High-temperature X-ray Diffraction Research Articles

Thermal Runaway Mechanism in Ni-Rich Cathode full-cells of Lithium-ion Batteries: The role of Multidirectional Crosstalk.

Crosstalk, the exchange of chemical species between battery electrodes, significantly accelerates thermal runaway (TR) of lithium-ion batteries (LIBs). To date, the understanding of their main mechanisms has centered on single-directional crosstalk of oxygen (O2) gas from the cathode to the anode, underestimating the exothermic reactions during TR. However, the role of multidirectional crosstalk in steering additional exothermic reactions has yet to be elucidated due to the difficulties of correlative in situ analyses of full cells. Herein, we elucidate the way in which such crosstalk triggers self-amplifying feedback that dramatically exacerbates TR within enclosed full cells, by employing synchrotron-based high-temperature X-ray diffraction, mass spectrometry, and calorimetry. Our findings reveal that ethylene (C2H4) gas generated at the anode promotes O2 evolution at the cathode. This O2 then returns to the anode, further promoting additional C2H4 formation and creating a self-amplifying loop, thereby intensifying TR. Furthermore, CO2, traditionally viewed as an extinguishing gas, engages in the crosstalk by interacting with lithium at the anode to form Li2CO3, thereby accelerating TR beyond prior expectations. These insights have led us to develop an anode coating that impedes the formation of C2H4 and O2, to effectively mitigate TR. This article is protected by copyright. All rights reserved.

Manufacturing of High Purity Cr2AlC MAX Phase Material and Its Characterization

AbstractPresent study discusses about a technique for producing high-purity Cr2AlC MAX phase materials and gaining insight into their thermal behavior for high-temperature applications. The research conducted involved synthesizing a pure layered ternary carbide Cr2AlC MAX phase material by mixing powders of Chromium, Aluminum, and Carbon and then subjecting them to two-step pressureless sintering process in argon atmosphere. First step involves the annealing of ball-milled mixture at 750 °C for 2 h followed by the second step in which the annealed mixture is subjected to heat-treatment at 1350 °C for 2 h. Analysis using XRD and Raman techniques revealed that the synthesized product consists of Cr2AlC phase, without any impurities. SEM studies confirmed that the Cr2AlC had a layered topography, while EPMA analysis indicated that the atomic percentage of Cr, Al, and C was consistent with the XRD phase analysis. XPS investigations confirmed the presence of Cr-C bonds representing Mn+1Xn of the MAX phase material. TG-DSC results showed an approximately 2% increase in weight. The Cr2AlC phase exhibited an endothermic pattern below 725 °C, an exothermic pattern above it, and did not decompose up to 1400 °C in vacuum environment. High-temperature XRD analysis at various temperatures also confirmed no formation of Al2O3 or CrO impurity compounds.

Reedmergnerite and stillwellite-(Ce) from the Dara-i-Pioz alkaline massif: insights into high-temperature behavior of borosilicates

Research subject. Reedmergnerite and stillwellite-(Ce) were obtained from the rocks of the Dara-i-Pioz alkaline massif located on the southern slope of the Alai Range in Tajikistan, which is characterized by the presence of rare mineral species including borosilicates and lithium minerals. Aim. To investigate the thermal behavior of reedmergnerite and stillwellite-(Ce) using high-temperature X-ray diffraction, including the determination of phase transition temperatures and expansion/compression of the unit cell parameters, as well as the calculation of thermal expansion coefficients. Materials and methods. Chemical analysis was performed using a TESCAN MIRA 3 microscope (EDS mode) and a JEOL JXA-8230 electron probe microanalyzer (WDS mode). High-temperature powder X-ray diffraction data were collected using a D8 ADVANCE Bruker diffractometer with an HTK16 heating chamber, covering temperatures from 30°C to 750°C in ambient air. Results. The thermal expansion coefficients of reedmergnerite and stillwellite-(Ce) were determined. Heating reedmergnerite resulted in slight changes in the unit cell parameters, with the parameter c experiencing the smallest change and the parameter a showing the greatest increase. The unit cell volume increased by 1.8% when heated to 750°C and returned to its initial value upon cooling. When stillwellite-(Ce) is heated in the temperature range of 400–450°C, a phase transition occurs, which is confirmed by previously recorded temperature values. The conducted heating and subsequent cooling experiments revealed that the volume and unit cell parameters of stillwellite-(Ce) did not fully revert to their original values. Conclusions. The coefficients of thermal expansion tensor (αij) of rhodmerdgnertite and stillwellite-(Ce) were investigated as a function of temperature using high-temperature in-situ experiments. The phases exhibited relatively low values of thermal expansion parameters compared to the general data for feldspars and borosilicates obtained from literature. These findings contribute to the understanding of the thermoelastic behavior of this group of minerals and their potential applications in various fields.

