High-temperature Crystalline Phases Research Articles

Selective Photocatalytic CO2 Reduction to CH4 on Tri-s-triazine-Based Carbon Nitride via Defects and Crystal Regulation: Synergistic Effect of Thermodynamics and Kinetics.

Realizing the high selectivity of CH4 from the photocatalytic CO2 reduction reaction (CO2 RR) remains a great challenge owing to the lower efficiency of multi-electron transfer and the similar thermodynamic properties of CH4 and CO. Herein, nitrogen-deficient carbon nitride two-dimensional (2D) nanosheets were prepared via the high-temperature crystalline phase transformation process. Optimizing crystallinity enhances the in-plane polarization along the a-axis. Owing to the increased electron density of the N defect, the kinetic possibilities of CH4 production have increased. Furthermore, the potential energy of the mid-gap states introduced by the N defect favors the thermodynamics of CH4 production. The selectivity values of CH4 based on yield and electrons are 87.1 and 96.4%. This work unravels the mechanism to selectively produce CH4 from CO2 photoreduction through the crystalline phase and defect regulation and provides significant guidance for the rational design of CO2 reduction photocatalysts for selective CH4 production.

Formation of L10-FeNi hard magnetic material from FeNi-based amorphous alloys

L10-FeNi hard magnetic alloy with coercivity reaching 861 Oe was synthesized through annealing Fe42Ni41.3Si8B4P4Cu0.7 amorphous alloy, and the L10-FeNi formation mechanism has been studied. It is found the L10-FeNi in annealed samples at 400 °C mainly originated from the residual amorphous phase during the second stage of crystallization which could take place over 60 °C lower than the measured onset temperature of the second stage with a 5 °C/min heating rate. Annealing at 400 °C after fully crystallization still caused a slight increase of coercivity, which was probably contributed by the limited transformation from other high temperature crystalline phases towards L10 phase, or the removal of B from L10 lattice and improvement of the ordering quality of L10 phase due to the reduced temperature from 520 °C to 400 °C. The first stage of crystallization has hardly direct contribution to L10-FeNi formation. Ab initio simulations show that the addition of Si or Co in L10-FeNi has the effect of enhancing the thermal stability of L10 phase without seriously deteriorating its magnetic hardness. The non-monotonic feature of direction dependent coercivity in ribbon segments resulted from the combination of domain wall pinning and demagnetization effects. The approaches of synthesizing L10-FeNi magnets by adding Si or Co and decreasing the onset crystallization temperature have been discussed in detail.

Towards Higher Electric Conductivity and Wider Phase Stability Range via Nanostructured Glass-Ceramics Processing.

This review article presents recent studies on nanostructured glass-ceramic materials with substantially improved electrical (ionic or electronic) conductivity or with an extended temperature stability range of highly conducting high-temperature crystalline phases. Such materials were synthesized by the thermal nanocrystallization of selected electrically conducting oxide glasses. Various nanostructured systems have been described, including glass-ceramics based on ion conductive glasses (silver iodate and bismuth oxide ones) and electronic conductive glasses (vanadate-phosphate and olivine-like ones). Most systems under consideration have been studied with the practical aim of using them as electrode or solid electrolyte materials for rechargeable Li-ion, Na-ion, all-solid batteries, or solid oxide fuel cells. It has been shown that the conductivity enhancement of glass-ceramics is closely correlated with their dual microstructure, consisting of nanocrystallites (5–100 nm) confined in the glassy matrix. The disordered interfacial regions in those materials form “easy conduction” paths. It has also been shown that the glassy matrices may be a suitable environment for phases, which in bulk form are stable at high temperatures, and may exist when confined in nanograins embedded in the glassy matrix even at room temperature. Many complementary experimental techniques probing the electrical conductivity, long- and short-range structure, microstructure at the nanometer scale, or thermal transitions have been used to characterize the glass-ceramic systems under consideration. Their results have helped to explain the correlations between the microstructure and the properties of these systems.

