Articles de revues sur le sujet « Solid State Physics - Crystalline Order »

One of the key obstacles in the progress of certain aspects of solid-state physics is the determination of the nature of irregularities in the atomic network of matter and their correlation with macroscopic properties. In this work, an original structural result is presented, namely the presence of icosahedral clusters in an Al solid solution, as deduced from the analysis of the total Fourier-space image. This work has led to the belief that these non-crystalline clusters create a fundamental irregularity in the network of a non-ideal solid solution.

Abstract The kinetics of the first-order solid-state structural transition in monodisperse n-alkanes samples of tricosane C23H48 and tetracosane C24H50 was studied by DSC and FTIR spectroscopy. The initial nuclei location of the new phase was revealed. The process of crystal structure rearrangement is initiated in the interlayers between neighboring lamellar for odd tricosane, while the nanonuclei in even tetracosane arise in the crystalline lamella cores. Thus, the influence of the number evenness of carbon atoms in the n-alkanes chains on the first-order structural phase transition has been proved.

Two-step nucleation and subsequent growth processes were investigated in the framework of the single mode phase-field crystal model combined with diffusive dynamics (corresponding to colloid suspensions) and hydrodynamical density relaxation (simple liquids). It is found that independently of dynamics, nucleation starts with the formation of solid precursor clusters that consist of domains with noncrystalline ordering (ringlike projections are seen from certain angles), and regions that have amorphous structure. Using the average bond order parameter q¯6, we distinguished amorphous, medium range crystallike order (MRCO), and crystalline local orders. We show that crystallization to the stable body-centered cubic phase is preceded by the formation of a mixture of amorphous and MRCO structures. We have determined the time dependence of the phase composition of the forming solid state. We also investigated the time/size dependence of the growth rate for solidification. The bond order analysis indicates similar structural transitions during solidification in the case of diffusive and hydrodynamic density relaxation.

An attempt has been made to interpret the experimentally reported transitions of layer sequences during the Co/Si, Ti/Si, and Ni/Si interfacial reactions in a consistent way, and to build a thermodynamic calculation scheme that enables it. The basic ideas are that the silicide with the highest driving force of formation under a metastable local equilibrium state at an interface would form first at the lowest temperature, and that when several silicides can nucleate simultaneously and compete for growth at an initial stage of a high temperature reaction, the one whose composition is closest to those of surrounding phases would form a continuous interfacial layer first and grow thicker. A critical review of literature information has also been made in order to clarify the first-forming silicide and silicide formation sequence in each metalySi interfacial reaction. The observed first-forming crystalline silicides, CoSi, Ti5Si3, and Ni2Si, in each metalySi interfacial reaction were in agreement with the present prediction based on the first idea. The reason why Co2Si and C49 TiSi2 have frequently been observed in high temperature Co/Si and TiySi reactions as if they were the first-forming crystalline silicides could also be explained based on the second idea. By combining both ideas, a general thermodynamic calculation scheme that can be applied for analysis, rationalization, and even prediction of interfacial reactions between different materials could be suggested.

Phase pure olivine LiNiPO4 and doped LiNi0.8Mn0.1Co0.1PO4 powders have been prepared by conventional solid state route. X-ray diffraction (XRD) combined with Rietveld refinements analysis reveals the formation of LiNiPO4 and doped LiNi0.8Mn0.1Co0.1PO4 with high crystalline nature at high temperature of 950 °C and 1000 °C. The lattice parameters of doped LiNi0.8Mn0.1Co0.1PO4 are significantly larger than LiNiPO4. It has been found out that the estimated crystallite size is in the order of nanometres for both samples. SEM analysis confirms that the particles have connected with each other in random shape and sub-microns size. The particle size has increased as small amount of Mn and Co are doped into LiNiPO4. The AC impedance spectroscopy measurements have revealed that the conductivity of LiNiPO4 is enhanced by around one order of magnitude by doping Mn and Co.

Aluminium-chromium based alloys are promising candidates for manufacture of light components exposed to elevated temperatures. The work describes properties of Al-6.0wt.%Cr- 2.1wt.%Fe-0.5wt.%Ti alloy. The rapidly solidified powder was prepared by the pressure nitrogen melt atomization. The powder was then subject to heat treatment in order to investigate solid state phase transformations. Compaction of the powder was carried out by hot extrusion after preheating at 450 °C. Microstructure, phase composition and structural transformations on heat treatment were investigated in the as-atomized powder, as well as in the as-extruded alloy. It is found that metastable state of the rapidly solidified powder is characterized by presence of quasi-crystalline phases and supersaturated solid solution. Heating before and during the hot extrusion induces decomposition of the supersaturated solid solution and quasicrystalline to crystalline phase transformations. The hot extruded alloy has a refined recrystallized structure that remains very stable aven after long-term annealing at 400 °C. Mechanical properties of the extruded alloy are discussed in terms of strengthening mechanisms.

The 71Ga NMR spectra of Ga[GaX4] melts and of solutions in benzene and other hydrocarbons show discrete sharp GaI and broad GaIII resonances. In the light of recent structure determinations, the solution GaI signals must be attributed to bis(arene)Ga+ complexes in which the gallium atom is η6-bonded to the hydrocarbons. The low line widths and strong high field shifts are attributed to an almost spherical shielding of the metal nucleus by the 4 s2 electrons. Solid state 69Ga and 71Ga NMR spectra of Ga[GaCl4] crystalline powder show only Ga1 resonances. While the 71GaI line is rather narrow, the 69GaI line has a complex fine structure. Consistent with the crystal structure of Ga[GaCl4], the Ga1 ion is calculated to have a very low quadrupole coupling constant e2q Q/h = 1.7 ± 0.1 MHz and an asymmetry parameter η = 0.44. Experimental and simulated line shapes (using literature models) are in satisfactory agreement, implying that the 69Ga signal splitting is due to second order quadrupolar effects for the central m = + 1/2 ⇋ - 1/2 transition. The analogous splitting of the 71Ga NMR line is too small to be detected.

A novel tree-like nano-cadmium sulfide (CdS) with the fractal feature is synthesized by solid-state reaction at room temperature from complex precursor with aminotrimethylenephosphonic acid (ATMP) as ligand. The obtained sample is the crystalline cubic beta cadmium sulfide. The tree is composed of nanorods with an average diameter of ca. 95 nm and a length of up to 100–650 nm. The nanorods grow in the asymmetrical "Y" shape. The amount of ATMP plays an important role in the formation of fractal structure. Nonlinear optical (NLO) measurements by the Z-scan technique exhibit that the tree-like fractal nano- CdS has the third-order nonlinear optical properties of both NLO absorption and NLO refraction with self-focusing effect and the optical limiting performance.

The amorphous form of a drug usually exhibits higher solubility, faster dissolution rate, and improved oral bioavailability in comparison to its crystalline forms. However, the amorphous forms are thermodynamically unstable and tend to transform into a more stable crystalline form, thus losing their advantages. In order to investigate and suppress the crystallization, it is vital to closely monitor the drug solids during the preparation, storage, and application processes. A list of advanced techniques—including optical microscopy, surface grating decay, solid-state nuclear magnetic resonance, broadband dielectric spectroscopy—have been applied to characterize the physicochemical properties of amorphous pharmaceutical solids, to provide in-depth understanding on the crystallization mechanism. This review briefly summarizes these characterization techniques and highlights their recent advances, so as to provide an up-to-date reference to the available tools in the development of amorphous drugs.