Evaluation of the effect of oxygen incorporation on the thermo–chemical–mechanical properties of the proton-conducting oxide BaZr0.8Yb0.2O3-δ

This study aims to evaluate the effects of multiple defect species produced by water and oxygen incorporation on the lattice parameters of BaZr0.8Yb0.2O3-δ (BZYb20) and model its chemical expansion considering these effects. In this study, the lattice constant of BZYb20 was investigated under oxygen partial pressure (pO2 = 1–10−3 bar), water vapor partial pressure (pH2O = 0.0023 bar and dry) and over a wide range of temperatures (473–1173 K) using two approaches: model calculations and high-temperature X-ray diffraction (HT-XRD). HT-XRD measurements revealed that the lattice expansion of BZYb20 changed within 700–900 K in a humidified atmosphere. In a nonhumidified atmosphere, this temperature range shifts lower. High-temperature gravimetric measurements of oxygen incorporation showed that the change in oxygen vacancy concentration was sufficiently small, and the effect of oxygen incorporation on the lattice constant was negligible. High-temperature gravimetric measurements of water incorporation yielded thermodynamic parameters for the hydration reaction. Based on these results, the HT-XRD results were reproduced by fitting a lattice constant model that neglects the effects of oxygen. Therefore, the effect of oxygen incorporation on chemical expansion can be ignored, and the chemical expansion can be estimated using the model developed in this study.

Negative thermal expansion of β-Rb<sub>2</sub>SO<sub>4</sub>

Research subject. The low-temperature modification of β-Rb2SO4 sulfate (Pmcn). Aim. Low-temperature study of the thermal expansion of β-Rb2SO4 by high-temperature powder X-ray diffraction in comparison with the crystal structure, as well as interpretation of the anisotropy of β-Rb2SO4 thermal expansion. Materials and Method. Powder X-ray diffraction and high-temperature powder X-ray diffraction. Results. The thermal expansion of β-Rb2SO4 sulfate was studied for the first time using low-temperature powder thermal X-ray diffraction in comparison with the crystal structure. The phase composition was confirmed by powder X-ray diffraction. The thermal expansion of β-Rb2SO4 is practically isotropic. Across the temperature range from –177 to –140°C, the sulfate experiences negative thermal expansion. A further increase in temperature leads to a change in its thermal expansion, which becomes positive. It is proposed to consider the crystal structure of β-Rb2SO4 sulfate as a mixed framework of [RbSO4]–1, which, in turn, consists of fundamental building units (microblocks) of Rb(SO4)6. Across the temperature range from room temperature to –100°C, the maximum expansion of β-Rb2SO4 sulfate occurs along the a axis. The minimum thermal expansion is observed along the c-axis, along the columns consisting of microblocks (αa = 65.4(3)∙10–6°C–1, αb = 59.7(2)∙10–6°C–1, αc = 58.6(2)∙10–6°C–1 at +25°C). In the temperature range from –177 to –140°C, thermal expansion is negative in all three directions (αa = –10.3(3)∙10–6°C–1, αb = –8.6(2)∙10–6°C–1, αc = –9.7(2)∙10–6°C–1 at –170°C). Conclusion. The thermal expansion of β-Rb2SO4 sulfate in the low-temperature range (from –177 to –25°C) was studied for the first time, its structural interpretation was performed. A comparison was given with the thermal expansion of isostructural β-K2SO4.

