Theoretical studies on the penta-atomic planar coordinate carbon molecules [CGa3Sn] and [CGa3Sn]−

The pentaatomic [CGa₃Sn] and [CGa₃Sn]^? species were studied via density functional theory (DFT). Six planar geometry isomeric structures were gained, and one of them exists tetracoordinate planar carbon atom, respectively. To gain a better understanding about which electronic factors contribute to the stabilization of tetracoordinate planar carbon structures, natural bond orbital (NBO) analysis and the nucleus independent chemical shifts (NICS) were calculated. This analysis suggests that the presence of 18 valence electrons is crucial for planar geometries to be stable and preferred over tetrahedral structures.     

The density and surface tension of In–Sn and Cu–In–Sn alloys

Abstract  

The density and surface tension of binary In–Sn and ternary Cu–In–Sn alloys have been measured by a sessile-drop method. Decrease of the density and of the surface tension was observed with rising temperature. With increased Sn content in the alloys, the density increased while the surface tension reduced slightly. Addition of Cu could significantly increase the density and surface tension in the Cu–In–Sn system. The surface tension of the Cu–In–Sn alloys was also calculated by means of Butler’s equation, and compared with experimental values, showing good agreement.     

Dependency of thermal and electrical conductivity on temperature and composition of Sn in Pb–Sn alloys

The variations of thermal conductivity with temperature for Pb–Sn alloys were measured using a radial heat flow apparatus. The variations of electrical conductivity with the temperature for same alloys were determined from the Wiedemann–Franz law by using the measured values of thermal conductivity. According to present experimental results, the thermal and electrical conductivity of Pb–Sn alloys linearly decrease with increasing temperature but exponentially increase with increasing the composition of Sn. The enthalpy of fusion and the change of specific heat for Pb–Sn alloys were also determined by means of differential scanning calorimeter (DSC) from heating trace during the transformation from eutectic liquid to eutectic solid.     

Über das Mischungsverhalten von Nb3Sn mit Ti3Sn,Mo3Al und verwandten Phasen

Zusammenfassung Nb₃Sn und Mo₃Al bilden eine lückenlose Mischreihe. Nb₃Sn löst bei 1600°C rd. 60 Mol% Ti₃Sn, 30 Mol% Zr(3)Sn, 40 Mol% Hf(3)Sn bzw. 50 Mol% Nb(3)Si.Mit 5 Abbildungen     

{Sn9[Si(SiMe3)3]3}− and {Sn8Si[Si(SiMe3)3]3}−: variations of the E9 cage of metalloid group 14 clusters

The disproportionation reaction of the subvalent metastable halide SnBr proved to be a powerful synthetic method for the synthesis of metalloid cluster compounds of tin. Hence, the neutral metalloid cluster compound Sn(10)[Si(SiMe(3))(3)](6) (3) was synthesized from the reaction of SnBr with LiSi(SiMe(3))(3). In the course of the reaction anionic clusters might also be present, and we now present the first anionic cluster compound {Sn(8)E[Si(SiMe(3))(3)](3)}(-) (E = Si, Sn), where one position in the cluster core is occupied by a silicon or a tin atom, giving further insight into structural variations of E(9) cages in metalloid group 14 cluster compounds.     

Synthesis,Crystal Structure and Band Structure of Tb3Co4Sn（13）

A new intermetallic compound,Tb3Co4Sn13,has been synthesized by solid-state reaction of the corresponding pure elements in a welded tantalum tube at high temperature.Its crystal structure was established by single-crystal X-ray diffraction.Tb3Co4Sn13 crystallizes in cubic,space group Pm3n(No.223) with a = 9.5072(2) ,V = 859.33(3) 3,Z = 2,Mr = 2255.45,Dc = 8.717 g/cm3,μ = 34.369 mm-1,F(000) = 1906,and the final R = 0.0140 and wR = 0.0312 for 199 observed reflections with I > 2σ(I).The structure of Tb3Co4Sn13 belongs to the Yb3Rh4Sn13 type.It is isostructural with RE3Co4Sn13(RE = La,Ce),featuring a 3D [Co4Sn12] framework based on [CoSn6] trigonal prisms.The [CoSn6] trigonal prisms are interconnected via corner-sharing and Sn-Sn bonds to form a 3D [Co4Sn12] framework.The other Sn and Tb atoms are located in the spacers of the 3D framework.Band structure calculations indicate that Tb3Co4Sn13 is metallic.     