The Influence of Carbon Black Content on the Phase Composition and Electric Conductivity of a Polymer Composite

We have studied the influence of the carbon black content on the phase composition of a polymer composite material based on ethylene vinyl acetate. It is established that there exists an additional (high-temperature) crystalline polymer phase the relative fraction of which depends on the content of carbon black. Saturation of the carbonaceous polymer composite with peroxide significantly influences the polymorphism of the material and its electric conductivity.

High-Temperature Evolution of the Incommensurate Composite Crystal Ca0.83CuO2

The crystal structure of the composite crystal Ca0.83CuO2 was investigated by synchrotron powder diffraction at high temperature. The incommensurate modulated structure was firstly analyzed at room temperature (RT) and successfully solved by adopting the (3D + 1)-dimensional symmetry P21/m(α0γ)0s. The composite crystal is featured by a non-uniform distribution of Ca ions occupying octahedral sites formed by the spatial arrangement by the infinite 1D CuO2 chains. By approaching 500 K, Ca0.83CuO2 undergoes a structural rearrangement ruled by the shrinking of the Ca interatomic distances. The high-temperature crystalline phase is characterized by a different incommensurate periodicity requiring the recombination of the Ca/CuO2 balance featuring the composite intergrowth of the two almost independent sub-structures. We ascertain that the new crystalline form is stable up to 950 K near to the limit of the thermal decomposition.

Influence of precursor characteristics on properties of porous calcium phosphate-titanium dioxide composite bioceramics

Highly porous (macroporosity 76–90%) bioceramics containing interconnected pores (>100 μm) with compressive strength between 0.54 and 0.32 MPa were prepared by polyurethane foam replica method. Effect of following variables, i.e., calcium phosphate/anatase ratio (30/70, 50/50, 70/30 wt%) in the ceramic slurry, anatase particle size (15 nm, 180 nm), Ca/P molar ratio of calcium phosphate (1.67 and 1.50 for hydroxyapatite and apatitic-tricalcium phosphate (ap-TCP), respectively), on the bioceramics properties was investigated. Bioceramics prepared using anatase and hydroxyapatite consisted of three high-temperature crystalline phases - β-tricalcium phosphate (β-TCP), rutile and CaTiO3. In case of anatase and ap-TCP, two phases (β-TCP and rutile) were obtained. Interaction of anatase and hydroxyapatite during sintering caused formation of CaTiO3 at β-TCP and rutile grain boundaries thus contributing to a denser grain packing. Combination of ap-TCP and nanosized anatase facilitated decrease of grain sizes. Correlation was found between compressive strength and calcium phosphate precursor in the ceramic slurry.

RE2O3-alkaline earth-aluminosilicate fiber glasses: Melt properties, crystallization, and the network structures

Glasses and/or glass fibers of a new glass system, RE2O3 (RE = Sc,Y, La)-MgO-CaO-Al2O3-SiO2, were studied in detail, covering rare earth (RE) effects on high temperature viscosity, liquidus temperature and crystalline phases, softening and glass transition temperature, and speciation reactions of aluminum (AlOx, x = 4, 5) and silicate network (Qn, n = 4, 3, 2) using 27Al and 29Si MAS NMR and Raman spectroscopic methods. Rare earth oxides (RE2O3) were shown to have a dual functionality, i.e., decreasing melt viscosity like a network modifier depolymerizing glass network, but increasing viscosity at low temperature, i.e., glass softening temperature (Tsoft) and transition temperature (Tg), strengthening the glass network functioning like Al2O3. Liquidus temperature (TLiq) was found to be sensitive to the type of RE2O3 modifications in terms of their ionic field strength (IFS); Sc3+ of the highest IFS increased, but La3+ of the lowest IFS decreased TLiq. Effect of Y3+ (intermediate IFS) on TLiq resembles Sc3+ only at higher concentration. The overall results suggest that RE ions of different IFS have different “true” solubility limits in the host glass matrix, above which RE2Si2O7 crystallizes. All of the glasses with and without RE2O3 contained predominately four-fold coordinated aluminum, AlO4; yet replacement of CaO by RE2O3 increased AlO5 according to 27Al MQMAS NMR spectroscopic measurements. Raman spectroscopic results suggested that depolymerization of the silicate network.