Oxoborates of the ludwigite group: Natural and mineral-like compounds as prospective materials

Research subject. Natural oxoborates of the ludwigite group, including azoproite, ludwigite, and vonsenite. Their empirical formulas based on five oxygen atoms have the following form: azoproite (Mg1.81Fe2+0.19)∑2.00(Fe3+0.36Ti0.26Mg0.26Al0.12)∑1.00 O2(BO3), ludwigite (Mg1.69Fe2+0.30Mn2+0.01)Σ2.00(Fe3+0.90Al0.07Mg0.02Sn0.01)Σ1.00O2(BO3) and vonsenite (Fe2+1.86Mg0.13)∑1.99 (Fe3+0.92Mn2+0.05Sn4+0.02Al0.02)∑1.01O2(BO3). Aim. To establish the relationship between the composition, crystal structure, and thermal behavior (293–1373 K) of the minerals. Materials and methods. Ludwigite was collected at the Iten’yurginskoe tin skarn deposit; vonsenite was collected at the Titovskoe magnesium-skarn boron deposit; azoproite was collected at magnesian skarns of the Tazheran alkaline massif. The methods of single crystal X-ray diffraction, energy dispersive X-ray spectroscopy, high-temperature X-ray diffraction, Mössbauer spectroscopy, and thermal analysis were used. Results. Low-charge cations (Fe2+, Fe2.5+, Mg2+) tend to occupy the M(1)–M(3) sites, and high-charge cations (Fe3+, Al3+, Ti4+, Sn4+) generally occupy the M(4) site. Azoproite is characterized by the highest melting temperature Tm > 1650 K. Due to the low Fe2+ content, azoproite does not undergo solid-phase decomposition across the investigated temperature range. The melting point of ludwigite exceeds 1582 K, which is due to the high Mg content; as a result of the Fe2+ → Fe3+ oxidation, it gradually decomposes with the formation of hematite, warwickite, and magnetite. The temperatures of oxidation and solid-phase decomposition in the Fe2+-rich vonsenite are approximately 100 K lower than those in ludwigite. The melting point of vonsenite is 1571 K. All the minerals are characterized by a weak degree of thermal expansion anisotropy. The main contribution to the thermal expansion anisotropy is due to the preferred orientation of the [BO3]3– triangles. Conclusions. The thermal properties of the oxoborates depend on their chemical composition. It was established that Tm increases with an increase in the Mg and Ti4+ content, and decreases with an increase in the Fe2+ content. The Fe2+ → Fe3+ oxidation is observed when the FeO component in the minerals exceeds 10 wt %, which leads to the solid-phase decomposition starting at temperatures of about 500–600 K. The values of the 293KαV volume thermal expansion of ludwigite and azoproite are comparable, while the largest values were observed for vonsenite. This is associated with the largest average bond lengths, primarily those of <Fe2+–O>6.

Synthesis of calcium aluminate hydrates, their characterization and dehydration

This study is focused on the description of the dehydration of calcium aluminate hydrates (CAHs) and their identification. Four calcium aluminates (CA, C12A7, C3A, CA2) prepared by high temperature solid-state synthesis or modified Pechini synthesis served as precursors for CAHs. Hydration was carried out at the various temperatures in a range of 5–60 °C for 48 h. CAHs were identified by X-ray diffraction analysis (XRD) and their dehydration was characterized by Thermogravimetry and effluent gas analysis (TG/EGA) and high temperature XRD. Pure C3AH6 and CAH10 were successfully prepared, other CAHs (C2AH8, C4AH19, AH3, C4A C‾ H11) were present in the mixtures. The results indicate that dehydration of C3AH6 takes place at a temperature of about 300 °C, followed by the formation of a new product with a structure similar to C12A7. C2AH8 dehydration can be described in three steps. The dehydration is accompanied by the formation of crystalline intermediate products. CAH10 dehydration can be assigned to a broad peak on the DTG curve with a maximum at approximately 100 °C. The decomposition of C4A C‾ H11 takes place in two steps, with CO2 evolving in the temperature range 500–700 °C.