The objective of this work is to embed liquid or volatile pharmaceuticals inside crystalline materials, in order to tune their delivery properties in medicine or agrochemistry, and to explore new regulatory and intellectual properties issues. Liquid or volatile formulations of active pharmaceutical ingredients (APIs) are intrinsically less stable and durable than solid forms; in fact most drugs are formulated as solid dosage because they tend to be stable, reproducible, and amenable to purification. Most drugs and agrochemicals are manufactured and distributed as crystalline materials, and their action involves the delivery of the active molecule by a solubilization process either in the body or on the environment. However some important compounds for the human health or for the environment occur as liquids at room temperature. The formation of co-crystals has been demonstrated as a means of tuning solubility properties of solid phases, and therefore it is widely investigated by companies and by solid state scientists especially in the fields of pharmaceuticals, agrochemicals, pigments, dyestuffs, foods, and explosives. In spite of this extremely high interest towards co-crystallization as a tool to alter solubility, practically no emphasis has been paid to using it as a means to stabilize volatile or labile or low-melting products. In this work we trap and stabilize volatile and liquid APIs and agrochemicals in crystalline matrices by engineering suitable co-crystals. These new materials alter the physic state of the active ingredients allowing to expand the phase space accessible to manufacturing and delivery. We have defined a benchmark of molecules relevant to human health and environment that have been combined with suitable partners according to the well known methods of crystal engineering in order to obtain cocrystals. The first successful results will be discussed; the Figure shows a cocrystal of propofol, a worldwide use anesthetic.

The application of atomic force microscopy (AFM) to solid-state photodimerizations revealed previously unexpected long-range molecular movements in the initial stages (phase rebuilding) and in the final stages (phase transformation and disintegration) of reaction. The consequences for the new understanding of solid-state photochemistry are discussed. The 4.2 Å criterion of organic topochemistry lacks a real basis and is not applicable to regular photolyses, even under tail irradiation conditions for instance ofα-cinnamic acid or inE/Z-isomerizations in the crystal bulk. The experimental observation of molecular movements in reacting crystals requires more elaborate use of X-ray structural data by invoking the molecular packing. If a crystal keeps its outer form upon photolysis this does not necessarily indicate a topotactic transformation, and submicroscopically resolved AFM investigations are in order. The applications of molecular movements or non-photoreactivities due to the prevention of movements by 3D-interlocked packing have numerous applications. Thus, amorphous solids or inclusion compounds may enable the movements in these cases. Hitherto puzzlingE/Z-photoisomerizations in the crystalline state can now be mechanistically understood. In some cases even rotational mechanisms can be modelled in combination with the movements. In others the space saving twist mechanism is the only choice. The benefits of the new solid-state mechanisms for crystal engineering, photochromism, mixed crystals, absolute asymmetric syntheses, and preparative photochemistry derive from its experimental basis. Numerous presumed puzzles from the postulate of minimal atomic and molecular movement vanish in a straightforward manner.

In order to create high-durable, wear-resistant materials for a wide range of functional applications, comparative investigations of the structure and mechanical characteristics of ion-plasma Ti-W-B nano-crystalline condensates were carried out. The range of condensation rates 0.11?0.25nm/s was found to be critical for the coatings obtained from the target with 80 vol% W2B5-20 vol% TiB2. Below this, a phase with a cubic lattice (W,Ti)B0.7?1.2(O,N,C)0.3?0.2 formed, while over this range, a solid solution (W,Ti)B2 with a hexagonal lattice and element composition close to the sputtered target was observed. The structure state of the material changed from cluster-crystalline (under low sputter potentials U=0.6?1.0 kV) to textured- crystalline (under U>2.2 kV). Structure perfection improvement with U increase results in higher hardness and elastic modulus of condensates. The conditions of cluster component formation and its effect on hardness and elastic modulus of condensates are discussed. .

Working with acylaminocarboxylate ligands, we used ethanol and water as a solvent, and the europium complexes were prepared using a chemical reaction method in solution. The elements were analyzed and characterized by polarizing microscope and XRD, respectively. The surfaces of complexes in the solid state were observed by polarizing microscope morphology. XRD diffraction data confirms the periodic long range order/disorder structure of these europium complexes. We also found that diversified material was easily formed by the rare earth complexes. Using the above tests, the structural information of the Eu complexes in the glassy state, liquid crystal glassy state and crystalline states was obtained

The thermophysical properties and microstructure of n-octadecane with crystalline and amorphous were investigated by employing the molecular dynamics (MD) simulation. The distribution of the end to end distance and bond torsion angle of the n-octadecane molecular chain and the mean square displacement and thermal conductivity before and after phase transition were also examined. MD simulation results indicates that the molecular chain conformation of amorphous n-octadecane in solid state is gradually changed from stretching to torsion by increasing temperature, and the chains will stretch out as the temperature rises in the liquid state. Compared with amorphous paraffin, the diffusion coefficient and the phase transition temperature of crystalline paraffin is lower than that of amorphous paraffin. The thermal conductivity of crystalline paraffin is much higher than that of amorphous paraffin. It is shown that improving the order degree of PCMs is an effective method to enhance their thermophysical properties.

Abstract New high-precision measurements of the isotropic as well as of three directional Compton spectra of lithium hydride have been carried out using241 Am as a γ-ray source. In order to account for the extreme sensitivity of LiH powder to atmospheric moisture, the final data (i.e. the reciprocal form factor) were corrected for the LiOH content determined by titrimetric analysis. For the interpretation of the data, theoretical calculations were carried out using a Hartree-Fock program for periodic systems (CRYSTAL). Basis sets published by Dovesi et al. were used, one of which allows for polarisation of both the hydride and lithium ions. Comparison of the theoretical data with the experiment shows much better agreement of the results of complete solid-state calculations that take into account higher-order effects (polarisation and covalency) than those obtained by Löwdin orthogonalisation of free-ion wave functions (which assumes pure ionicity, neglecting all but first-order effects). The influence of further polarisation functions on the reciprocal form factor is inves-tigated and discussed. The remaining discrepancies are attributed to electron-electron correlation.

DyFe[Formula: see text]Mn[Formula: see text]O3 (x[Formula: see text]=[Formula: see text]0, 0.025, 0.075, 0.15) polycrystalline samples were prepared using a traditional solid-state reaction route. The structural, magnetic and magnetocaloric properties of these samples were investigated. X-ray diffraction patterns showed that the samples exist as single-phase crystallines without peaks. The results of the Scanning Electron Microscopy (SEM) revealed that the average size of the polycrystalline particles decreased from 4.34 to 3.00 [Formula: see text]m as the Mn doping amount increased from 0.00 to 0.15. The magnetization versus temperature (M[Formula: see text]−[Formula: see text]T[Formula: see text]) plots showed that the order temperature of dysprosium (Dy) ions gradually decreased and the Morin-like transition temperature moved to the high-temperature region as x increased. The T[Formula: see text] gradually decreased from 13 to 10 K and the isotropic interaction of Fe[Formula: see text]-Fe[Formula: see text] was weakened as x increased from 0.00 to 0.15. The polycrystalline samples appeared as pre-formed clusters. The magnetization (M[Formula: see text]−[Formula: see text]H[Formula: see text]) plots revealed that all the samples underwent a first-order magnetic phase transition. The maximum magnetic entropy change, occurring near the Curie temperature, obtained at a magnetic-field span of 7 T, was 18.2 J/kg K. The maximum cooling capacity of the polycrystalline DyFe[Formula: see text]Mn[Formula: see text]O3 (x[Formula: see text]=[Formula: see text]0, 0.025, 0.075, 0.15) samples was 441 J/kg.