Influence of the Ag concentration on the medium-range order in a CuZrAlAg bulk metallic glass

Fluctuation electron microscopy of bulk metallic glasses of CuZrAl(Ag) demonstrates that medium-range order is sensitive to minor compositional changes. By analyzing nanodiffraction patterns medium-range order is detected with crystal-like motifs based on the B2 CuZr structure and its distorted structures resembling the martensitic ones. This result demonstrates some structural homology between the metallic glass and its high temperature crystalline phase. The amount of medium-range order seems slightly affected with increasing Ag concentration (0, 2, 5 at.%) but the structural motifs of the medium-range ordered clusters become more diverse at the highest Ag concentration. The decrease of dominant clusters is consistent with the destabilization of the B2 structure measured by calorimetry and accounts for the increased glass-forming ability.

Technical replicas of Portuguese ceramic tile bodies produced in the Oporto region in the late nineteenth to early twentieth centuries

Portugal is well known for its facades decorated entirely with ornamented glazed ceramic wall tiles called azulejos. On ageing, the tiles may detach and fall off, or deteriorate to such an extent that it becomes necessary to replicate them. Hence tile replication is a common practice in Portugal for façade restoration, but very often these new tiles do not have the same physical and/or chemical properties as the original ones. Such differences might be a factor in differential deterioration of the façades after restoration. One step toward an improvement in compatibility is to make new ceramic bodies with the same characteristics as the original ones. This study focuses on two types of glazed ceramic wall tiles from the Oporto region in Portugal: ‘calcic faience’ and pó de pedra. A total of 25 samples from the late nineteenth to early twentieth centuries were studied systematically as an attempt to improve knowledge of these materials and to create a basis for their replication. All samples were collected from facades that were under conservation/restoration at the time when sampling was performed. The original traditional ceramic bodies were analyzed by X-ray diffraction and X-ray fluorescence. Total open porosity, capillary absorption coefficient, and mercury intrusion porosimetry were also measured in order to gain knowledge on their physical characteristics in addition to their chemical and mineralogical compositions. High-temperature crystalline phases such as diopside, gehlenite, and mullite were found in the calcic faience, suggesting that the firing temperature of calcic faience bodies was within the range of 1100–1150 °C. Calcination trials were also performed in order to determine the most probable firing temperatures of the ceramic bodies. Collected data led to the assumption that the raw materials used for the ceramic bodies were kaolinitic clay, quartz sand, limestone, and talc. The raw materials for pó de pedra tiles were found to include kaolinite clay and quartz with firing temperatures estimated within the temperature range of 1150–1360 °C. Technical replicas made on the basis of these investigations were found to have the same mineralogical and capillary properties as the original tiles.

On the structure of crystalline and molten cryolite: Insights from the ab initio molecular dynamics in NpT ensemble.

Ab initio molecular dynamics simulations in isobaric-isothermal ensemble have been performed to study the low- and the high-temperature crystalline and liquid phases of cryolite. The temperature induced transitions from the low-temperature solid (α) to the high-temperature solid phase (β) and from the phase β to the liquid phase have been simulated using a series of MD runs performed at gradually increasing temperature. The structure of crystalline and liquid phases is analysed in detail and our computational approach is shown to reliably reproduce the available experimental data for a wide range of temperatures. Relatively frequent reorientations of the AlF6 octahedra observed in our simulation of the phase β explain the thermal disorder in positions of the F(-) ions observed in X-ray diffraction experiments. The isolated AlF6(3-), AlF5(2-), AlF4(-), as well as the bridged Al2Fm(6-m) ionic entities have been identified as the main constituents of cryolite melt. In accord with the previous high-temperature NMR and Raman spectroscopic experiments, the compound AlF5(2-) has been shown to be the most abundant Al-containing species formed in the melt. The characteristic vibrational frequencies for the AlFn(3-n) species in realistic environment have been determined and the computed values have been found to be in a good agreement with experiment.