Zinc triggers favorable hydrogenation reaction in double perovskite PrBaCo2O6-δ: Applications in protonic ceramic cells

Protonic ceramic cell is seen as the next-generation energy conversion device designed to efficiently and reversibly convert chemical energy into electricity working at intermediate temperatures. However, their practical application heavily relies on the development of high-performance air electrodes. Mixed proton/electron/oxygen-ion conducting materials have promising potential as superior air electrodes, as they can significantly boost activity by extending active sites to the entire air electrode. Herein, we introduce 5 mol% hydrophilic Zn into PrBaCo2O6-δ resulting in the PrBaCo1.9Zn0.1O6-δ (PBCZn10), which exhibits enhanced proton uptake ability and excellent stability in steam-concentrated atmospheres. The electrochemical characterization results demonstrate that introducing Zn into PBC significantly reduces the polarization resistance by 45 % under 10% H2O/air at 550 °C. Applying such novel air-electrode on real electrochemical devices nearly doubled the out-put performance to 655 mW cm−2 at 650 °C. This confirms that the enhanced proton uptake ability in PBCZn10 facilitates proton interfacial transport and extends the reaction zone. Importantly, our study offers an insightful view into the proton uptake process and the surface evolution of the material before and after proton uptakes, employing high-temperature XRD and depth-profiling XPS. This work provides valuable guidance for developing triple electronic-ionic conducting oxides by shedding light on the proton uptake process on electrode materials.

Stability of Iodine Species Trapped in Titanium-Based MOFs: MIL-125 and MIL-125_NH2.

Two titanium-based MOFs MIL-125 and MIL-125_NH2 are synthesized and characterized using high-temperature powder X-ray diffraction (PXRD), thermogravimetric analysis(TGA), N2 sorption, Fourier transformed infrared spectroscopy (FTIR), Raman spectroscopy, ultraviolet-visible spectroscopy (UV-Vis), and electron paramagnetic resonance (EPR). Stable up to 300°C, both compounds exhibited similar specific surface areas (SSA) values (1207 and 1099m2g-1 for MIL-125 and MIL-125_NH2, respectively). EPR signals of Ti3+ are observed in both, whith MIL-125_NH2 also showing ─NH2 ●+ signatures. Both MOFs efficiently adsorbed iodine in continuous gas flow over five days, with MIL-125 trapping 1.9g.g-1 and MIL-125_NH2 trapping 1.6g.g-1. MIL-125_NH2 exhibited faster adsorption kinetics due to its smaller band gap (2.5 against 3.6eV). In situ Raman spectroscopy conducted during iodine adsorption revealed signal evolution from "free" I2 to "perturbed" I2, and I3 -. TGA and in situ Raman desorption experiments showed that ─NH2 groups improved the stabilization of I3 - due to an electrostatic interaction with NH2 ●+BDC radicals. The Albery model indicated longer lifetimes for iodine desorption in I2@MIL-125_NH2, attributed to a rate-limiting step due to stronger interaction between the anionic iodine species and the ─NH2 ●+ radicals. This study underscores how MOFs with efficient charge separation and hole-stabilizer functional groups enhance iodine stability at higher temperatures.

Crystal chemistry, Raman and FTIR spectroscopy, optical absorption, and luminescence study of Fe-dominant sogdianite

Abstract Fe-dominant sogdianite, a cyclosilicate compound with the chemical formula (Fe3+ 0.74Zr0.64Ti0.46 Al0.15)(□1.02Na0.98)K[Li3Si12O30], was studied. The investigation involved a comprehensive analysis of the mineral sample, including crystal-chemical analysis, Raman and FTIR spectroscopy, optical absorption, and luminescence study. Crystallographic site populations were determined through single crystal structure refinement and electron probe microanalysis. The thermoelastic behavior of a powder was studied using in situ high-temperature X-ray diffraction (30–750 °C). Notably, no phase transition was detected; sogdianite exhibited anisotropic thermal expansion. The first time study of vibrational spectra and spectral bands assigning were performed. The electronic transitions in d 5-ion impurities of sogdianite were studied using optical absorption and luminescence spectroscopy. The origin of pink color and luminescence of sogdianite was clarified. The broad spectral bands in the visible UV spectral region are responsible for the pink color exhibited by sogdianite and could be attributed to d–d transitions occurring in Fe3+ ions.

