First principles study of structural,electronic, elastic and thermal properties of YX (X = Cd,In, Au,Hg and Tl) intermetallics

The structural, electronic, elastic and thermal properties of YX (X = Cd, In, Au, Hg and Tl) intermetallic compounds crystallizing in B₂-type structure have been studied using first principles density functional theory within generalized gradient approximation (GGA) for the exchange correlation potential. Amongst all the YX compounds, YIn is stable in distorted tetragonal (P4/mmm) CuAu-type structure at ambient pressure with very small energy difference of 0.00681 Ry. but it undergoes to CsCl-type (B₂ phase) structure at 23.3 GPa. Rest of the compounds are stable in B₂ structure at ambient condition. The values of elastic moduli as a function of pressure are also reported. The ductility of these compounds has been analyzed using the Pugh rule. Our calculated results indicate that YTl is the most ductile amongst all the B₂-YX compounds. YAu is the hardest and less compressible compound due to the largest bulk modulus. The elastic properties such as Young's modulus (E), Poisson's ratio (σ) and anisotropic ratio (A) are also predicted. The anisotropic factor is found to be unity for YHg which shows that this compound is isotropic.     

The first silver bismuth borate,AgBi2B5O11

The first silver bismuth borate, AgBi₂B₅O₁₁ (silver dibismuth pentaborate), has been prepared via glass crystallization in the Ag₂O–Bi₂O₃–B₂O₃ system and characterized by single‐crystal X‐ray diffraction. Its structure is derived from that of centrosymmetric Bi₃B₅O₁₂ by ordered substitution of one Bi³⁺ ion for Ag⁺, which results in the disappearance of the mirror plane and inversion centre. Second harmonic generation (SHG) measurements confirm the acentric crystal structure. It is formed by [Bi₂B₅O₁₁]_∞ layers stretched along c and comprised of vertex‐sharing B₅O₁₀ and BiO₃ groups which incorporate the Ag⁺ cations. The new compound was characterized by thermal analysis, high‐temperature powder X‐ray diffraction, and vibrational and UV–Vis–NIR (near infrared) spectroscopy. Its thermal expansion is strongly anisotropic due to the presence of rigid B₅O₁₀ groups aligned in a parallel manner. The minimal value is observed along their axis [parallel to c, α_c = 3.1 (1) × 10^?6 K^?1], while maximal values are observed in the ab plane [α_a = 20.4 (2) and α_b = 7.8 (2) × 10^?6 K^?1]. Upon heating, AgBi₂B₅O₁₁ starts to decay above 684 K due to partial reduction of silver; incongruent melting is observed at 861 K. According to density functional theory (DFT) band‐structure calculations, the new compound is a semiconductor with an indirect energy gap of 3.57 eV, which agrees with the experimental data (absorption onset at 380 nm).     

B2O3 reinforced polylactic acid/thermoplastic polyethylene glycol shape memory composites

Recently, there has been a great demand for boron-containing compounds (BCCs) with unique biological properties. The demand for the use of these compounds not alone but as additives in composite materials is increasing day by day. In this study, the effect of adding B₂O₃ compound to the blend of PLA and PEG polymers, which is an important biocompatible shape memory polymer, was investigated. In order to examine the effect of increasing B₂O₃ additive on the thermal properties of PLA-PEG blend, it was determined by using a Differential Scanning Calorimetry (DSC) and thermogravimetric analyzer (TGA), and it was seen that while the melting temperature of PEG decreased, the melting temperature of PLA increased. In addition, when the thermal stability of the composites was examined, increasing of thermal stability was observed with the addition of B₂O₃ and a three-step degradation occurred. It was determined that the B₂O₃/PLA-PEG composite was homogeneous by taking X-ray measurements and SEM measurements. The antimicrobial property of the PLA-PEG blend improved with the increasing B₂O₃ contribution were observed from the antimicrobial activity measurements of the composite against 4 different bacteria. However, it was determined that the PLA-PEG blend preserved its shape memory effect with increasing diboron trioxide contribution.     