Compositional dependent high temperature crystalline phase formation on manganese–silicon thin film combinatorial libraries in controlled oxidizing atmospheres

Wide compositional range Mn–Si thin film combinatorial libraries were used for studying the influence of the oxidation potential of the annealing atmosphere (510–12,500 ppm H2O at 900 °C) on phase formation. For all annealing conditions, the formation of silicide phases was evidenced. A threshold for O incorporation in newly formed crystalline phases was found to be related to water contents between 510 and 2880 ppm. In spite of the influence of high potential for oxidation on phase formation, silicide phases were identified for Si-rich alloys. The formation of higher manganese silicide (HMS) phases was identified in the compositional zone ranging from 56 at.% to 80 at.% Si and the exact phases were determined to be influenced by the annealing conditions. With higher water content in the atmosphere, the formation of Mn4Si7 was favored. However, independent on the increase in the water content the HMS formation was generally not inhibited by the applied annealing atmosphere. Given the wide range of possible application of HMS, this is highly relevant for the formation of HMS bulk or thin film materials.

Conversion of low spin states in a monochelate complex of Fe(III) with an asymmetric tridentate azomethine ligand

An iron(III)-containing complex with the asymmetric tridentate azomethine ligand 4,4′-dodecyloxybenzoyloxybenzoyl-4-salicylidene-N′-ethyl-N-ethylenediamine with a PF 6 − counterion is obtained. The presence of the complexing ion is confirmed by far IR Fourier spectra. The structure of the compounds is determined by matrix-assisted laser desorption/ionization with a time-of-flight mass analyzer (MALDI-ToF). The results of mass spectrometric studies are consistent with the elemental analysis data. It is found that the complexation of iron salt with an asymmetric tridentate ligand results in the formation of compounds of the composition 1:1 with octahedral packing of a metal ion in the complex. The electrochemical behavior of the compound in organic solvents is examined. The EPR study shows that iron(III) ions are in both low spin (LS) and high spin (HS) states in the complex. The LS and HS iron(III) centers are coupled into dimers in which a water molecule and the PF 6 − counterion act as bridges. It is also found that for LS complexes in the lowtemperature phase (4.2–300 K), the (d xz ,d yz )4(d xy )1 electronic state is the ground state. It is revealed that the conversion of the sample into a high-temperature liquid crystalline (387–405 K) phase is accompanied by the conversion of the LS states of the Fe(III) ion: (d xz ,d yz )4(d xy )1 ↔ (d xy )2(d xz ,d yz )3. The conversion of LS states is temperature reversible and is driven by the temperature. X-ray crystallographic data confirm that the compound obtained consists of dimer formed by a hydrogen (O-H...F) bond.

Transmission Electron Microscopy of CONCORDIA UltraCarbonaceous Antarctic MicroMeteorites (UCAMMs): Mineralogical properties

We performed mineralogical and petrographic studies of three UltraCarbonaceous Antarctic Micrometeorites (UCAMMs) by analytical transmission electron microscopy (TEM). The UCAMMs were identified in the CONCORDIA micrometeorite collection (2002 and 2006) recovered from central Antarctic snow, and are of probable cometary origin. UCAMMs are dominated by disordered carbonaceous matter that extends over surfaces of up to ∼90% of the particle. Embedded in this carbonaceous matter, we observed small and complex assemblages of fine-grained mineral phases, isolated minerals, glassy phases that resemble Glass with Embedded Metal and Sulfides (GEMS) that were first found in Interplanetary Dust Particles (IDPs), and rounded objects containing both glass and crystalline materials. The mineral assemblages are chondritic in composition, within a factor of 2. Crystalline materials represent at least 25% of mineral phases. This value is much larger than the upper limit of crystallinity measured in the diffuse interstellar medium (<2.2 wt%). Crystalline phases are dominated by low-Ca, Mg-rich pyroxenes, Mg-rich olivine and low-Ni Fe-sulfides. Exotic phases such as Mn-, Zn-rich sulfide and perryite have also been found as accessory minerals. The variety of high temperature mineral phases observed in UCAMMs is similar to that reported in chondritic porous IDPs and 81P/Wild 2 samples. The close association of high temperature crystalline phases with the low temperature carbonaceous matter in UCAMMs supports the hypothesis of a large-scale radial mixing in the early solar nebula. This new type of carbon-rich micrometeorites containing crystalline material provides the opportunity to analyze in situ, without any chemical processing, the association of materials formed at both low and high temperatures in the protoplanetary disk. A better knowledge of these samples is also important to prepare for future cometary missions, like ROSETTA in 2014.