Phase equilibria in the Sn–As–Ge and Sn–As–P systems

T–x diagrams of polythermal GeAs–SnAs, GeAs–Sn₄As₃ sections of the Sn–As–Ge system and Sn₄P₃–Sn₄As₃ section of the Sn–As–P system were constructed using the results of X-ray powder diffraction and differential thermal analyses. It was found that the section GeAs–Sn₄As₃ is not quasi-binary due to realization of four-phase peritectic transformation L + SnAs ? GeAs + Sn₄As₃ at the temperature of 834 K. The quasi-binary section GeAs–SnAs represents a phase diagram of the eutectic type with the following coordinates of eutectic reaction: temperature of the eutectic point is 840 K, and composition is 20 mol% GeAs. In the Sn–As–P system, the existence of the solid-solution range indicated as (Sn₄As₃) _x (Sn₄P₃)_1?x  was defined. The polythermal section Sn₄P₃–Sn₄As₃ is not quasi-binary due to the fact that in the composition range with a high content of tin arsenide discussed section intersects the peritectic part of the three-phase volume (L + SnAs + α) of the ternary diagram.     

Influence of Sn and Sn/Mg doping on structural features and visible absorption properties of α-Fe2O3 hematite

Pure, Sn-doped and Mg/Sn co-doped α-Fe₂O₃ hematite samples were synthesized by precipitation process. Fe₂O₃ is the most popular red mineral pigment which is used largely in traditional ceramics, tar and concrete. The compounds were characterized by powder X-ray diffraction (XRD), scanning transmission electronic microscopy (energy dispersive X-ray cartography), Mössbauer spectroscopy, magnetic investigations versus temperature and visible-NIR spectroscopy. Both ⁵⁷Fe and ¹¹⁹Sn Mössbauer analyses combined with rietveld XRD refinements are the ideal techniques to characterize tin-iron oxides. Hence, thanks to these techniques it was shown how the synthesis temperature influences directly the grain size and the dopants concentration limit which can be incorporated into the host hematite matrix. The stabilization of these tetravalent and divalent dopants into the hematite framework leads to reduce the crystal growth and to limit the (AF) ordering due to the formation of cationic vacancies. The study of the Morin magnetic transition emphasizes this demonstration. In a second part, the influence of the dopants incorporation on the material color was investigated in order to show which key parameters allow improving the red color saturation of iron oxides. In order to improve the red color of the hematites, it was shown that the introduction of cationic vacancies—limiting the octahedral distortion thanks to the interruption of the dissymmetric metal-metal orbital coupling—is the key point. Vacancies are created by Sn⁴⁺, doping for an increase of the introduced Sn⁴⁺ concentration; it acts to the detriment of the color saturation.     

Hydrogen evolution reaction on Sn, In, and Sn–In alloys in carboxylic acids

The cathodic behavior of tin, indium, and tin–indium alloys in 0.5-M solutions of oxalic, malic, and citric acids has been investigated using potentiodynamic techniques at temperature range of 30–60 °C. The results showed that the corrosion rate (I _corr) is higher at lower indium percent (0.5% In) and starts to decrease gradually as increase of the In percent up to 5% In (although it is still higher than that of pure tin and lower than that of indium at 5% In) in all examined acids. The positive shift in corrosion potential with simultaneous increase in corrosion rate can be explained on the basis of the depolarizing action of β-InSn₄ phase compared with pure tin. The negative shift in the corrosion potential with much higher corrosion rate in case of alloys IV and V (10% and 20% In, respectively) can be ascribed to the formation of γ-In₃Sn phase which leads to the increase in the anodic to cathodic area ratio. The corrosion of the two investigated metals and their alloys is affected by the formation of soluble complex species with organic acid anions. The aggressiveness of the studied metals and their alloys decreases in the following order of the organic acids employed oxalic > malic > citric acid. The observed activation energy values support that the tested electrodes exhibit higher corrosion rates in oxalic acid solution than the corresponding values in the other investigated acids. X-ray diffraction and scanning electron microscopy photographs elucidated the types of phases formed in the prepared alloys. The presence of a definite amount of indium in tin alloy improves the hardness.     

Novel Low Dimensional Cluster Compounds: Syntheses and Crystal Structures of Cs[{Me3Sn}3{Re6Se8(CN)6}], [{Me3Sn(H2O)}2{Me3Sn}{Re6Se8(CN)6}] · H2O, and [(Me3Sn)3(OH)2][{Me3Sn}3{Re6Se8(CN)6}]. pH Control of the Structural Dimensionality

Three novel cluster complex compounds Cs[{Me₃Sn}₃{Re₆Se₈(CN)₆}] (1), [{Me₃Sn(H₂O)}₂{Me₃Sn}{Re₆Se₈(CN)₆}] · H₂O (2) and [(Me₃Sn)₃(OH)₂][{Me₃Sn}₃{Re₆Se₈(CN)₆}] (3) have been synthesized by reaction of Cs₃KRe₆Se₈(CN)₆ with SnMe₃Cl in aqueous solutions at different pH values (pH ～7 for 1, pH <7 for 2 and pH >7 for 3). The crystal structures of all compounds have low dimensional features (linear chains in 1, zig-zag chains in 2; layers in 3), they are polymeric ones based on ${-}{\rm Re}_{6}{-}{\rm CN}{-}{\rm SnMe}_{3}{-}{\rm NC}{-}{\rm Re}_{6}{-}$ bonding. The connectivity of these structures is determined strongly by reaction conditions, in particular, pH of reaction solutions.     