Colossal Anisotropic Thermal Expansion through Coupling Spin Crossover and Rhombus Deformation in a Hexanuclear {FeIII4FeII2} Compound

Colossal and anisotropic thermal expansion is a key function for microscale or nanoscale actuators in material science. Herein, we present a hexanuclear compound of [(Tp*)Fe^III(CN)₃]₄[Fe^II(Ppmp)]₂⋅2 CH₃OH ( 1 , Tp*=hydrotris(3,5-dimethyl-pyrazol-1-yl)borate and Ppmp=2-[3-(2′-pyridyl)pyrazol-1-ylmethyl]pyridine), which has a rhombic core structure abbreviated as {Fe^III₂Fe^II₂}. Magnetic susceptibility measurements and single-crystal X-ray diffraction analyses revealed that 1 underwent thermally-induced spin transition with the thermal hysteresis. The Fe^II site in 1 behaved as a spin crossover (SCO) unit, and significant deformation of its octahedron was observed during the spin transition process. Moreover, the distortion of the Fe^II centers actuated anisotropic deformation of the rhombic {Fe^III₂Fe^II₂} core, which was spread over the whole crystal through the subsequent molecular rearrangements, leading to the colossal anisotropic thermal expansion. Our results provide a rational strategy for realizing the colossal anisotropic thermal expansion and shape memory effects by tuning the magnetic bistability.     

The study of Bi3B5O12: synthesis, crystal structure and thermal expansion of oxoborate Bi3B5O12

The paper presents a new data on the crystal structure, thermal expansion and IR spectra of Bi₃B₅O₁₂. The Bi₃B₅O₁₂ single crystals were grown from the melt of the same stoichiometry by Czochralski technique. The crystal structure of Bi₃B₅O₁₂ was refined in anisotropic approximation using single-crystal X-ray diffraction data. It is orthorhombic, Pnma, a=6.530(4), b=7.726(5), c=18.578(5) Å, V=937.2(5) Å³, Z=4, R=3.45%. Bi³⁺ atoms have irregular coordination polyhedra, Bi(1)O₆ (d(B-O)=2.09-2.75 Å) and Bi(2)O₇ (d(B-O)=2.108-2.804 Å). Taking into account the shortest bonds only, these polyhedra are considered here as trigonal Bi(1)O₃ (2.09-2.20 Å) and tetragonal Bi(2)O₄ (2.108-2.331 Å) irregular pyramids with Bi atoms in the tops of both pyramids. The BiO₄ polyhedra form zigzag chains along b-axis. These chains alternate with isolated anions [B₂^IVB₃^IIIO₁₁]⁷⁻ through the common oxygen atoms to form thick layers extended in ab plane. A perfect cleavage of the compound corresponds to these layers and an imperfect one is parallel to the Bi-O chains. The Bi₃B₅O₁₂ thermal expansion is sharply anisotropic (α₁₁≈α₂₂=12, α₃₃=3×10⁻⁶ °C⁻¹) likely due to a straightening of the flexible zigzag chains along b-axis and decreasing of their zigzag along c-axis. Thus the properties like cleavage and thermal expansion correlate to these chains.     

Evolution structurale d'oxydes isomorphes MeX2O4: Relation entre dilatation,vibrations et rigidite

The neutron diffraction studies at low temperatures of the isomorphic compounds MeX₂O₄ (Pb₃O₄, SnPb₂O₄, NiSb₂O₄, ZnSb₂O₄) are discussed and correlated. Only powdered samples were used. The various thermal expansion tensors (α_a, α_c) of these tetragonal structures are interpreted from the thermal expansion of some MeO or XO bonds, the values of which are compared to simulated values. The relation between the temperature factor $\text{B}$ and the volume V gives the mean elastic constant. From elementary hypothesis, the compressibility is evaluated for each compound with a mean calculated value $\text{χ}\text{= 1.8 ×}$ 10^?11 Pa^?1. The Grüneisen parameters γ might vary from 0.34 to 0.65. From the crystallographic data, the Debye temperatures are evaluated and the anisotropic rigidity is discussed. Knowing χ it is possible to evaluate the s_ij elastic constants indirectly and so to interpret the anisotropic thermal expansion.     