Ab initioquality neural-network potential for sodium

An interatomic potential for high-pressure high-temperature (HPHT) crystalline and liquid phases of sodium is created using a neural-network (NN) representation of the ab initio potential energy surface. It is demonstrated that the NN potential provides an ab initio quality description of multiple properties of liquid sodium and bcc, fcc, cI16 crystal phases in the P-T region up to 120 GPa and 1200 K. The unique combination of computational efficiency of the NN potential and its ability to reproduce quantitatively experimental properties of sodium in the wide P-T range enables molecular dynamics simulations of physicochemical processes in HPHT sodium of unprecedented quality.

Effect of thickness on the crystallinity and Curie transition behavior in P(VDF/TrFE) (72/28) copolymer thin films using FTIR-transmission spectroscopy

The effect of thickness on the ferroelectric behavior in spin-cast poly(vinylidene fluoride/trifluoroethylene) (P(VDF/TrFE)) (72/28 mol%) random copolymer films with varying degree of crystallinity was analyzed qualitatively and quantitatively using Fourier transform infrared-transmission spectroscopy (FTIR-TS) data. From the qualitative analysis of raw IR data, the critical thickness of crystallization was observed near 130 nm, below which the films exhibited significant changes in crystalline peak (1292 cm −1) absorption. Using factor analysis (FA) of their raw IR data, we have isolated the pure crystalline and amorphous phase spectra, and also quantitatively calculated their degree of crystallinity as a function of thickness. FA of the mixture spectra obtained at varying temperatures during a heating–cooling cycle (30 °C → 140 °C → 30 °C) was conducted to isolate the pure spectra of the low-temperature (ferroelectric) and high-temperature (paraelectric) crystalline phases and to determine the content of each phase quantitatively as functions of thickness and temperature. Curie transition temperature during heating ( T c ↑ ) and cooling ( T c ↓ ) decreased and increased, respectively, resulting in reduced temperature range between T c ↑ ↔ T c ↓ with decreasing film thickness used in our study and the quantitative data obtained from FA were quite comparable with the qualitative data obtained from raw IR analysis.

Phase behavior and dynamics of a micelle-forming triblock copolymer system

Synperonic F-108 (generic name, "pluronic") is a micelle forming triblock copolymer of type ABA , where A is polyethylene oxide (PEO) and B is polypropylene oxide (PPO). At high temperatures, the hydrophobicity of the PPO chains increase, and the pluronic molecules, when dissolved in an aqueous medium, self-associate into spherical micelles with dense PPO cores and hydrated PEO coronas. At appropriately high concentrations, these micelles arrange in a face centered cubic lattice to show inverse crystallization, with the samples exhibiting high-temperature crystalline and low-temperature fluidlike phases. By studying the evolution of the elastic and viscous moduli as temperature is increased at a fixed rate, we construct the concentration-temperature phase diagram of Synperonic F-108. For a certain range of temperatures and at appropriate sample concentrations, we observe a predominantly elastic response. Oscillatory strain amplitude sweep measurements on these samples show pronounced peaks in the loss moduli, a typical feature of soft solids. The soft solidlike nature of these materials is further demonstrated by measuring their frequency-dependent mechanical moduli. The storage moduli are significantly larger than the loss moduli and are almost independent of the applied angular frequency. Finally, we perform strain rate frequency superposition experiments to measure the slow relaxation dynamics of this soft solid.

