Siliconization of titanium oxycarbides by silicon monoxide

Siliconization of titanium oxycarbides TiC _x O _y by gaseous SiO at 1350°C was studied. The reaction source of SiO was a powder mixture of silicon and silicon dioxide. It was found that the main siliconization product is Ti₅Si₃ and the siliconization of high-carbon (x > 0.70) oxycarbides also gives Ti₃SiC₂ and TiSi₂.     

XRD-Studies of SiC/Si layers on carbon substrates

Structural investigations of thin films of SiC, SiC with free silicon and various titanium suicides (TiSi₂, TiSi and Ti₅Si₃) are described. The crystal phases have been identified using X-ray diffractometry. The growth of reaction products from surface reactions between silicon and deposited titanium can be observed.Dedicated to Professor Dr. rer.nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

Synthesen,IR- und 15N-Kernresonanzspektren isotopen-markierter Nitridokomplexe des Wolframs

Isothermal Section at 1273 K in the System Ti? Si? O The isothermal section at 1273 K of the system Ti? Si? O has been investigated by means of phase analysis in quenched samples as well as by the investigation of the phase sequence in chemical vapour transport experiments. In equilibrium with SiO₂ only TiSi₂, TiSi, and Ti₅Si₃(O), respectively, can coexist as Si-containing compounds. Only Ti₅Si₃(O) can coexist with titanium oxides (Ti₂O₃ or TiO, respectively). Ti₅Si₄ is stable only if oxygen is absent.     

Structural chemistry of complex carbides and related compounds

Complex carbides formed in ternary systems of a transition element (M), a B-group element (M′), and carbon and having a formula M₂M′C (H-phase) or M₃M′C (perovskite carbide) occur frequently. This reflects the simple geometry of the atomic arrangement of the metals and the filling mode by an interstitial stabilizer such as carbon or nitrogen. The phase relationship of the ternary combinations {Ti, Zr, Hf, V, Nb, Ta, Cr, Mn, and Ni}-aluminum-carbon was investigated. New complex carbides were found with the corresponding zirconium, hafnium, and tantalum combinations. The crystal structures in the case of Zr- and Hf-containing complex carbides can be characterized by a twelve-metal-layer sequence and by a ten-metal-layer sequence with carbon atoms again filling octahedral voids. The transition of structure types from TiC, Ti₂AlC, Ti₃SiC₂, ZrAlC₂, Zr₂Al₃C₅, to Al₄C₃ is also discussed.     

A theoretical study of protonation of triatomic silicon–carbon compounds

Ab initio molecular orbital methods are employed to study the low-lying states of C₃H⁺, SiC₂H⁺, Si₂CH⁺, and Si₃H⁺. Special attention is paid to a comparative study between C₃H⁺ and Si₃H⁺. In both cases a ³B₂ state is found to lie the lowest at the HF level, although inclusion of correlation effects favor a linear structure (¹Σ⁺ state) for C₃H⁺, which lies 25 kcal/mol below the ³B₂ state at the MP 4 level, and a bent structure (¹A′ state) for Si₃H⁺, which lies just 2 kcal/mol below the ³B₂ state. The proton affinities of C₃, SiC₂, Si₂C, and Si₃ are estimated at different levels of theory. Both protonation at carbon and silicon atoms are considered for SiC₂ and Si₂C. It is found that C₃ comparatively has a low proton affinity. On the other hand, Si₃ has a relatively high proton affinity compared with the protonation at silicon atom for both SiC₂ and Si₂C. These results are discussed on the basis of electronic structure arguments.     

Room‐Temperature Carbide‐Derived Carbon Synthesis by Electrochemical Etching of MAX Phases

Porous carbons are widely used in energy storage and gas separation applications, but their synthesis always involves high temperatures. Herein we electrochemically selectively extract, at ambient temperature, the metal atoms from the ternary layered carbides, Ti₃AlC₂, Ti₂AlC and Ti₃SiC₂ (MAX phases). The result is a predominantly amorphous carbide‐derived carbon, with a narrow distribution of micropores. The latter is produced by placing the carbides in HF, HCl or NaCl solutions and applying anodic potentials. The pores that form when Ti₃AlC₂ is etched in dilute HF are around 0.5 nm in diameter. This approach forgoes energy‐intensive thermal treatments and presents a novel method for developing carbons with finely tuned pores for a variety of applications, such as supercapacitor, battery electrodes or CO₂ capture.     