Synthesis, crystal structure and thermal behavior of a novel oxoborate SrBi2B4O10

A new compound, SrBi₂B₄O₁₀, has been grown by cooling a melt with the stoichiometric composition. It is triclinic, P−1, a=6.819(1), b=6.856(1), c=9.812(2) Å, α=96.09(1), β=109.11(1), γ=101.94(1)°, V=416.5(1) Å³, Z=2. The crystal structure of the compound has been solved by direct methods and refined to R₁=0.050 (wR₂=0.128). The structure contains Bi-O pseudolayers build up from Bi-O chains involving oxocentred OBi₃ triangles. Sr atoms and [B₄O₉]⁶⁻ isolated anions (4B:3Δ□:<2Δ□>Δ) are located between the Bi-O packages.The thermal treatment as well as DSC experiment showed that the compound melts above 800 °C presumably according to the peritectic reaction: SrBi₂B₄O₁₀ ↔ SrB₂O₄+SrB₄O₇+ Liquid. According to high-temperature X-ray powder diffraction study thermal expansion of SrBi₂B₄O₁₀ structure is anisotropic (α₁₁=13, α₂₂=9, α₃₃=2, α_V=24×10⁻⁶ °C⁻¹).     

Subsolidus phase equilibria in the SrO-Bi2O3-B2O3 system

Phase equilibria in the SrO-Bi₂O₃-B₂O₃ system were studied using powder X-ray diffraction (XRD) and differential thermal analysis (DTA). Quasi-binary sections were determined, and an isothermal section of the system in the subsolidus region at 600°C was constructed using the crossing spections method. A new ternary compound was found: SrBi₂B₄O₁₀. The existence of SrBi₂B₂O₇ was verified. Bi₂O₃-SrB₂O₄ and Bi₄B₂O₉-2SrO: 3B₂O₃ polytherms were constructed.     

Mullitization behavior and microstructural development of B2O3–Al2O3–SiO2 mixtures activated by high-energy ball milling

This paper reports on phase formation and microstructural development of mullite, derived from B₂O₃–Al₂O₃–SiO₂ mixtures activated with different milling methods. It is found that the addition of B₂O₃ has a positive effect on mullite phase formation from the mixture of Al₂O₃–SiO₂, which can be qualitatively attributed to the fact that B₂O₃ brought out higher nucleation density and enhanced reaction kinetics. Anisotropic grain growth of mullite was not observed in the unmilled mixture since mullite phase formation occurred after densification. Dense and interlocking microstructures of mullite ceramics were produced from the mixture activated with stainless steel milling media, whereas mullite whiskers were formed in the samples milled with tungsten carbide media. The high-energy ball milling refined the precursors and thus reduced the mullitization temperature. As a result, anisotropic microstructures and mullite whiskers could be derived from the milled mixtures. This way to produce anisotropic microstructures of mullite ceramics is very simple and requires temperatures much lower than those reported in the literature. This method is believed to be useful to fabricate reinforced mullite or mullite-related materials via in-situ anisotropic grain growth.     

Phase behaviour of thermotropic banana-shaped compounds under pressure

The phase behaviour of two achiral bent core banana-shaped compounds, the hexyloxy (compound I) and decyloxy (compound II) members of the 1,3-phenylene bis[N-(2-hydroxy-4-n-alkoxybenzylidene)-4′-aminobenzoate] series was investigated under hydrostatic pressures up to 300?MPa using high pressure differential thermal analysis and light transmission methods. The reversible transition sequence crystal (Cr₁)–B₁ phase–isotropic liquid (I), observed at room pressure for compound I, remains in the pressure region up to c 70?MPa. At higher pressures a pressure-induced crystalline phase (Cr_i) appears between the Cr₁ and B₁ phases, its temperature region becoming wider with increasing pressure. The temperature vs. pressure phase diagram shows a triple point of 72.9?MPa and 160.3°C for the Cr₁, Cr_i and B₁ phases, indicating the lower limit of pressure for the Cr_i phase. In compound II the reversible transition sequence crystal (Cr₁)–B₂ phase–I is seen over the whole pressure region, and the temperature range of the B₂ phase remains unaltered. It is concluded that both the B₁ and B₂ banana phases are stable over the whole pressure region studied.     

