quenching, and quantum yield of the deep red Mn4+ ion. The present study provides detailed insights into temperature and concentration quenching of Mn4+ emission and can be used to realize superior narrow-band red Mn4+ phosphors for horticultural lighting.

Impacts of vacancy-induced polarization and distortion on diffusion in solid electrolyte Li 3 OCl

Lithium-rich oxychloride antiperovskites are promising solid electrolytes for enabling next-generation batteries. Here, we report a comprehensive study varying Li + concentrations in Li 3 OCl using ab initio molecular dynamics simulations. The simulations accurately capture the complex interactions between Li + vacancies ( V Li ′ ), the dominant mobile species in Li 3 OCl . The V Li ′ polarize and distort the host lattice, inducing additional non-vacancy-mediated diffusion mechanisms and correlated diffusion events that reduce the activation energy barrier at concentrations as low as 1.5% V Li ′ . Our analyses of discretized diffusion events in both space and time illustrate the critical interplay between correlated dynamics, polarization and local distortion in promoting ionic conductivity in Li 3 OCl . This article is part of the Theo Murphy meeting issue ‘Understanding fast-ion conduction in solid electrolytes’.

Genuine divalent magnesium-ion storage and fast diffusion kinetics in metal oxides at room temperature

Rechargeable magnesium batteries represent a viable alternative to lithium-ion technology that can potentially overcome its safety, cost, and energy density limitations. Nevertheless, the development of a competitive room temperature magnesium battery has been hindered by the sluggish dissociation of electrolyte complexes and the low mobility of Mg2+ ions in solids, especially in metal oxides that are generally used in lithium-ion batteries. Herein, we introduce a generic proton-assisted method for the dissociation of the strong Mg–Cl bond to enable genuine Mg2+ intercalation into an oxide host lattice; meanwhile, the anisotropic Smoluchowski effect produced by titanium oxide lattices results in unusually fast Mg2+ diffusion kinetics along the atomic trough direction with a record high ion conductivity of 1.8 × 10−4 S ⋅ cm−1 on the same order as polymer electrolyte. The realization of genuine Mg2+ storage and fast diffusion kinetics enabled a rare high-power Mg-intercalation battery with inorganic oxides. The success of this work provides important information on engineering surface and interlayer chemistries of layered materials to tackle the sluggish intercalation kinetics of multivalent ions.

Environmentally Benign Rare Earth Pigments: Effect of Calcium Dopant and Tuning of Bandgaps for Different Color Hues

Environmentally benign rare earth pigments having the general formula Ca0.1 Ln0.9 PO4 ( Ln = Y , Pr , mixed rare rearth oxides, RE and Di ) have been prepared by a traditional solid state route. The samples were characterized by X–ray diffraction diffraction, UV–vis Spectroscopy, scanning electron microscope (SEM), particle size distribution, color coordinates determination, acid/alkali test, thermo gravimetric (TG) analysis and CIE–1976 L*a*b* color scales. Among the various lanthanide ions and calcium ion as dopant, the pigment composition shows various hues ranges from green to yellow. The coloring mechanism is based on the tuning of band gap by the dopant like calcium in various rare earth host lattice. The designed pigments consist of non–toxic elements and were further found to possess high thermal and chemical stability. The pigments were also found to be appropriate candidates for the coloration of polymer substrates.Thus, the present environmental friendly pigment powders may find potential alternative to the classical toxic inorganic pigments for various applications.

Energy Level Locations of Lanthanide Ions in Strontium-Aluminosilicate Phosphors

This paper determines the position of energy levels of lanthanide ions in Sr2Al2SiO7 (SAS) phosphor by a combining analysis of the lowest 4f-5d transition of Ce3+ ions and the charge transfer of Eu3+ ions-doped SAS phosphor. The SAS samples were successfully synthesized via solid state reaction, and their structure phase was further confirmed by X-ray diffraction. In the case of Eu3+-doped SAS phosphors, the energy of the charge transfer (CT) transition of the Eu3+ is about 4.70 eV (264 nm) and this energy is applied to determine the position 4f level of all divalent lanthanides relating to the top of the valence band in the SAS host lattice. For Ce3+ activated SAS samples, the lowest 4f1→4f05d1 excitation energy is determined around 3.71 eV (334 nm) and it is used to estimate the lowest 4f-5d transitions for all lanthanide (Ln) ions in host lattice. A broad band emission of the 5d→4f transition of Ce3+ ions includes two peaks emission with different energy about 1997 cm-1 that coincides with the theoretical value of 2000 cm-1. The host referred binding energy (HRBE) diagram of all Ln2+ and Ln3+ ions relating to the valance band of SAS materials has been constructed by using the data of fluorescent properties of Ce3+ and Eu3+ ions. The energy of 4f→5d transitions of Eu2+ ions that was predicted from the energy level scheme matches well with the observed experimental energy.