Synthesis, negative thermal expansion and optical performances of In0.5Sc1.5Mo3O12 thin films via sol-gel spin coating

Orthorhombic In0.5Sc1.5Mo3O12 thin films have been synthesized using the sol-gel spin coating. Influences of post-annealing temperatures on crystal structure, morphology, negative thermal expansion (NTE) and optical performances of the thin films were studied using XRD, SEM, XPS, high-temperature XRD and UV–Vis–NIR spectrophotometer. XRD and SEM results show that as-prepared thin film is in an amorphous state with a smooth and dense surface. Orthorhombic In0.5Sc1.5Mo3O12 thin films were obtained after post-annealing in 550–750 °C. The higher the annealing temperature in 550–750 °C, the better the crystallinity of orthorhombic In0.5Sc1.5Mo3O12 thin films. In addition, the grain size of the In0.5Sc1.5Mo3O12 thin film also grows as the annealing temperature increases. The resulting orthorhombic In0.5Sc1.5Mo3O12 thin films exhibit anisotropic NTE. Its volumetric coefficient of thermal expansion (CTE) is −3.44 × 10−6 °C−1, while the CTEs in a-, b- and c-axis directions are −4.70 × 10−6 °C−1, 5.37 × 10−6 °C−1, and -4.10 × 10−6 °C−1 in 25–700 °C, respectively. In addition, the transmittance of orthorhombic In0.5Sc1.5Mo3O12 thin films post-annealed at 750 °C is around 87.75 %–95.03 %.

Microstructure, adsorption site energetics, and formation enthalpy control for FAU-Zeolite Cs+ exchange

Cs-137 is a radionuclide fission product that poses a significant risk to life, making it crucial to develop effective methods for its separation and sequestration from nuclear waste streams. Zeolitic structures have emerged as promising materials. This work examines the influence of structure, exchange site energetics, and formation enthalpies of nascent and cation-exchanged Faujasite-X, -Y, and -HY zeolites in terms of their Cs-exchange selectivity. Their interplay was quantified with the application of high-temperature calorimetry, adsorption isotherms, X-ray diffraction and density functional theory (DFT) calculations. Greater efficacy of Cs+ exchange was demonstrated for the Na+-substituted Fau-Y (NaY) zeolite than that of the Fau-X (NaX) and Fau-HY (Na-HY) zeolites. This is explained by a higher amount of Na+ in un-exchangeable sites in the case of NaX and a lower stability in NaY that favors the ionic exchange with Cs+. Moreover, Cs+ incorporation in the structure increases the stability of each kind of zeolite. Correspondingly, structure and DFT analyses demonstrated site-exchange thermodynamic favorability as well as the contribution from cage cell, which resulted in an energy landscape far more conducive to Cs+ incorporation for NaY than either NaX or Na-HY.

Crystal structure solution and high-temperature thermal expansion in NaZr2(PO4)3-type materials.

The NaZr2P3O12 family of materials have shown low and tailorable thermal expansion properties. In this study, SrZr4P6O24 (SrO·4ZrO2·3P2O5), CaZr4P6O24 (CaO·4ZrO2·3P2O5), MgZr4P6O24 (MgO·4ZrO2·3P2O5), NaTi2P3O12 [½(Na2O·4TiO2·3P2O5)], NaZr2P3O12 [½(Na2O·4ZrO2·3P2O5)], and related solid solutions were synthesized using the organic-inorganic steric entrapment method. The samples were characterized by in-situ high-temperature X-ray diffraction from 25 to 1500°C at the Advanced Photon Source and National Synchrotron Light Source II. The average linear thermal expansion of SrZr4P6O24 and CaZr4P6O24 was between -1 × 10-6 per°C and 6 ×10-6 per °C from 25 to 1500°C. The crystal structures of the high-temperature polymorphs of CaZr4P6O24 and SrZr4P6O24 with R3c symmetry were solved by Fourier difference mapping and Rietveld refinement. This polymorph is present above ∼1250°C. This work measured thermal expansion coefficients to 1500°C for all samples and investigated the differences in thermal expansion mechanisms between polymorphs and between compositions.