Thermal conversions of chitosanium dodecahydro-<Emphasis Type="Italic">closo</Emphasis>-dodecaborate

The thermal behavior of chitosanium dodecahydro-closo-dodecaborate, (C₆O₄H₉NH₃)₂B₁₂H₁₂, was studied by thermal analysis, X-ray diffraction, and IR and X-ray photoelectron spectroscopy. As this compound is heated at a rate above 10–20 K/min, it ignites at a temperature of about 300°C. As the compound is heated to 1000°C at a rate below 10 K/min in an inert atmosphere, it yields a mixture of carbon and amorphous boron and/or boron carbides. The presence of a small amount of boron oxide in the product is explained by the formation of a partially oxidized hydroborate anion at the early stages of (C₆O₄H₉NH₃)₂B₁₂H₁₂ decomposition via the interaction between oxygen of the chitosanium cation and the B₁₂H₁₂²⁻ anion. Heating the initial compound in air at a rate below 10 K/min yields carbon and boron oxide as the main products. Molten boron oxide protects boron and/or boron carbides and boron nitride forming in small amounts in the particle bulk from oxidation.     

Composés isomorphes MeX2O4: Dilatation thermique anisotrope et ordre magnétique dans MnSb2O4

Using X-ray diffraction data, the anisotropic thermal expansion coefficients α_a and α_c of two isomorphic compounds MnSb₂O₄ and NiSb₂O₄ are linked to the anisotropic elastic constants of these tetragonal structures and compared to the ZnSb₂O₄, SnPb₂O₄ thermal expansion coefficients. The anomalous thermal expansion observed for MnSb₂O₄ in the 6–115 K range (maximum of α_c at 70 K) is related to the ordering of Mn²⁺ ion magnetic moments. Using neutron diffraction, two kinds of antiferromagnetic order are observed for MnSb₂O₄ and NiSb₂O₄. At 6 K the value of the resultant moment is approximately 1.8 μ_B for NiSb₂O₄ and 3.8 μ_B for MnSb₂O₄. A critical temperature of T_c = 115 K is proposed for MnSb₂O₄ based on the use of X-ray diffraction data alone.     

Structure de SnPb2O4 à quatre températures: relation entre dilatation et agitation thermiques

The structural study of SnPb₂O₄ oxide, an isomorphic compound belonging to the general family “MeX₂O₄” like Pb₃O₄, is made from accurate X-ray and neutron diffraction techniques on powdered samples. The structural evolution of SnPb₂O₄ is analyzed from 300 to 5 K: no phase transition is observed, contrary to Pb₃O₄, which exhibits a tetragonal → orthorhombic transition at 170 K. The thermal expansion tensor is practically isotropic in this temperature range: the α_a, α_c and α_V coefficients are neighboring those observed in the Pb₃O₄ tetragonal phase at the same temperature. On the other hand, the thermal vibrations are strongly anisotropic, with large amplitudes in the (a, b) plane. In this study the thermal vibrations are connected to the thermal expansion. $\text{B}\text{ab}$ and $\text{B}\text{c}$ temperature factors are considered as functions of the a and c cell parameters. The relation established by Grüneisen between the mean-square amplitudes of vibrations and the thermal volume expansion is discussed. The interatomic distances found show that the bindings are similar to that of Pb₃O₄: only the [Sn⁴⁺O₆] octahedrons are smaller than [Pb⁴⁺O₆] octahedrons.     