Cellulose nanocrystals (CNCs) are polydisperse rod-shaped particles of crystalline cellulose I, typically prepared by sulfuric acid hydrolysis of natural cellulose fibres to give aqueous colloidal suspensions stabilized by sulfate half-ester groups. Sufficiently dilute suspensions are isotropic fluids, but as the concentration of CNC in water is increased, a critical concentration is reached where a spontaneously ordered phase is observed. The (equilibrium) phase separation of the ordered chiral nematic phase is in competition with a tendency of the CNC suspension to form a gel. Qualitatively, factors that reduce the stability of the CNC suspension favour the onset of gelation. The chiral nematic structure is preserved, at least partially, when the suspension dries. Solid chiral nematic films of cellulose are of interest for their optical and templating properties, but the preparation of the films requires improvement. The processes that govern the formation of solid chiral nematic films from CNC suspensions include phase separation, gelation and also the effects of shear on CNC orientation during evaporation. Some insight into these processes is provided by polarized light microscopy, which indicates that the relaxation of shear-induced orientation to give a chiral nematic structure may occur via an intermediate twist-bend state. This article is part of a discussion meeting issue ‘New horizons for cellulose nanotechnology’.

Abstract Solid-state reactions, induced by ion-beam mixing (IBM) and thermal annealing, in Ni/Si multilayered films (MLF) with an overall stoichiometry of Ni2Si, NiSi and NiSi2, and with a constant Ni sublayer thickness (nominally, 3.0 nm), were studied by optical and magneto-optical spectroscopies as well as X-ray diffraction (XRD). The layer mixing was performed with Ar+ ions of an energy of 80 keV and a dose of 1.5 × 1016 Ar+/cm2. It was shown that the IBM leads to structural changes in the Ni/Si MLF, which cannot be easily detected by XRD but are recognized by optical tools. An annealing at 1073 K of the Ni/Si MLF with an overall stoichiometry of NiSi and NiSi2 induces formation of predominantly the η-NiSi and the NiSi2 phases, respectively. IBM of all the investigated Ni/Si MLF leads to the formation of regions with a short-range order of the crystalline NiSi silicide, and of Ni2Si (and/or Ni3Si) additionally for the Ni/Si MLF with an overall stoichiometry of Ni2Si.

In crystalline molecular solids, in the absence of strong intermolecular interactions, entropy-driven processes play a key role in the formation of dynamically modulated transient phases. Specifically, in crystalline simvastatin, the observed fully reversible enantiotropic behavior is associated with multiple order–disorder transitions: upon cooling, the dynamically disordered high-temperature polymorphic Form I is transformed to the completely ordered low-temperature polymorphic Form III via the intermediate (transient) modulated phase II. This behavior is associated with a significant reduction in the kinetic energy of the rotating and flipping ester substituents, as well as a decrease in structural ordering into two distinct positions. In transient phase II, the conventional three-dimensional structure is modulated by periodic distortions caused by cooperative conformation exchange of the ester substituent between the two states, which is enabled by weakened hydrogen bonding. Based on solid-state NMR data analysis, the mechanism of the enantiotropic phase transition and the presence of the transient modulated phase are documented.

Sputter-deposited Co–Gd and Cr–Gd multilayer films were studied by high resolution transmission electron microscopy (HRTEM). These two systems are expected to give rise to quite different structures. In good agreement with predictions, the individual Cr and Gd layers were found to be 100% crystalline with sharp interfaces and no noticeable intermixing. Conversely, the Co–Gd multilayer system underwent a solid state amorphization reaction during the deposition itself. This reaction has been found elsewhere to show an asymmetric character with the order of deposition, strong evidence for which is observed in this work.

The electronic structure of crystalline Li21Si5 is investigated by semiempirical MO (molecular orbital) calculations of the INDO (intermediate neglect of differential overlap) type in the framework of a finite cluster approach. The complex solid-state ensemble with 416 atoms per unit cell is divided into 16 cluster units M26 that form the three-dimensional structure. These M26 clusters have two different chemical compositions and act as formal donor and acceptor fragments, namely D = (Li20Si6) and A = (Li22Si4), having the formal net charges q(D ) = - 4 and q(A) = + 4. The electronic structures of these finite building units are rationalized by the semiempirical MO model. The one-electron energies of (Li20Si6)4- and (Li22Si4)4+ are derived on the basis of fragment interactions between the site sets (tetrahedral, octahedral, cube-octahedral) that build up the different M26 units. The canonical MO’s are transformed by means of the Edmiston-Ruedenberg localization procedure in order to come to a clear representation of the chemical bond in the two clusters. In (Li20Si6)4- a coincidence of the classical valence rules and the existence of nonclassical many-center bonds is found. (Li22Si4)4+ on the other side violates the counting schemes because of an excess of 2 electrons (electron octets at Si). The model calculations show however that the octet rule is strictly fulfilled in the Si subspace. The Li centers allow for the formation of an additional bonding cage orbital due to in-phase interactions between the Li 2s AO’s. This MO is occupied by the two excess electrons which are left after filling the valence orbitals associated to Si. The formation of such a one-electron level is not considered in classical models. The Li-Si interaction in Li21Si5 is of covalent nature and is comparable to the metal-nonmetal bonds in other lithium silicides. The Li-Li contacts are nonbonding in the framework of the Hartree-Fock approximation. The observed solid-state structure of the binary phase can be explained by intercluster interactions between the different donor and acceptor fragments.

We have used a combination of techniques to examine modifications in the structural characteristics of carbon nanofibers produced from the interaction of cobalt and copper-cobalt powders with ethylene at temperatures over the range 425 to 700 °C. The nanofibers generated from the interaction of cobalt with ethylene at 600 °C were found to be highly crystalline in nature. Incorporation of as little as 2% copper into the cobalt created a major modification in the conformation of the solid carbon deposit, which was composed of multiple nanofiber limbs emanating from a single catalyst particle, and in this state the carbon structures tended to be disordered. As the composition of the bimetallic was progressively changed to the point where copper became the major component, there was a significant increase in the degree of crystalline perfection of the nanofibers even though they maintained their multidirectional form. The transformation in structural characteristics of the carbon nanofibers is rationalized, according to a concept wherein the crystalline order of the deposit is related to the wetting properties of the bimetallic particles with graphite.