Die Kristallstruktur von Ti3SiC2—ein neuer Komplexcarbid-Typ

Zusammenfassung Die Struktur von Ti₃SiC₂ wird aus Einkristallaufnahmen bestimmt. Die Gitterparameter der hexagonalen Zelle sind:a=3,06₈,c=17,66₉ Å undc/a=5,75₉. Die Titan-Atome besetzen die Punktlagen 2a) und 4f) (z_Ti=0,135), die Silicium-Atome die Punktlage 2b) und die Kohlenstoff-Atome die Punktlage 4f) (z_C=0,567₅) in der Raumgruppe D _6h ⁴ –P6₃/mmc. Die Struktur gehört zu den Komplexcarbiden mit oktaedrischen Bauelementen [T ₆C].

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The crystal structure of Ti₃SiC₂ has been determined by means of single crystal photographs; the lattice parameters of the hexagonal cell were found to be:a=3.06₈,c=17.66₉ Å andc/a=5.75₉. The titanium atoms occupy the positions 2a) and 4f) (z_Ti=0.135), the silicon atoms 2b) and the carbon atoms 4f) (z_C=0.567₅) of the space group D _6h ⁴ –P6₃/mmc. The crystal structure type belongs to the class of complex carbides having octahedral groups [T ₆C].

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Quantum-chemical modelling of nanotubes of titanium silicocarbides Ti<Subscript>2</Subscript>SiC,Ti<Subscript>3</Subscript>SiC<Subscript>2</Subscript>, and Ti<Subscript>4</Subscript>SiC<Subscript>3</Subscript>

Atomic models are proposed for nanotubes of the titanium silicocarbides Ti₂SiC, Ti₃SiC₂, and Ti₄SiC₃, and their electronic structure and interatomic interactions are investigated by the density functional tight-binding method (DFTB) in comparison with the corresponding crystalline phases. Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 45, No. 2, pp. 88-92, March-April, 2009.     

Selective Etching of Silicon from Ti3SiC2 (MAX) To Obtain 2D Titanium Carbide (MXene)

Until now, MXenes could only be produced from MAX phases containing aluminum, such as Ti₃AlC₂. Here, we report on the synthesis of Ti₃C₂ (MXene) through selective etching of silicon from titanium silicon carbide—the most common MAX phase. Liters of colloidal solutions of delaminated Ti₃SiC₂‐derived MXene (0.5–1.3 mg mL^?1) were produced and processed into flexible and electrically conductive films, which show higher oxidation resistance than MXene synthesized from Ti₃AlC₂. This new synthesis method greatly widens the range of precursors for MXene synthesis.     

In situ Hochdruck- und Hochtemperatur-Untersuchungen an Siliciumsuboxiden mittels energiedispersiver Röntgenbeugung

In situ High-Pressure- and High-Temperature Studies of Siliconsuboxides via Energy Dispersive X-ray Diffraction The amorphous silicon compounds Si₂O₃, H₂Si₂O₄, HSiO_1.5, and SiO have been investigated under High-Pressure- and High-Temperature conditions in situ via energy dispersive X-ray diffraction with synchrotron radiation. The studies have been performed using the Multi Anvil High Pressure Device MAX-80, at HASYLAB, DESY-Hamburg, Germany. Except for SiO, at a pre-set pressure of 45 kbars the formation of Coesite was observed at heating. Commercially available SiO did not crystallize in any way, indicating that it seems not to consist of silicon(II)-oxide, but is in fact a mixture of silicon and silicondioxide, disproportionated on an atomic scale.     

Mechanochemical synthesis and high-frequency induction heated consolidation of nanostructured Ti5Si3 and its mechanical properties

Pure Ti and Si powders were milled in a horizontal-rotation ball mill and in a high-energy ball mill to synthesize Ti₅Si₃ powders. The high-energy ball milling produced nanosized single-phase Ti₅Si₃ particles. Meanwhile, no reaction occurred during the horizontal milling. The two milled powders were consolidated using the high-frequency induction heated sintering method. A dense nanostructured Ti₅Si₃ compact was consolidated within 2 min using the mechanically synthesized Ti₅Si₃ powder. The retainment of nanoscale structure during sintering is believed to be the reason for the good mechanical properties of the Ti₅Si₃ compact. In comparison, the horizontally milled powder reacted to form Ti₅Si₃ partially on sintering. It is believed that the enhanced toughness of the horizontally milled samples may be due to the crack-deterring effect of softer Si/Ti grains.     