Anisotropic Electrical,Magnetic, and Thermal Properties of In3Ni2 Intermetallic Catalyst

We present the anisotropic electrical and thermal transport coefficients (electrical resistivity, magnetoresistance, thermoelectric power, thermal conductivity), the magnetic properties, the specific heat and the electronic density of states of a monocrystalline In₃Ni₂ intermetallic compound, representing a precious-metal-free (and noble-metal-free) intermetallic catalyst for the selective hydrogenation of α,β-unsaturated aldehydes. The investigated physical parameters were determined along three orthogonal crystal-symmetry directions of the trigonal structure, the twofold axis, the 3 axis and within the mirror plane. All the investigated tensorial and vectorial quantities show the same anisotropy, with the quantities being isotropic for the twofold direction and in the mirror plane, whereas there is small, though still significant anisotropy to the 3 direction. The In₃Ni₂ crystal conducts the electricity and heat somewhat less efficiently along the 3 direction than along the twofold direction and in the mirror plane, but the differences are not large, of about 20 %. In₃Ni₂ is a diamagnetic intermetallic compound, with a presumably simple Fermi surface and electrons as the majority charge carriers.     

Synthesis, crystal structure and thermal behavior of Sr3B2SiO8 borosilicate

Single crystals of Sr₃B₂SiO₈ were obtained by solid-state reaction of stoichiometric mixture at 1200 °C. The crystal structure of the compound has been solved by direct methods and refined to R1=0.064 (wR=0.133). It is orthorhombic, Pnma, a=12.361(4), b=3.927(1), c=5.419(1) Å, V=263.05(11) Å³. The structure contains zigzag pseudo-chains running along the b axis and built up from corner sharing (Si,B)−O polyhedra. Boron and silicon are statistically distributed over one site with their coordination strongly disordered. Sr atoms are located between the chains providing three-dimensional linkage of the structure.The formation of Sr₃B₂SiO₈ has been studied using annealing series in air at 900-1200 °C. According powder XRD, the probe contains pure Sr₃B₂SiO₈ over 1100 °C. The compound is not stable below 900 °C. In the pseudobinary Sr₂B₂O₅-Sr₃B₂SiO₈ system a new series of solid solutions Sr_3−xB₂Si_1−xO_8−3x (x=0-0.9) have been crystallized from melt. The thermal behavior of Sr₃B₂SiO₈ was investigated using powder high-temperature X-ray diffraction (HTXRD) in the temperature range 20-900 °C. The anisotropic character of thermal expansion has been observed: α_a= −1.3, α_b=23.5, α_c=13.9, and α_V=36.1×10⁻⁶ °C⁻¹ (25 °C); α_a= −1.3, α_b=23.2, α_c=5.2, and α_V=27.1×10⁻⁶ °C⁻¹ (650 °C). Maximal thermal expansion of the structure along of the chain direction [0 1 0] is caused by the partial straightening of chain zigzag. Hinge mechanism of thermal expansion is discussed.     

Densities of Melts of the System KF?K2MoO4?B2O3

The density of melts of the system KF? K₂MoO₄? B₂O₃ was measured. The molar volume in the binary system KF? K₂MoO₄ deviates only little from the ideal course, which indicates the extended thermal dissociation of the congruently melting additive compound K₃FMoO₄. In the KF? B₂O₃ binary system the formation of KBF₄ and K₂B₄O₇ leads to the volume expansion, like in the K₂MoO₄? B₂O₃ system, where the volume expansion may be described by the formation of the heteropolyanions [BMo₆O₂₄]^9?. The significant deviation from the ideal behaviour in the ternary system KF? K₂MoO₄? B₂O₃ refers to the pronounced interaction, most probably due to the substitution of oxygen atoms in the coordination sphere of the heteropolyanion with the fluorine ones.     