Band-edge properties of layered germanium dichalcogenides

The band-edge characteristic of germanium dichalcogenides $\mathrm{Ge}{(\mathrm{Se},\mathrm{S})}_{2}$ has been characterized using thermoreflectance (TR) and resistivity measurements at $300\phantom{\rule{0.3em}{0ex}}\mathrm{K}$. Two band-edge excitonic transitions denoted as ${E}_{A}$ and ${E}_{B}$ are found in each TR spectrum of $\mathrm{Ge}{({\mathrm{Se}}_{1\ensuremath{-}x}{\mathrm{S}}_{x})}_{2}$ $(0\ensuremath{\le}x\ensuremath{\le}1)$. A Rydberg excitonic series that contains two excitonic levels of $n=1$ and $n=2$ are simultaneously detected in the ${E}_{A}$ and ${E}_{B}$ transitions of $\mathrm{Ge}{\mathrm{Se}}_{2}$. For the other layered crystals, only the ground-state level $(n=1)$ is observed. Angular-dependent and polarization-dependent TR measurements of $\mathrm{Ge}{({\mathrm{Se}}_{1\ensuremath{-}x}{\mathrm{S}}_{x})}_{2}$ were carried out to identify the transition origins of the band-edge transitions. The experimental TR results show that $\mathrm{Ge}{({\mathrm{Se}}_{1\ensuremath{-}x}{\mathrm{S}}_{x})}_{2}$ with $x=0$, 0.2, 0.4, 0.6, and 0.8 are crystallized in the high-temperature crystalline phase, while the $\mathrm{Ge}{\mathrm{S}}_{2}$ belongs to the high-temperature and low-temperature mixed phases. The high in-plane resistivities of the $\mathrm{Ge}{({\mathrm{Se}}_{1\ensuremath{-}x}{\mathrm{S}}_{x})}_{2}$ indicate the high purity of the layer crystals.

Infrared and Raman spectra of silica polymorphs from an ab initio parametrized polarizable force field

The general aim of this study is to test the reliability of polarizable model potentials for the prediction of vibrational (infrared and Raman) spectra in highly anharmonic systems such as high temperature crystalline phases. By using an ab initio parametrized interatomic potential for SiO2 and molecular dynamics simulations, we calculate the infrared and Raman spectra for quartz, cristobalite, and stishovite at various thermodynamic conditions. The model is found to perform very well in the prediction of infrared spectra. Raman peak positions are also reproduced very well by the model; however, Raman intensities calculated by explicitly taking the derivative of the polarizability with respect to the atomic displacements are found to be in poorer agreement than intensities calculated using a parametrized "bond polarizability" model. Calculated spectra for the high temperature beta phases, where the role of dynamical disorder and anharmonicities is predominant, are found to be in excellent agreement with experiments. For the octahedral phases, our simulations are able to reproduce changes in the Raman spectra across the rutile-to-CaCl2 transition around 50 GPa, including the observed phonon softening.

Effect of γ-radiation on the molecular-topological structure of polytetrafluoroethylene

Four topological structures of polytetrafluoroethylene (PTFE): amorphous and three crystalline (high-melting, intermediate, and low-melting forms) blocks, were revealed by the technique of thermomechanical spectroscopy. The γ-irradiation of PTFE leaves both free volume and the molecular-mass characteristics in the pseudo-network structure of the amorphous block practically intact. In the crystalline phase, γ-irradiation decreases the molecular mass of crystallized chains of the low-temperature modification and leads to the disappearance of the intermediate and high-temperature crystalline phases as a result of their transformation into the amorphous phase.

Structural investigations and luminescence properties of nanocrystalline europium-doped yttrium silicates prepared by a sol–gel technique

Luminescent yttrium silicate powders doped with europium ions (Eu x Y 2− x SiO 5) were obtained by a sol–gel method after thermal treatment at 1300 °C. The crystalline phases retrieved from X-ray diffraction (XRD) patterns were quantitatively evaluated through Rietveld analysis, which showed that the formation and stability of high-temperature crystalline phases is affected by the europium ions. In fact, the X 2 monoclinic oxyorthosilicate Y 2SiO 5 is the dominant phase in all the samples and decreases on increasing europium content, while the relative amount of the additional apatite and disilicate phases increase. Small amounts of cubic yttria are also present. The Rietveld analysis evidences also an increase of the cell volume of the phases, except for the disilicate one, indicating that trivalent europium ions enter preferentially into the X 2 oxyorthosilicate, apatite and yttria structures. TEM observations indicate that the samples exhibit a rather large distribution of particle sizes from values lower than 20 nm up to higher than 100 nm. The emission spectra in the 5D 0 → 7F 0 region allowed to assign the occupation of the sites for the europium ions in the various phases in good agreement with XRD results. These materials appear to be interesting as phosphors for application in luminescent devices.