Formation mechanisms of Si3N4 and Si2N2O in silicon powder nitridation

Commercial silicon powders are nitrided at constant temperatures (1453 K; 1513 K; 1633 K; 1693 K). The X-ray diffraction results show that small amounts of Si₃N₄ and Si₂N₂O are formed as the nitridation products in the samples. Fibroid and short columnar Si₃N₄ are detected in the samples. The formation mechanisms of Si₃N₄ and Si₂N₂O are analyzed. During the initial stage of silicon powder nitridation, Si on the outside of sample captures slight amount of O₂ in N₂ atmosphere, forming a thin film of SiO₂ on the surface which seals the residual silicon inside. And the oxygen partial pressure between the SiO₂ film and free silicon is decreasing gradually, so passive oxidation transforms to active oxidation and metastable SiO(g) is produced. When the SiO(g) partial pressure is high enough, the SiO₂ film will crack, and N₂ is infiltrated into the central section of the sample through cracks, generating Si₂N₂O and short columnar Si₃N₄ in situ. At the same time, metastable SiO(g) reacts with N₂ and form fibroid Si₃N₄. In the regions where the oxygen partial pressure is high, Si₃N₄ is oxidized into Si₂N₂O.     

Theoretical Studies on the Structures and Stabilities of Charged, Titanium-Doped, Small Silicon Clusters, TiSi n ? /TiSi n + (n?=?1–8)

The structures and stabilities of charged, titanium-doped, small silicon clusters TiSi _n ⁺ /TiSi _n ^? (n?=?1–8) have been systematically investigated using the density functional theory method at the B3LYP/6-311+G* level. For comparison, the geometries of neutral TiSi_n clusters were also optimized at the same level, although most of them have been reported previously (Guo et al., J Chem Phys 126: 234704, 2007). Our results indicate that all neutral TiSi_n clusters favor Si-capped TiSi_n?1 structures, with the lowest energy structure of TiSi₂, TiSi₃, TiSi₄, TiSi₅, TiSi₆, TiSi₇ and TiSi₈ being Si-side-on TiSi adduct, Si-face-capped TiSi₂ triangle, Si-face-capped TiSi₃ trigonal pyramid, Si-face-capped TiSi₄ trigonal bipyramid, Si-face-capped TiSi₅ square bipyramid, Si-face-capped TiSi₆ pentagonal bipyramid, and Si-face-capped TiSi₇ capped pentagonal bipyramid, respectively. The ground state structures obtained herein for the neutral TiSi_n clusters agree well with those of Guo et al. except for TiSi₃ and TiSi₈. Adding or removing an electron greatly changes some ground state structures, i.e. for TiSi₃ ^?/TiSi₃ ⁺, TiSi₅ ^?, TiSi₆ ^?/TiSi₆ ⁺ TiSi₇ ^? and TiSi₈ ^?/TiSi₈ ⁺; others are almost unchanged, e.g. TiSi₂ ^?/TiSi₂ ⁺, TiSi₄ ^?/TiSi₄ ⁺, TiSi₅ ⁺ and TiSi₇ ⁺. Based on the optimized geometries, various energetic properties, including binding energies, fragmentation energies, second-order difference energies, HOMO–LUMO energy gaps, ionization potentials and electron affinities, were calculated for all the most stable isomers. The average binding energies reveal that all of TiSi_n/TiSi _n ⁺ /TiSi _n ^? (n?=?1–8) clusters can continue to gain energy as the size increasing. The fragmentation energies and second-order energy differences suggest that neutral TiSi₅, anionic TiSi₅ ^? and cationic TiSi₆ ⁺ are relatively stable.     

Ba2Ti2Si2O9F2, a new titanium silicate

Dibarium dititanium difluoride dioxide heptaoxidodisilicate, Ba₂Ti₂Si₂O₉F₂, is a new edge‐sharing titanate with a unique titanium silicate framework. All atoms in the structure are in general positions. Titanium oxyfluoride octahedra combine with silicon tetrahedra to form a double stacked chain, which is the base unit of the layered framework. The Ba atoms lie in channels that extend along the a axis.     