Crystal growth, crystal structure of new polymorphic modification, β-Bi2B8O15 and thermal expansion of α-Bi2B8O15

Single crystals of α- and β-polymorphs of Bi₂B₈O₁₅ were grown by Czochralski method from a charge of the stoichiometric composition. The crystal structure of β-Bi₂B₈O₁₅ was solved by direct methods from a twinned crystal and refined to R1=0.081 (wR=0.198) on the basis of 1584 unique observed reflections (I>2σ(I)). The compound is triclinic, space group , a=4.3159(8), b=6. 4604(12), c=22.485(4) Å, α=87.094(15)°, β=86.538(15)°, γ=74.420(14)°, V=602.40(19) Å³, Z=2. The B-O layered anion of β-Bi₂B₈O₁₅ is topologically identical to the anion of α-Bi₂B₈O₁₅ but the orientation of neighboring layers is different. Thermal expansion of α-Bi₂B₈O₁₅ has been investigated by X-ray powder diffraction in air in temperature range from 20 to 700 °C. It is strongly anisotropic, which can be explained by the hinge mechanism applied to chains of Bi-O polyhedra. While the anisotropy of thermal expansion is rather high, the volume thermal expansion coefficient α_V=40×10⁶ °C⁻¹ for α-Bi₂B₈O₁₅ is close to those of other bismuth borates.     

α‐Tris(2,4‐pentanedionato‐κ2O,O′)cobalt(III) at 240, 210, 180, 150 and 110 K

The crystal structure of the title compound, [Co(C₅H₇O₂)₃], has been investigated by a multi‐temperature measurement. In contrast to the isomorphous Al compound, the title compound exists in the studied temperature range as its monoclinic α polymorph (space group P2₁/c) and does not undergo a phase transition. Rigid‐body TLS analyses have been performed and the anisotropic thermal expansion tensor α_ij has been determined. The cell axes show a linear expansion behavior with respect to the temperature, but the slope is significantly different. A possible explanation are the different strengths of different intermolecular C—H...O contacts, which run in different crystallographic directions.     

Mechanochemical Synthesis of High Crystalline Cerium Hexaboride Nanoparticles from CeO2‐B2O3‐Mg Ternary System

High crystalline cerium hexaboride (CeB₆) nanoparticles (NPs) were synthesized using mixture of mag‐ nesium (Mg), cerium oxide (CeO₂) and boron oxide (B₂O₃) via the mechanochemical process at room tem‐ perature. Based on the results, magnesiothermic reduction of B₂O₃ occurred after about 2 h of milling in a mechanically induced self‐sustaining reaction (MSR). The significant amount of heat produced by the reduction reaction resulted in CeO₂ reduction to elemental Ce which finally reacted with elemental B and formed CeB₆ compound. According to XRD analyses, the degree of crystallinity and lattice parameter of the product was calculated about 93 % and 4.1458 Å, respectively. The morphology observations revealed that the synthesized CeB₆ had semi‐cubic shape with the range of size 25–60 nm. The synthesis of CeB₆ during the thermal treatment was studied by simultaneous thermal analysis (STA) technique. It was found that the reduction of B₂O₃ took place after melting of Mg meanwhile, no CeB₆ phase achieved even up to 1100 °C.     

Synergistic flame‐retardant effect and mechanisms of boron/phosphorus compounds on epoxy resins

To explore the component synergistic effect of boron/phosphorus compounds in epoxy resin (EP), 3 typical boron compounds, zinc borate (ZB), boron phosphate (BPO₄), and boron oxide (B₂O₃), blended with phosphaphenanthrene compound TAD were incorporated into EP, respectively. All 3 boron/phosphorus compound systems inhibited heat release and increased residue yields and exerted smoke suppression effect. Among 3 boron/phosphorus compound systems, B₂O₃/TAD system brought best flame‐retardant effect to epoxy thermosets in improving the UL94 classification of EP composites and also reducing heat release most efficiently during combustion. B₂O₃ can interact with epoxy matrix and enhance the charring quantity and quality, resulting in obvious condensed‐phase flame‐retardant effect. The combination of condensed‐phase flame‐retardant effect from B₂O₃ and the gaseous‐phase flame‐retardant effect from TAD effectively optimized the action distribution between gaseous and condensed phases. Therefore, B₂O₃/TAD system generated component synergistic flame‐retardant effect in epoxy thermosets.