Temperature and Oxygen Partial Pressure Dependences of the Surface Tension of Liquid Sn–Ag and Sn–Cu Lead-free Solder Alloys

Summary. Temperature dependence of the surface tension of liquid Sn–Ag and Sn–Cu base lead-free solder alloys and oxygen partial pressure dependence of liquid Sn–Ag alloy were evaluated using the experimental data obtained, respectively, by the constrained drop method and the sessile drop method in the previous studies [1, 2]. The temperature dependences of the surface tension have maximum positive values when the mol fraction of Ag and Cu is about 0.7, while those for pure liquid Sn, Ag, and Cu have negative values. The calculated values based on Butler’s equations were found to be in reasonable agreement with those of the experimental data. The oxygen partial pressure dependences of the surface tension of liquid Sn–Ag alloys at 1253 K have a minimum value when the mol fraction of Ag is about 0.9 and the oxygen partial pressure is less than about 10⁻¹³ atm. From this, it is considered that the oxygen adsorption increased by adding Ag to Sn when the mol fraction of Ag is less than 0.9.     

Calorimetric study and thermal analysis of Al–Sn system

The results of calorimetric study and thermal analysis of binary Al–Sn system are presented in this paper. The Oelsen calorimetry was used in thermodynamic analysis. Following thermodynamic properties were determined at 727 °C: activities, activity coefficients, partial/integral molar Gibbs excess, and mixing energies. The energetics of mixing in liquid Al–Sn alloys has been analyzed through the study of concentration fluctuation in the long-wavelength limit. Thermal analysis of selected alloys in Al–Sn system was done using differential thermal analysis. Defined characteristic phase transition temperatures were used for comparison with calculated phase diagram of investigated system. Good agreement with available literature data was obtained. Structural analysis of selected alloys was done using optic microscopy.     

Experimental Study and 3D Modeling of the Phase Diagram of the Ag–Sn–Se System

In connection with the contradictoriness of literature data, phase equilibria in the Ag–Sn–Se system were restudied by differential thermal analysis and X-ray powder diffraction analysis. A number of polythermal sections and the isothermal section at room temperature of the phase diagram were constructed, and a projection of the liquidus surface was built. The primary crystallization fields of phases and the types and coordinates of in- and monovariant equilibria were determined. It was demonstrated that, in the system, two ternary compounds, Ag₈SnSe₆ and Ag_xSn_{2 – x}Se₂ (0.84 < x < 1.06), form. The former melts congruently at 1015 K and undergoes a polymorphic transformation at 355 K, and the latter melts with decomposition by a peritectic reaction at 860 K. The formation of the compound Ag₂SnSe₃, which was previously reported in the literature, was not confirmed. Based on the phase diagrams of boundary binary systems and the results of the differential thermal analysis of a limited number of samples of the ternary system, equations were obtained for calculation and 3D modeling of the liquidus and phase-separation surfaces.     

Syntheses and structures of Sc2Nb(4–x)Sn5, YNb6Sn6, and ErNb6Sn5: exploratory studies in ternary rare-earth niobium stannides

Three new rare-earth (RE) niobium stannides, namely, Sc(2)Nb(4-x)Sn(5) (x = 0.37, 0.52), YNb(6)Sn(6), and ErNb(6)Sn(5), have been obtained by reacting the mixture of corresponding pure elements at high temperature and structurally characterized by single-crystal X-ray diffraction studies. Sc(2)Nb(4-x)Sn(5) crystallizes in the orthorhombic space group Ibam (No. 72) and belongs to the V(6)Si(5) type. Its structure features a three-dimensional (3D) network composed of two-dimensionally (2D) corrugated [Nb(2)Sn(2)] and [Nb(2)Sn(3)] layers interconnected via Nb-Sn bonds, forming one type of one-dimensional (1D) narrow tunnels along the c axis occupied by Sc atoms. YNb(6)Sn(6) crystallizes in the hexagonal space group P6/mmm (No. 191) and adopts the HfFe(6)Ge(6) type, and ErNb(6)Sn(5) crystallizes in the trigonal space group R3m (No. 166) and belongs to the LiFe(6)Ge(5) type. Their structures both feature 3D networks based on 2D [Nb(3)Sn], [Sn(2)], and [RESn(2)] layers (RE = Y, Er). In YNb(6)Sn(6), one type of [Nb(3)Sn] layer is interconnected by [Sn(2)] and [YSn(2)] layers via Nb-Sn bonds to form a 3D network. However, in ErNb(6)Sn(5), two types of [Nb(3)Sn] layers are interlinked by [Sn(2)] and [ErSn(2)] layers via Nb-Sn bonds into a 3D framework. Electronic structure calculations and magnetic property measurements for "Sc(2)Nb(4)Sn(5)" and YNb(6)Sn(6) indicate that both compounds show semimetallic and temperature-independent diamagnetic behavior.     