Effect of Modifying Additives on the Sintering and Properties of SiC/SiC<Subscript>w</Subscript> Ceramic Composite Material

Spark plasma sintering and hot compaction methods were used to obtain experimental samples of a composite material of the SiC?SiC_w system with various modifying additives (AlN, B₄C, HfB₂, Y₂O₃, Al₂O₃, Si₃N₄). The effect of the modifying additives on the sintering process, physicomechanical, and thermal properties of the ceramic composite material was examined. The introduction of the modifying additives lowered the sintering temperature of silicon carbide produced by the hot compaction method by 200°C and that formed with spark plasma spark sintering by 300?450°C as compared with the sintering temperature of silicon carbide without additives.     

Electrochemical Synthesis of Ti–Si–B Compounds in Chloride–Fluoride Molten Salts

Metals, semiconductors, and their binary and ternary compounds can be produced by electrolyzing molten salts of the components. For a Ti–Si–B system, reduction potentials of all three elements are close, which significantly alleviates the problem. Using thermodynamic calculations, voltammetric measurements, and electrolysis we demonstrate the possibility of producing metal-like refractory compounds. Binary compounds TiB₂, Ti₅Si₃, and SiB₄ and a new ternary compound Ti₅Si₃B₃ are produced electrochemically.     

Disilizidsysteme

Zusammenfassung Mit Hilfe röntgenographischer und thermoanalytischer Methoden wurden weitere Systeme von Disiliziden der 4., 5. und 6. Gruppe untersucht.Interessante Befunde ergeben sich bei: Cr(Ta)Si₂–TiSi₂–Mo(W)Si₂, TiSi₂–TaSi₂–CrSi₂ und CrSi₂–TaSi₂–MoSi₂. Zwischen Cr(Ta)Si₂ und (Ti, Mo)Si₂ bzw. (Ti, W) Si₂ mitC 40-Typ besteht ein lückenloser Übergang. Außerdem wird die Mischungslücke im System CrSi₂–TaSi₂ durch TiSi₂ bzw. MoSi₂ geschlossen.Mit 23 Abbildungen     

The Ternary System Nickel/Silicon/Titanium Revisited

The constitution of the ternary system Ni/Si/Ti is investigated over the entire composition range using X‐ray diffraction (XRD), energy dispersive X‐ray spectroscopy (EDS), differential thermal analysis (DTA), and metallography. The solid state phase equilibria are determined for 900 °C. Eight ternary phases are found to be stable. The crystal structures for the phases τ₁NiSiTi, τ₂Ni₄Si₇Ti₄, τ₃Ni₄₀Si₃₁Ti₁₃, τ₄Ni₁₇Si₇Ti₆, and τ₅Ni₃SiTi₂ are corroborated. For the remaining phases the compositions are determined as Ni₆Si₄₁Ti₅₃ (τ₆), Ni₁₆Si₄₂Ti₄₂(τ₇), and Ni₁₂Si₄₅Ti₄₃ (τ₈). The reaction scheme linking the solid state equilibria with the liquidus surface is amended to account for these newly observed phases. The discrepancies between previous experimental conclusions and modeling results are addressed. The liquidus surface is dominated by the primary crystallisation field of τ₁NiSiTi, the only congruently melting phase.     

Neue Abkömmlinge der TiSi2-Struktur

Zusammenfassung In Mn-Defektdisiliciden führt Substitution von Mn durch Cr, Fe oder Co zur Ausbildung neuer Phasen, die durch bestimmte Vielfache derc-Achse einer charakteristischen Unterzelle repräsentiert werden. Das Verhältnis Metall/Silicium ist eine Funktion der Valenzelektronenkonzentration. Os₂Ge₃ erweist sich als isotyp mit Os₂Si₃ und gehört damit ebenfalls zu den TiSi₂-Abkömmlingen.

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Substitution of Mn by Cr, Fe or Co within Mn-defect disilicides leads to a series of new phases characterized by various multiples of thec-axis of the subcell. The metal/silicon ratio depends on the valence electron concentration. Os₂Ge₃ has been found to be isotypic with Os₂Si₃, another derivative of the TiSi₂-structure type.

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