Ionic liquid composites with garnet-type Li6.75Al0.25La3Zr2O12: Stability, electrical transport, and potential for energy storage applications

Garnet composites with ionic liquid dispersion have been prepared for electrolytic applications. Various ionic liquids (ILs) in small amounts were added to garnet type Li6.75Al0.25La3Zr2O12 (LALZO) to improve its ionic conductivity and electrode-electrolyte interfacial compatibility. The optimal composition having ∼6 wt% EMIM BF4 in LALZO showed a high ionic conductivity of 6 × 10-4 Ω-1cm-1 at room temperature, which is almost two orders of magnitude higher than the pristine garnet pellet. Such a high conductivity is attributed to the alteration of the ionic liquid-garnet interface by a weak non-uniform chemisorption. The thermal stability of the composites was confirmed by high-temperature X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry (DSC), and dynamic electrical transport measurements, which suggested their stability at least up to 200 °C. The electrochemical performance of the composite was evaluated by assembling 2032-type LFP//LALZO-IL//Li cell, which displayed promising candidature for energy storage applications.

Growth, crystal structure and IR luminescence of KSrY1-xErx(BO3)2.

A series of novel KSrY1-xErx(BO3)2 (x = 0-1) phosphors that emit near-infrared radiation was synthesized using solid-state methods. Pure Y and Er crystals were grown using a KF flux via the top-seeded solution growth technique. In situ high-temperature single crystal X-ray diffraction, Raman spectroscopy and DFT calculations were used for characterization. Within the series, a polymorphic phase transition from space group P21/m to R3m was discovered between 550 and 600°C. The concentration dependence of the luminescence intensity was measured for the samples. A strong emission of Er3+ electron transition 4I13/2 → 4I15/2 was detected within the 1529-1549 nm range, with the maximum observed for the KSrY0.4Er0.6(BO3)2 composition.

Charge Transport in the A6B2O17 (A = Zr, Hf; B = Nb, Ta) Superstructure Series

The electrical properties of the entropy stabilized oxides: Zr6Nb2O17, Zr6Ta2O17, Hf6Nb2O17 and Hf6Ta2O17 were characterized. The results and the electrical properties of the products (i.e. ZrO2, HfO2, Nb2O5 and Ta2O5) led us to hypothesize the A6B2O17 family is a series of mixed ionic-electronic conductors. Conductivity measurements in varying oxygen partial pressure were performed on A6Nb2O17 and A6Ta2O17. The results indicate that electrons are involved in conduction in A6Nb2O17 while holes play a role in conduction of A6Ta2O17. Between 900 °C–950 °C, the charge transport in the A6B2O17 system increases in Ar atmosphere. A combination of DTA/DSC and in situ high temperature X-ray diffraction was performed to identify a potential mechanism for this increase. In-situ high temperature X-ray diffraction in Ar does not show any phase transformation. Based on this, it is hypothesized that a change in the oxygen sub-lattice is the cause for the shift in high temperature conduction above 900 °C–950 °C. This could be: (i) Nb(Ta)4+- oxygen vacancy associate formation/dissociation, (ii) formation of oxygen/oxygen vacancy complexes (iii) ordering/disordering of oxygen vacancies and/or (iv) oxygen-based superstructure commensurate or incommensurate transitions. In-situ high temperature neutron diffraction up to 1050 °C is required to help elucidate the origins of this large increase in conductivity.

Real Competitors to Ruby: The Triel Oxonitridoborates AlB4O6N, Al0.97Cr0.03B4O6N, and Al0.83Cr0.17B4O6N

AbstractAlB4O6N, Al0.97Cr0.03B4O6N, and Al0.83Cr0.17B4O6N are the first representatives of the recently established structure‐family of oxonitridoborates containing Al3+. These compounds are isotypic to CrB4O6N and are synthesized in a multi‐anvil press under high‐pressure/high‐temperature conditions of 7.0 GPa/1350 °C. Structural refinement by single‐crystal X‐ray diffraction shows that they crystallize in the space group P63mc (no. 186) with two formula units per cell. Detailed characterization including high‐temperature X‐ray powder diffraction (HT‐XRD), electron probe microanalysis (EPMA), measurements of second harmonic generation (SHG), hardness, photoluminescence properties, vibrational spectroscopy, and band structure calculations reveal intriguing physicochemical properties that strongly resemble the famous material ruby.