In this study, Mn(x)Zn(1-x)Fe2O4 ferrite samples with x=0.4 and 0.6 were synthesized using a solid-state method and co-precipitation method. In order to determine the effects of various concentrations (x) on the ferrite's structure, particle size, and crystalline phases, prepared samples were analysed using X-ray diffraction (XRD). The XRD patterns revealed that the synthesized samples display a single-phase cubic spinel structure.FTIR analysis showed for both synthesis method have absorption band in the range 400 to 1000 cm-1.SEM analysis shows extreme homogeneity of all the samples. EDX analysis was used to examine for Mn0.4Zn0.6Fe204,The prepared ferrites powders contain Mn, Zn, and Fe, as shown in both synthesis methods.In this approach, alternative synthesis routes for these ferrites are suggested in this study in order to get around some limitations of the traditional preparation method.

The thermal conductivity, κ, of solid triphenyl phosphite was measured by using the transient hot-wire method, and its temperature and pressure dependencies were analyzed to understand heat transfer processes in the solid polymorphic phases, as well as in the glass and the exotic glacial state. Phase transformations and the structural order of the phases are discussed, and a transitional pressure–temperature diagram of triphenyl phosphite is presented. The thermal conductivity of both the crystalline and disordered states is described within the theory of two-channel heat transfer by phonons and diffusons in dielectric solids. In the glass and glacial states, the weakly temperature-dependent (glass-like) κ is described well by the term associated with heat conduction of diffusons only, and it can be represented by an Arrhenius-type function. In the crystal phases, the strongly temperature-dependent (crystal-like) κ associated with heat transfer by phonons is weakened by significant heat transfer by diffusons, and the extent of the two contributions is reflected in the temperature dependence of κ. We find that the contribution of diffusons in the crystal phases depends on pressure in the same way as that in amorphous states, thus indicating that the same mechanism is responsible for this channel of heat transfer in crystals and amorphous states.

In this work, co-crystal screening was carried out for two important dihydrofolate reductase (DHFR) inhibitors, trimethoprim (TMP) and pyrimethamine (PMA), and for 2,4-diaminopyrimidine (DAP), which is the pharmacophore of these active pharmaceutical ingredients (API). The isomeric pyridinecarboxamides and two xanthines, theophylline (THEO) and caffeine (CAF), were used as co-formers in the same experimental conditions, in order to evaluate the potential for the pharmacophore to be used as a guide in the screening process. In silico co-crystal screening was carried out using BIOVIA COSMOquick and experimental screening was performed by mechanochemistry and supported by (solid + liquid) binary phase diagrams, infrared spectroscopy (FTIR) and X-ray powder diffraction (XRPD). The in silico prediction of low propensities for DAP, TMP and PMA to co-crystallize with pyridinecarboxamides was confirmed: a successful outcome was only observed for DAP + nicotinamide. Successful synthesis of multicomponent solid forms was achieved for all three target molecules with theophylline, with DAP co-crystals revealing a greater variety of stoichiometries. The crystalline structures of a (1:2) TMP:THEO co-crystal and of a (1:2:1) DAP:THEO:ethyl acetate solvate were solved. This work demonstrated the possible use of the pharmacophore of DHFR inhibitors as a guide for co-crystal screening, recognizing some similar trends in the outcome of association in the solid state and in the molecular aggregation in the co-crystals, characterized by the same supramolecular synthons.

A new tri-axial pressure-based constitutive expression has been found using Cauchy's stress tensor. This stress state emphasizes pressure and shear stress. The description is a pressure plus an effective shear stress allowing for a constitutive law based on atomic solid-state phase changes in crystalline cells due to pressure plus shear-based dislocation motion commonly associated with plasticity. Pressure has a new role in the material's constitutive response as it is separated from plasticity. The thermo-mechanical system describes third-order Gibbs’ expressions without specific volume restrictions placed upon the material. Isothermally, the ratio of heat to shear work in elastic copper is shown to approach zero at a very low temperature and become larger than one as temperature approaches melting. Wave compression models investigated are elastic and plastic: in fully elastic materials, the planar wave is restricted by Poisson's effect although plastic shear changes this constraint. Plastic deformation, dominated by dissipative shear stresses in uniaxial strain, heats the material while excluding phase changes from hydrostatic pressures. The material properties per se across Hugoniot shocks are described with entropy concepts. Shock waves are exceedingly complex since the constitutive laws are linked at extreme temperatures, pressures, and shear stresses. Isothermal, isentropic, isochoric, and iso-shear conditions are used throughout with Jacobian algebra.

A new tri-axial pressure-based constitutive expression has been found using Cauchy's stress tensor. This stress state emphasizes pressure and shear stress. The description is a pressure plus an effective shear stress allowing for a constitutive law based on atomic solid-state phase changes in crystalline cells due to pressure plus shear-based dislocation motion commonly associated with plasticity. Pressure has a new role in the material's constitutive response as it is separated from plasticity. The thermo-mechanical system describes third-order Gibbs’ expressions without specific volume restrictions placed upon the material. Isothermally, the ratio of heat to shear work in elastic copper is shown to approach zero at a very low temperature and become larger than one as temperature approaches melting. Wave compression models investigated are elastic and plastic: in fully elastic materials, the planar wave is restricted by Poisson's effect although plastic shear changes this constraint. Plastic deformation, dominated by dissipative shear stresses in uniaxial strain, heats the material while excluding phase changes from hydrostatic pressures. The material properties per se across Hugoniot shocks are described with entropy concepts. Shock waves are exceedingly complex since the constitutive laws are linked at extreme temperatures, pressures, and shear stresses. Isothermal, isentropic, isochoric, and iso-shear conditions are used throughout with Jacobian algebra.

We have prepared a series of pyridinium-based gemini amphiphiles. They exhibit thermotropic liquid–crystalline behavior depending on their alkyl chain lengths and anion species. By adjusting the alkyl chain lengths and selecting suitable anions, we have obtained an ionic amphiphile that exhibits a normal-type bicontinuous cubic phase from 38 °C to 12 °C on cooling from an isotropic phase. In the bicontinuous cubic liquid–crystalline assembly, the pyridinium-based ionic parts align along a gyroid minimal surface forming a 3D continuous ionic domain while their ionophobic alkyl chains form 3D branched nanochannel networks. This ionic compound can form homogeneous mixtures with a lithium salt and the resultant mixtures keep the ability to form normal-type bicontinuous cubic phases. Ion conduction measurements have been performed for the mixtures on cooling. It has been revealed that the formation of the 3D branched ionophobic nanochannels does not disturb the ion conduction behavior in the ionic domain while it results in the conversion of the state of the mixtures from fluidic liquids to quasi-solids, namely highly viscous liquid crystals. Although the ionic conductivity of the mixtures is in the order of 10–7 S cm–1 at 40 °C, which is far lower than the values for practical use, the present material design has a potential to pave the way for developing advanced solid electrolytes consisting of two task-specific nanosegregated domains: One is an ionic liquid nano-domain with a 3D continuity for high ionic conductivity and the other is ionophobic nanochannel network domains for high mechanical strength.