Thermodynamics and vacuum distillation studies of liquid Al–Ga and In–Sn alloys

Activities of components in liquid Al–Ga and In–Sn alloys, the separation coefficients and vapour–liquid phase equilibrium in vacuum distillation were predicted using the molecular interaction volume model as a function of the activity coefficients. The results indicated that both Al and In are preferentially volatilised into vapour phase while Ga and Sn remain in residue. Similarly, we found that both the mass fraction and the content of Al and In in vapour phase increase as distillation temperature increases such that when the content of Al is 0.005985 wt% and In is 0.004141 wt% in vapour phase, respectively, in liquid phase, it was 70 wt% at T = 1073 K for both. The calculated values of activity and activity coefficients at various temperatures are presented. Comparison of the predicted values with experimental data indicates good agreement, thus verifying from statistical thermodynamics viewpoint that the model is stable and reliable.     

Viscosity of liquid Co–Sn alloys: thermodynamic evaluation and experiment

Shear viscosity measurements were performed for liquid Co–Sn alloys over a wide temperature range above the respective liquidus temperatures. A high temperature oscillating-cup viscometer was used. It was found experimentally that viscosity as a function of temperature obeys an Arrhenius law. The data were compared with calculated values, obtained from different thermodynamic approaches. A good agreement was found between experimental results and calculated ones by the Budai–Benkö–Kaptay model.     

Host–guest supramolecular polymers constructed of aniline derivatives and three-dimensional coordination polymers [(n-Bu3Sn)2(R3Sn)Fe(CN)6] n,R = n-Bu or Ph

The straightforward self-assembly reaction of R₃Sn⁺ and [Fe(CN)₆]^3? affords three-dimensional (3-D) coordination polymers [(n-Bu₃Sn)₂(R₃Sn)Fe(CN)₆] _n , R = n-Bu(I) or Ph(II). The architecture of these coordination polymers is closely related to zeolite and acts as a host with wide internal cavities or channels capable of encapsulating voluminous organic compounds. Aniline derivatives acting as guest are encapsulated within the cavities of the 3-D-polymeric hosts I and II by tribochemical reaction producing host–guest supramolecular polymers. The structures and physical properties of these hosts and their host–guest systems were investigated by elemental analysis, X-ray powder diffraction, IR, UV-vis, EPR, and magnetic measurements. The morphology of these systems was examined by scanning electron microscopy (SEM). The interesting feature of these host–guest supramolecular polymers is the enhanced electrical conductivities over those of the 3-D-coordination polymeric hosts upon encapsulation of conductive polymers within their cavities.     

Initial 119Sn Mössbauer Spectroscopy and X-ray Diffractometry Investigations of Electrodeposited Tin-Chromium and Tin-Zinc-Chromium Alloys

¹¹⁹Sn conversion electron Mössbauer spectroscopy, X-ray diffractometry and energy dispersive X-ray analysis (EDAX) were employed to investigate microstructure, composition and phases present in as-electroplated Sn-Cr and Sn-Cr-Zn alloys deposited on copper substrates. In the Sn-Cr deposits Cu, -Sn, Cr-Sn phases can be identified by X-ray diffractometry. The phase composition is significantly different between the samples prepared with relatively higher and lower current densities. In the diffractograms of Sn-Cr-Zn deposits Cu, -Sn, Zn phases can be well identified. A small intensity amorphous peak is also present, which can perhaps be associated with the presence of some amorphous Zn and Sn alloy. ¹¹⁹Sn Mössbauer spectra of Sn-Cr deposits exhibit an asymmetric broad main line centered near the isomer shift characteristic of -Sn as well as they contain a small component near the zero velocity which can be attributed to a SnO₂ phase based upon its characteristic. ¹¹⁹Sn Mössbauer spectra of Sn-Cr-Zn deposits are roughly similar to those of Sn-Cr deposits although the Mössbauer parameters of the third phase are different and vary with the Zn content. The presence of SnO₂ on the surface mainly in the Sn-Cr samples can be attributed to the corrosion process in the air.