Investigation of the anisotropic thermal expansion of PbIn6Te10 crystal by high temperature x-ray diffraction measurements

The PbIn6Te10 crystal, an IR laser frequency conversion material, grown via the Bridgman method with dimensions ϕ35 mm × 90 mm in a four-zone furnace, was subject to the investigation of its thermal expansion behavior using high-temperature x-ray diffraction in the range of 25–450 °C. Based on the obtained data, the average thermal expansion coefficients of 15.21 × 10−6 K−1 for α a and 6.44 × 10−6 K−1 for α c were determined utilizing the least square method. The study revealed that the linear and volume thermal expansion coefficients of PbIn6Te10 crystals satisfy the relationships α a > α c > 0, α V = 2α a + α c , and α a increased while α c decreased with increasing temperature, accentuating a substantial anisotropy in thermal expansion between the crystal’s principal axes. A detailed exploration pinpointed that the variations in the PbTe6 octahedron primarily governed the changes in the PbIn6Te10 unit cells, with further investigation uncovering its association with variations in the nearest neighboring bonds, which is mainly related to Pb-Te4 and Pb-Te2 bonds. Additionally, the determination of temperature-dependent anisotropic thermal expansion coefficient α was complemented by calculating Grüneisen parameter γ using Quasi-harmonic Debye model. Remarkably, these parameters also exhibited anisotropic behaviors ( γ⊥ increases with temperature whereas γ// decreases, α ⊥ > α ∥), contributing additional insights into the crystal thermal characteristics.

Synthesis and characterization of luminescent cerium-doped hydroxyapatite

Hydroxyapatite (HAp) biomaterials are intended for use as bone substitutes, target functional agents in theranostics or bioimaging due to affinity for hard tissues, biocompatibility, and bioactivity. This study is devoted to HAp doped with cerium, having distinctive feature to change the oxidation state (3+/4+), which affects the physico-chemical and optical properties of the obtained powders. Cerium-doped HAp nanopowders with Ce content up to 0.5 wt% were obtained through precipitation technique and then were heat treated. The following conditions for heat treating were used: (i) heating in air atmosphere, (ii) hot pressing, (iii) heating in a carbon filling. For characterization, the complex methodology was implemented, including X-ray diffraction (XRD) analysis and high temperature XRD, X-ray absorption near edge structure (XANES) spectroscopy, Fourier transform infrared (FTIR) spectroscopy, inductively coupled plasma atomic emission spectrometry (ICP-AES), transmission electron microscopy (TEM), electron paramagnetic resonance (EPR) spectroscopy, and, finally, photoluminescence (PL) spectroscopy. It was shown that the monophase cerium-HAp is stable up to a temperature of 1000 °C in the oxidizing atmosphere, above 1000 °C cerium(4+) oxide forms. Using reducing atmosphere during heating prevents the transition of Ce3+ to Ce4+. PL, EPR and XANES studding clarified obviously the Ce3+ content in the materials obtained under different processing conditions. It was shown, that Ce-HAp powders produced by precipitation and hot pressing contain Ce3+ and exhibit luminescence. The significant luminescence of hot pressed Ce-HAps was caused by a higher concentration of Ce3+ ions and incorporation of carbonate ions as a result of the processing.

Thermal behaviour of filatovite – a rare aluminoarsenate mineral of the feldspar group

AbstractThe high-temperature behaviour of a feldspar-group mineral, filatovite (with the simplified formula: K(Al,Zn)2(As,Si)2O8), in which the Al:As:Si ratio is close to 2:1:1), was studied by in situ high-temperature single-crystal X-ray diffraction and in situ high-temperature (hot stage) Raman spectroscopy up to 600°C. In the temperature range studied (25–600°С) filatovite does not undergo any phase transition, whereas at 800°C it decomposes to X-ray amorphous phase(s). The evolution of 12 main Raman bands was traced during heating, which indicates a gradual change in the crystal structure. The thermal expansion coefficients of filatovite demonstrate a sharply anisotropic character of thermal expansion: the maximal expansion is close to the a axis (α11 = 17.7(1) × 10–6 °C–1), whereas along the b and c axes the thermal expansion coefficients are close to zero. Such behaviour is typical for minerals with a similar crystal structure topology; it indicates the dominant role of structure geometry in the thermal behaviour of the mineral.