Recently, transition-metal-based kagome metals have aroused much research interest as a novel platform to explore exotic topological quantum phenomena. Here we report on the synthesis, structure, and physical properties of a bilayer kagome lattice compound V3Sb2. The polycrystalline V3Sb2 samples were synthesized by conventional solid-state-reaction method in a sealed quartz tube at temperatures below 850 °C. Measurements of magnetic susceptibility and resistivity revealed consistently a density-wave-like transition at T dw ≈ 160 K with a large thermal hysteresis, even though some sample-dependent behaviors were observed presumably due to the different preparation conditions. Upon cooling through T dw, no strong anomaly in lattice parameters and no indication of symmetry lowering were detected in powder x-ray diffraction measurements. This transition can be suppressed completely by applying hydrostatic pressures of about 1.8 GPa, around which no sign of superconductivity was observed down to 1.5 K. Specific-heat measurements revealed a relatively large Sommerfeld coefficient γ = 18.5 mJ⋅mol–1⋅K–2, confirming the metallic ground state with moderate electronic correlations. Density functional theory calculations indicate that V3Sb2 shows a non-trivial topological crystalline property. Thus, our study makes V3Sb2 a new candidate of metallic kagome compound to study the interplay between density-wave-order, nontrivial band topology, and possible superconductivity.

The static and dynamics properties of hydration water molecules in (±)-[Co(en)3]Cl3 were studied by means of 1H, 2H, and , 17O solid state NMR. By 'H pulsed field gradient (PFG) NMR the apparent diffusion coefficient of mobile water through a micropore along the crystalline unique c-axis was found to be 1.0 x 10-9 m2 s-1 . The 2H NMR spectrum at 141 K consists of two components, one being a Pake doublet corresponding to a quadrupole coupling constant (QCC) of (226 ± 2) kHz and an asymmetry parameter of the electric field gradient η of 0.08 ± 0.01, and another being a Gaussian line with a linewidth of 3.5 kHz. The 17O NMR spectrum at 300 K also consists of a narrow Gaussian peak and a broad powder pattern with a second order quadrupole effect corresponding to QCC = (6.3 ± 0.5) MHz and η = 0.55±0.02. The broad and narrow components are assigned to water molecules accommodated at general 12g positions and special 2a and 2b positions in the trigonal lattice with space group P1c1. From the ratio of the populations at these positions their potential energy difference was estimated to be between (2.7 ±0.1) and (3.5 ± 0.1) kJmol-1 . The 2H NMR spectrum at room temperature indicates a finite quadrupole interaction which is attributable to the rapid rotation of water molecule about the molecular C2-axis. When the water content exceeds 2.7, the QCC is reduced sharply to (5.0 ±0.1) kHz at 285 K, suggesting that there occurs rapid rotation of water and rapid exchange of 2H between nonequivalent positions.

The benefits of miniemulsion and emulsion polymerization are combined in a seeded emulsion polymerization process with functional seed particles synthesized by miniemulsion polymerization. A systematic study on the influence of different reaction parameters on the reaction pathway is conducted, including variations of the amount of monomer fed, the ratio of initiator to monomer and the choice of surfactant and composition of the continuous phase. Critical parameters affecting the control of the reaction are determined. If carefully controlled, the seeded emulsion polymerization with functional seed particles yields monodisperse particles with adjustable size and functionalities. Size-adjusted platinum-acetylacetonate containing latex particles with identical seed particles and varied shell thicknesses are used to produce arrays of highly ordered platinum nanoparticles with different interparticle distances but identical particle sizes. For that, a self-assembled monolayer of functional colloids is prepared on a solid substrate and subsequently treated by oxygen plasma processing in order to remove the organic constituents. This step, however, leads to a saturated state of a residual mix of materials. In order to determine parameters influencing this saturation state, the type of surfactant, the amount of precursor loading and the size of the colloids are varied. By short annealing at high temperatures platinum nanoparticles are generated from the saturated state particles. Typically, the present fabrication method delivers a maximum interparticle distance of about 260 nm for well-defined crystalline platinum nanoparticles limited by deformation processes due to softening of the organic material during the plasma applications.

A dodecadepsipeptide valinomycin (VLM) has been most recently reported to be a potential anti-coronavirus drug that could be efficiently produced on a large scale. It is thus of importance to study solid-phase forms of VLM in order to be able to ensure its polymorphic purity in drug formulations. The previously available solid-state NMR (SSNMR) data are combined with the plane-wave DFT computations in the NMR crystallography framework. Structural/spectroscopical predictions (the PBE functional/GIPAW method) are obtained to characterize four polymorphs of VLM. Interactions which confer a conformational stability to VLM molecules in these crystalline forms are described in detail. The way how various structural factors affect the values of SSNMR parameters is thoroughly analyzed, and several SSNMR markers of the respective VLM polymorphs are identified. The markers are connected to hydrogen bonding effects upon the corresponding (13C/15N/1H) isotropic chemical shifts of (CO, Namid, Hamid, Hα) VLM backbone nuclei. These results are expected to be crucial for polymorph control of VLM and in probing its interactions in dosage forms.

Transmission electron microscopy (TEM) techniques have been employed to study the room temperature solid state form of chromatographically purified C70. Tilting and electron diffraction experiments in three-dimensional reciprocal space, on samples prepared by crystallization from several different solvents, show that C70 crystallites adopt hexagonal close packed (hcp) structure with a = 1.01 ± 0.05 nm and c = 1.70 ± 0.08 nm. The extinctions and observed reflections conform to the P63/mmc space group. High resolution TEM images reveal the molecular order and periodicity associated with C70 crystallites in real space. The experimental results are in agreement with the preliminary computations of crystal structure within acceptable error limits.

Three crystalline N-trimethyltriindoles endowed with different functionalities at 3, 8 and 13 positions (either unsubstituted or with three methoxy or three acetyl groups attached) are investigated, and clear correlations between the electronic nature of the substituents and their solid-state organization, electronic properties and semiconductor behavior are established. The three compounds give rise to similar columnar hexagonal crystalline structures; however, the insertion of electron-donor methoxy groups results in slightly shorter stacking distances when compared with the unsubstituted derivative, whereas the insertion of electron-withdrawing acetyl groups lowers the crystallinity of the system. Functionalization significantly affects hole mobilities with the triacetyl derivative showing the lowest mobility within the series in agreement with the lower degree of order. However, attaching three methoxy groups also results in lower hole mobility values in the OFETs (0.022 vs. 0.0014 cm2 V−1 s−1) in spite of the shorter stacking distances. This counterintuitive behavior has been explained with the help of DFT calculations performed to rationalize the interplay between the intramolecular and intermolecular properties, which point to lower transfer integrals in the trimethoxy derivative due to the HOMO wave function extension over the peripheral methoxy groups. The results of this study provide useful insights into how peripheral substituents influence the fundamental charge transport parameters of chemically modified triindole platforms of fundamental importance to design new derivatives with improved semiconducting performance.

Nanocrystallized oxide precursors of colored (oxy)nitrides related to the system Yb-(Zr-W)-O have been successfully prepared using a chimie douce process—the amorphous citrate route. The process involves first a formation of fine and homogeneous powdered solids obtained by calcination at 600 °C, a temperature much lower than that of the conventional solid-state method. At this stage, the X-ray diffraction patterns exhibit large line broadening effects. Finally, two well-crystallized and pure quaternary oxides have been readily obtained by heating and under annealing conditions at 850 and 900 °C for 12 h. For one of the patterns, all the X-ray diffraction lines can be easily indexed to a cubic phase with the fluorite structure conforming to the Fm3m space group [Yb2Zr1.21W0.41O6.65◻1.35 called C-phase: a=5.1864(2) Å]. The second phase adopts the sheelite-type structure [Yb2ZrWO8 called T-phase: space group I41/a, a=5.1584(5), and c=10.8246(6) Å]. By taking into account the present compositions determined by EDS measurements, Rietveld structure refinements produce final RB factors of 0.015 and 0.044, and Rwp factors of 0.069 and 0.089, respectively. In order to characterize the microstructure of the materials (crystallite size and lattice distortion) at the nanometer scale, a study based on diffraction line broadening analysis applying the whole pattern refinement method was also undertaken with confidence. The results show smooth angular variations of the values of FWHMs, indicating that the microstructural properties are isotropic for the cubic and tetragonal oxides. More precisely, the results indicate that whatever the profile fitting approach used (“profile matching” procedure and Rietveld method), the reliability factors Rwp are systematically better with a combined size strain than with zero strain considerations. The strain magnitudes observed for the C-phase-850 °C as well as for the T-phase-900 °C should be viewed as realistic strain.

Silver nanoparticles were synthesized by an enzyme-induced growth process on solid substrates. In order to customize the enzymatically grown nanoparticles (EGNP) for analytical applications in biomolecular research, a detailed study was carried out concerning the time evolution of the formation of the silver nanoparticles, their morphology, and their chemical composition. Therefore, silver-nanoparticle films of different densities were investigated by using scanning as well as transmission electron microscopy to examine their structure. Cross sections of silver nanoparticles, prepared for analysis by transmission electron microscopy were additionally studied by energy-dispersive X-ray spectroscopy in order to probe their chemical composition. The surface coverage of substrates with silver nanoparticles and the maximum particle height were determined by Rutherford backscattering spectroscopy. Variations in the silver-nanoparticle films depending on the conditions during synthesis were observed. After an initial growth state the silver nanoparticles exhibit the so-called desert-rose or nanoflower-like structure. This complex nanoparticle structure is in clear contrast to the auto-catalytically grown spherical particles, which maintain their overall geometrical appearance while increasing their diameter. It is shown, that the desert-rose-like silver nanoparticles consist of single-crystalline plates of pure silver. The surface-enhanced Raman spectroscopic (SERS) activity of the EGNP structures is promising due to the exceptionally rough surface structure of the silver nanoparticles. SERS measurements of the vitamin riboflavin incubated on the silver nanoparticles are shown as an exemplary application for quantitative analysis.

A complex perovskite oxide Sr 2 YSbO 6 has been synthesized by solid-state reaction. X-ray diffraction (XRD) pattern reveals that Sr 2 YSbO 6 has an ordered complex cubic structure characteristic of A 2 BB ' O 6 crystalline structure with lattice constant a=8.2561 Å which has a fairly good lattice matching (lattice mismatch of the order of 8%) with YBa 2 Cu 3 O 7-δ. Energy dispersive X-ray (EDX) analysis shows that Sr 2 YSbO 6 is free of impurity traces. The chemical stability of Sr 2 YSbO 6 with YBa 2 Cu 3 O 7-δ superconducting has been studied by X-ray diffraction and magnetic measurements on Sr 2 YSbO 6– YBa 2 Cu 3 O 7-δ composites. XRD patterns of the composite show that all the XRD peaks could be indexed for either Sr 2 YSbO 6 or YBa 2 Cu 3 O 7-δ with no extra peak detectable. This implies that YBa 2 Cu 3 O 7-δ and Sr 2 YSbO 6 remain as two different separate phases in the composite with no chemical interaction. Magnetic measurements show that superconducting transition temperature of pure YBa 2 Cu 3 O 7-δ and Sr 2 YSbO 6– YBa 2 Cu 3 O 7-δ composites is 90 K. These favorable characteristics of Sr 2 YSbO 6 show that it can be used as a potential substrate material for fabrication of YBa 2 Cu 3 O 7-δ superconducting films.

Ionic liquid crystals (ILCs) present a new class of non-molecular soft materials with a unique combination of high ionic conductivity and anisotropy of physicochemical properties. Symmetrically-substituted long-chain imidazolium-based mesogenic ionic liquids exhibiting a smectic liquid crystalline phase were investigated by solid state NMR spectroscopy and computational methods. The aim of the study was to reveal the correlation between cation size and structure, local dynamics, and orientational order in the layered mesophase. The obtained experimental data are consistent with the model of a rod-shaped cation with the two chains aligned in opposite directions outward from the imidazolium core. The alignment of the core plane to the phase director and the restricted conformations of the chain segments were determined and compared to those in single-chain counterparts. The orientational order parameter S~0.5–0.6 of double-chain ionic liquid crystals is higher than that of corresponding single-chain analogues. This is compatible with the enhanced contribution of van der Waals forces to the stabilization of smectic layers. Increased orientational order for the material with Br− counterions, which exhibit a smaller ionic radius and higher ability to form hydrogen bonds as compared to that of BF4−, also indicated a non-negligible influence of electrostatic and hydrogen bonding interactions. The enhanced rod-shape character and higher orientational order of symmetrically-substituted ILCs can offer additional opportunities in the design of self-assembling non-molecular materials.

We report on structural and superconducting properties of La3-xRxNi2B2N3- where La is substituted by the magnetic rare-earth elements Ce, Pr, Nd. The compounds Pr3Ni2B2N3- and Nd3Ni2B2N3- are characterized for the first time. Powder X-ray diffraction confirmed all samples R3Ni2B2N3- with R = La, Ce, Pr, Nd and their solid solutions to crystallize in the body centered tetragonal La3Ni2B2N3 structure type. Superconducting and magnetic properties of La3-xRxNi2B2N3- were studied by resistivity, specific heat and susceptibility measurements. While La3Ni2B2N3- has a superconducting transition temperature Tc ~ 14 K, substitution of La by Ce, Pr, and Nd leads to magnetic pair breaking and, thus, to a gradual suppression of superconductivity. Pr3Ni2B2N3- exibits no long range magnetic order down to 2 K, Nd3Ni2B2N3- shows ferrimagnetic ordering below TC =17 K and a spin reorientation transition to a nearly antiferromagnetic state at 10 K.

Our long-term investigations have been devoted the characterization of intramolecular hydrogen bonds in cyclic compounds. Our previous work covers naphthazarin, the parent compound of two systems discussed in the current work: 2,3-dimethylnaphthazarin (1) and 2,3-dimethoxy-6-methylnaphthazarin (2). Intramolecular hydrogen bonds and substituent effects in these compounds were analyzed on the basis of Density Functional Theory (DFT), Møller–Plesset second-order perturbation theory (MP2), Coupled Clusters with Singles and Doubles (CCSD) and Car-Parrinello Molecular Dynamics (CPMD). The simulations were carried out in the gas and crystalline phases. The nuclear quantum effects were incorporated a posteriori using the snapshots taken from ab initio trajectories. Further, they were used to solve a vibrational Schrödinger equation. The proton reaction path was studied using B3LYP, ωB97XD and PBE functionals with a 6-311++G(2d,2p) basis set. Two energy minima (deep and shallow) were found, indicating that the proton transfer phenomena could occur in the electronic ground state. Next, the electronic structure and topology were examined in the molecular and proton transferred (PT) forms. The Atoms In Molecules (AIM) theory was employed for this purpose. It was found that the hydrogen bond is stronger in the proton transferred (PT) forms. In order to estimate the dimers’ stabilization and forces responsible for it, the Symmetry-Adapted Perturbation Theory (SAPT) was applied. The energy decomposition revealed that dispersion is the primary factor stabilizing the dimeric forms and crystal structure of both compounds. The CPMD results showed that the proton transfer phenomena occurred in both studied compounds, as well as in both phases. In the case of compound 2, the proton transfer events are more frequent in the solid state, indicating an influence of the environmental effects on the bridged proton dynamics. Finally, the vibrational signatures were computed for both compounds using the CPMD trajectories. The Fourier transformation of the autocorrelation function of atomic velocity was applied to obtain the power spectra. The IR spectra show very broad absorption regions between 700 cm−1–1700 cm−1 and 2300 cm−1–3400 cm−1 in the gas phase and 600 cm−1–1800 cm−1 and 2200 cm−1–3400 cm−1 in the solid state for compound 1. The absorption regions for compound 2 were found as follows: 700 cm−1–1700 cm−1 and 2300 cm−1–3300 cm−1 for the gas phase and one broad absorption region in the solid state between 700 cm−1 and 3100 cm−1. The obtained spectroscopic features confirmed a strong mobility of the bridged protons. The inclusion of nuclear quantum effects showed a stronger delocalization of the bridged protons.

As devices for amplifying or transforming electronic signals into audible signals through electromechanical operations, acoustic actuators in the form of loudspeakers are usually solid structures in three dimensional space. Recently there has been increasing demand for mobile electronic devices, such as mobile phones, to become smaller, thinner, and lighter. In contrast to a three dimensional audio system with magnets, we have invented a new type of flexible two dimensional device by utilizing the reverse piezoelectric effect in certain piezoelectric materials. Crystalline piezoelectric materials show electromechanical interaction between the mechanical state and the electrically-charged state. The piezoelectric effect is a reversible process in that materials exhibiting the direct piezoelectric effect (the internal generation of electrical charge resulting from an applied mechanical force) also exhibit the reverse piezoelectric effect (the internal generation of a mechanical strain resulting from an applied electrical field). We have adopted the plasma surface treatment in order to put coating materials on the surface of piezoelectric film. We compared two kinds of coating material, indium tin oxide and single-walled carbon nanotube, and found that single-walled carbon nanotube shows better performance. The results showed improvement of output power in a wider range of operating frequency; for the surface resistance of 0.5 kΩ/square, the single-walled CNT shows the range of operating frequency to be 0.75–17.5 kHz, but ITO shows 2.5–13.4 kHz. For the surface resistance of 1 kΩ/square, single-walled CNT shows the range of operating frequency to be 0.81–17 kHz, but ITO shows it cannot generate audible sound.

Changes in the magnetic behavior of Fe1–xAlx (x = 0.3, 0.4, 0.5, 0.6) powders during mechanical alloying have been studied. The ball milling process leads to formation of solid state reaction assisted by severe plastic deformation because of which crystallite size is reduced and as a result of which interesting magnetic properties are developed. The evolution of magnetic order in high-energy ball-milled Fe–Al solid solution is investigated using 57Fe Mössbauer spectroscopy and vibrating sample magnetometer. Mössbauer spectra and the hyperfine field distributions of all the samples show the presence of both magnetic and paramagnetic components in the samples. The corresponding bulk magnetization studies also show that the Al rich samples are also ferromagnetic, which can be attributed to the presence of disordered Fe-rich phases due to the non-equilibrium process of alloying. In Fe-rich samples, the formation of an off stoichiometric Fe3Al phase is favored while in the case of Al-rich samples both Al-rich phases and clustering of Fe and Al atoms are present. The systematic variation in the magnetic properties has been qualitatively correlated with the evolution of microstructure, reduction in grain size (obtained using transmission electron microscopy) and enhanced intergranular exchange coupling.

The random first order transition theory (RFOT) describing the transition from a supercooled liquid to an ideal glass has been actively developed over the last twenty years. This theory is formulated in a way that allows a description of the transition from the initial equilibrium state to the final metastable state without considering any kinetic processes. The RFOT and its applications for real molecular systems (multicomponent liquids with various intermolecular potentials, gel systems, etc.) are widely represented in English-language sources. However, these studies are practically not described in any Russian sources. This paper presents an overview of the studies carried out in this field. REFERENCES 1. Sanditov D. S., Ojovan M. I. Relaxation aspectsof the liquid—glass transition. Uspekhi FizicheskihNauk. 2019;189(2): 113–133. DOI: https://doi.org/10.3367/ufnr.2018.04.0383192. Tsydypov Sh. B., Parfenov A. N., Sanditov D. S.,Agrafonov Yu. V., Nesterov A. S. 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High-Tcsuperconducting cuprates (HTSC) such as YBa2Cu3O7 − x(YBCO) are promising candidates for solid-state THz applications based on stacks of intrinsic Josephson junctions (IJJs) with atomic thickness. In view of future exploitation of IJJs, high-quality superconducting YBCO tape-like single crystals (whiskers) have been synthesized from Ca–Al-doped precursors in the presence of Te. The main aim of this paper is to determine the importance of the simultaneous use of Al, Te and Ca in promoting YBCO whiskers growth with good superconducting properties (Tc= 79–84 K). Further, single-crystal X-ray diffraction (SC-XRD) refinements of tetragonal YBCO whiskers (P4/mmm) are reported to fill the literature lack of YBCO structure investigations. All the as-grown whiskers have also been investigated by means of X-ray powder diffraction (XRPD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). Our results demonstrate that the interplay of Ca, Te and Al elements is clearly necessary in order to obtain superconducting YBCO whiskers. The data obtained from SC-XRD analyses confirm the highly crystalline nature of the whiskers grown. Ca and Al enter the structure by replacing the Y and the octahedral coordinated Cu1 site, respectively, as in other similar orthorhombic compounds, while Te does not enter the structure of whiskers but its presence in the precursor is essential to the growth of the crystals.

Abstract Pb2Sc2Si2O9 and Pb2In2Si2O9, respectively, the scandium and indium containing structural analogues of the mineral kentrolite are grown by spontaneous crystallization from a PbO flux. The corresponding polycrystalline powder samples are synthesized by conventional solid-state approach. The compounds are thoroughly characterized using temperature-dependent single crystal and powder X-ray diffraction, heat capacity measurements, second harmonic generation experiments and Raman spectroscopy. At ambient conditions, both compounds crystallize in the non-centrosymmetric Pna21 space group and undergo phase transitions to the centrosymmetric Pbcn space group at elevated temperatures. The Pbcn into Pna21 phase transitions are complemented by the signals of the temperature-dependent second harmonic generation. The specific heat capacity exhibits distinct cusp, supporting the λ-type second-order phase transition. The temperature dependency of some selective Raman modes further complements the findings, showing softening and hardening of the phonons across the phase transitions.

In order to identify ways to improve the technological process of smelting metallic (crystalline) silicon of technical purity, a thermodynamic analysis of the interaction of components in the SiO2-C system is carried out that reveals the main factor in obtaining high-quality technical silicon is the elimination of superposition of the silicon carbonization process that is possible by carrying out a two-stage carbothermal reduction reaction, in that firstly the incomplete reduction of silica (SiO2) by solid carbon (C) is provided, accompanied by the release of new reacting gas components - SiO and CO, the subsequent interaction of which leads to the formation of the target product - technical silicon that is suitable for the production of modern solar energy converters. It is determined that main condition for highly efficient reduction reactions is the fine fractionness (<1 mm) of the used quartzite ore with keeping of a rational temperature range for its carbothermal reduction (1688-2000 K). It has been shown experimentally that the optimal technical solution for the implementation of this reduction process is to performt melting in a special plasma-chemical furnace-reactor with one liquid-metal subconducting electrode, with a reverse vertical feed of the reaction gases released at the first stage. The degree of extraction of silicon was on average 95%, and the degree of its purity was 97.2%.

The flavin derivatives 10-methyl-isoalloxazine (MIA) and 6-fluoro-10-methyl-isoalloxazine (6F-MIA) were incorporated in two alternative metal-organic frameworks, (MOFs) MIL-53(Al) and MOF-5. We used a post-synthetic, diffusion-based incorporation into microcrystalline MIL-53 powders with one-dimensional (1D) pores and an in-situ approach during the synthesis of MOF-5 with its 3D channel network. The maximum amount of flavin dye incorporation is 3.9 wt% for MIA@MIL-53(Al) and 1.5 wt% for 6F-MIA@MIL-53(Al), 0.85 wt% for MIA@MOF-5 and 5.2 wt% for 6F-MIA@MOF-5. For the high incorporation yields the probability to have more than one dye molecule in a pore volume is significant. As compared to the flavins in solution, the fluorescence spectrum of these flavin@MOF composites is broadened at the bathocromic side especially for MIA. Time-resolved spectroscopy showed that multi-exponential fluorescence lifetimes were needed to describe the decays. The fluorescence-weighted lifetime of flavin@MOF of 4 ± 1 ns also corresponds to those in solution but is significantly prolonged compared to the solid flavin dyes with less than 1 ns, thereby confirming the concept of “solid solutions” for dye@MOF composites. The fluorescence quantum yield (ΦF) of the flavin@MOF composites is about half of the solution but is significantly higher compared to the solid flavin dyes. Both the fluorescence lifetime and quantum yield of flavin@MOF decrease with the flavin loading in MIL-53 due to the formation of various J-aggregates. Theoretical calculations using plane-wave and QM/MM methods are in good correspondence with the experimental results and explain the electronic structures as well as the photophysical properties of crystalline MIA and the flavin@MOF composites. In the solid flavins, π-stacking interactions of the molecules lead to a charge transfer state with low oscillator strength resulting in aggregation-caused quenching (ACQ) with low lifetimes and quantum yields. In the MOF pores, single flavin molecules represent a major population and the computed MIA@MOF structures do not find π-stacking interactions with the pore walls but only weak van-der-Waals contacts which reasons the enhanced fluorescence lifetime and quantum yield of the flavins in the composites compared to their neat solid state. To analyze the orientation of flavins in MOFs, we measured fluorescence anisotropy images of single flavin@MOF-5 crystals and a static ensemble flavin@MIL53 microcrystals, respectively. Based on image information, anisotropy distributions and overall curve of the time-resolved anisotropy curves combined with theoretical calculations, we can prove that all fluorescent flavins species have a defined and rather homogeneous orientation in the MOF framework. In MIL-53, the transition dipole moments of flavins are orientated along the 1D channel axis, whereas in MOF-5 we resolved an average orientation that is tilted with respect to the cubic crystal lattice. Notably, the more hydrophobic 6F-MIA exhibits a higher degree order than MIA. The flexible MOF MIL-53(Al) was optimized essentially to the experimental large-pore form in the guest-free state with QuantumEspresso (QE) and with MIA molecules in the pores the structure contracted to close to the experimental narrow-pore form which was also confirmed by PXRD. In summary, the incorporation of flavins in MOFs yields solid-state materials with enhanced rigidity, stabilized conformation, defined orientation and reduced aggregations of the flavins, leading to increased fluorescence lifetime and quantum yield as controllable photo-luminescent and photo-physical properties.

AbstractThe phase diagram of the binary system [2,2-dimethyl-1,3-propanediol]x (1) / [2,2-dimethyl-1,3- diaminopropane]1-x (2) was studied by X-ray diffraction and DTA/DSC, for (2) also by 1H-NMR. The system is miscible over the whole concentration range 0 ≤ x ≤ 1 in the liquid state and in the plastic solid state, phase I, just below the melting point. At lower temperatures the system is demixing, and at room temperature two plastic mixed crystals coexist. The plastic phases of (1), (2), and (l)x(2)1-x crystallize face centered cubic, Fm3m, Z = 4, the lattice constants decreasing linearely with increasing x, and the lattice constants are: (1) a(327K) = 880.3 pm , (2) a(243K) = 905.6 pm. By single crystal X-ray diffraction the structure of the ordered phase II of (1) was refined at room temperature, monoclinic, P21/n, Z = 4, a = 596.9 pm, b = 1090.2 pm, c = 1011.0 pm, β = 99.74°. The results are in good agreement with the literature. The phase transition temperatures (in Kelvin) are T1→m = 399.2, TMm→1 = 399.7, T11→1 = 316.2, T1→11 = 308.2 for (1); = 300.2, = 301.7, T11→1 = 228.7, T1→n = 194.2 for (2). Strong hysteresis is observed for the transition T1→11 in (2). In the mixed systems (1)x(2)1-x, 0 < x < 1, the disordered phases do not order even by quenching to liquid nitrogen temperature. High resolution 1 H-NMR measurements are reported for phase I of (2) as a function of temperature. The “liquid” 1H-NMR spectrum is present far below the thermodynamic phase transition temperature T11-1, overlapping the wide line unresolved powder spectrum of phase II.

Four coals samples at different ranks were analyzed by Fourier transform infrared (FTIR), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and solid-state 13C nuclear magnetic resonance (NMR). The calculated coal molecular model was constructed according to the experimental data. The mode of evolution of four coal molecules with different metamorphic degrees was explored. The results indicate that the nanostructures of these four coal molecules mainly consist of aromatic structures, aliphatic structures and oxygen-containing functional groups. The coal metamorphic degree is the most important factor affecting the evolution of the coal molecular nanostructure. By increasing the coal rank, the aromatic carbon content and aromatic system increase, while the aliphatic carbon content and aliphatic system decrease, and the species and content of oxygen containing functional groups are also reduced. During the evolution of the molecular microcrystalline structure, the degree of vertical order of the aromatic structural unit, the flatness of the aromatic structural unit (La), the average crystallite stacking height (Lc), and the average number of crystallites in a stack (n) increase, while the interlayer distance between aromatic sheets (d002) decreases; the short-range ordering of the coal structure is mainly caused by changes in the orientational arrangement from intramolecular aromatic layers to intermolecular aromatic layers when low-rank coal molecules evolve to high rank coal molecules. The structural evolution mechanism of coal molecules of different ranks has been revealed through the analysis of the mode of evolution of the molecular structure the coal. This study enables us to better understand the nanostructure evolution mechanism of coal molecules at different ranks.