The site preference and doping effect on mechanical properties of Ni3Al-based γ′ phase in superalloys by combing first-principles calculations and thermodynamic model

The fundamental aspects of site preference of alloying elements on sublattice of the strengthen γ′ phase with L1₂ structure have not been well understood, which hinders the optimized design of advanced Ni-based high-temperature alloys. In this contribution, the temperature- and composition-dependent site occupying preferences of the binary, ternary, and quaternary of Ni₃Al-based γ′ phase alloyed with M_i where M_i represents the additional transitional metals Co, Cr, Cu, Fe, Mn, Mo, Re, Ta, Ti, V, or W atoms (arranged in alphabetical order) chosen frequently, were studied using a two-sublattice thermodynamic model (Ni, Al, M_i)_1a(Ni, Al, M_i)_3c. The site occupying fractions (SOFs) were calculated based on a thermodynamic database established in this work, where the thermodynamic data of the end-members involved were obtained using first-principles calculations and phonon spectrum calculations. The calculated SOFs results show that there is an obvious site preference for stoichiometry binary Ni₃Al, and its site configuration changes from (Al)_1a(Ni)_3c at room temperature to (Al_0.9984Ni_0.0015)_1a (Al₀Ni_0.9994)_3c at 1273 K. For the γ′ phase with the composition 78Ni-26Al-4M_i (atom ratio and x_Ni/x_Al = 3:1), Mo atoms always preferred to occupy the 1a sublattice (Al site), Co, Mn, and Ti atoms always prefer the 3c sublattice (Ni site) in the whole temperature range, while the site preference of Cr, Cu, Fe, Re, Ta, V, or W atom is affected by temperature. For example, when the heat treatment temperature is lower than 700 K, Cr, Cu, Fe, Ta, V, and W atoms occupy the 1a and 3c sublattice randomly, and Re atoms prefer to 3c sublattice, while when the heat treatment temperature is higher than 1273 K, Cr, Cu, and W atoms prefer 3c sublattice, Fe and Ta atoms prefer to 1a sublattice, while all Re atoms occupy the 3c sublattice exclusively, and all V atoms occupy the 1a sublattice exclusively, respectively. Likewise, the site preference of the quaternary system with selective compositions 78Ni-26Al-2 M₁-2 M₂ was also predicted. Based on calculated SOFs results, the mechanical and thermodynamic properties were studied at the ground state. It has been revealed that Cr, Re, and V doping can improve the microhardness of Ni₃Al alloys; in particular, the effect of Cr is extraordinary; and all elements, except Mn, Mo, and Ti, would enhance the bulk modulus of Ni₃Al-based γ′ phase, in which Mn have the greatest influence on reducing the bulk and shear modulus, respectively. Furthermore, all the B/G ratios of the computed Ni₃Al-based γ′ phase are >1.75, showing inherent ductility. Only Cr doping significantly enhances the Debye temperature of the Ni₃Al-based γ′ phase.     

A boundary for reaction mechanisms within the transition metals interacting with nitrogen oxides is observed in DSIMS experiments

Summary Dynamic secondary ion mass spectrometry (DSIMS) investigations have been carried out with Cr, Mn, Fe, Co, Mo, Rh, W, Re, Os and Ir under 4 mPa N₂O, NO and 3 mPa NO₂ as reactant gases. Results indicate similar behaviour in adsorption for Cr, Mn, Fe, Mo, W on the one hand and for Co, Rh, Os and Ir on the other. For the first group of metals the nitrogen oxide molecules are always totally destroyed in adsorption whereas the second group shows evidence for surface compounds such as MeNO (Me=metal) indicating only a partial dissociation in the case of N₂O and NO₂, and molecular adsorption under NO respectively. Re does not belong uniquely to either group because it reacts with N₂O and NO₂ dissociatively whereas under NO only partial dissociation is observed.Abbreviations SIMS Secondary ion mass spectrometry - SSIMS Static SIMS - AES Auger electron spectroscopy - EELS Electron energy-loss spectroscopy - LEED Low energy electron diffraction - TDS Thermal desorption spectroscopy - XPS, UPS X-ray/Ultraviolet photoelectron spectroscopy     

Metal oxide promoted TiO2 catalysts for photo-assisted selective catalytic reduction of NO with NH3

The photo-assisted selective catalytic reduction (SCR) of NO with NH₃ (Photo-SCR) was performed over TiO₂ modified by supporting 1 wt% of various transition metal (V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Ta or W) oxides aiming at the improvement of the photo-SCR activity. The addition of Nb, Mo or W oxide to TiO₂ was found to enhance the photo-SCR activity. We have reported that the amount of acid sites on TiO₂ is one of the key factors to the photo-SCR activity. The increase in the activity depends on the enhancement of acidity of catalyst by the addition of Nb, Mo or W oxide. In contrast, the addition of V, Cr, Mn, Fe, Co, Ni or Cu oxide to TiO₂ lowered the photo-SCR activity, although addition of metal cations also changed the acidity of TiO₂. We guess that the reduction of the activity was caused by two reasons; the first is that the sites newly formed on these transition metal oxides is not photoactive and the second is that TiO₂ supporting V, Cr, Mn, Fe, Co, Ni or Cu oxides had low stabilities under the reaction conditions, i.e., the chemical state of the cations changed during the reaction. Therefore, we concluded that the increase in the acid sites that are active sites for photo-SCR and the stability of the catalysts are important for the photo-SCR.     

Magnetic behavior of new ternary metal borides with YCrB4-type structure

New ternary metal borides YbRuB₄, YbOsB₄ and GdFeB₄ have been prepared. The compounds were found to crystallize with the structure type of YCrB₄. Magnetic measurements (80–300°K) were performed on compounds of the isostructural series MM′B₄ (YCrB₄-type; M = Y, Gd, Tb, Dy, Ho, Er, Tm, Yb; M′ = Ru, Os and M = U, Gd; M′ = Cr, Mn, Fe, Co). Paramagnetic Curie-Weiss behavior is shown in all cases; Y and the R.E. (Rare Earth) metals are trivalent in these compounds.     

Synthesis and electrical properties of perovskite oxides, LnB0.75B′0.25O3

A series of ordered perovskite oxides of the type Ln²⁺_0.75B′⁶⁺_0.25O₃ (Ln = rate earth or Y; B = Mn, Fe, Co, Ni; B′ = Mo, W, Re) has been synthesized and characterized by X-ray analysis and density measurements. Compounds with Ln = La are easily formed in all cases as single-phase materials and have either cubic or orthorhombic symmetry. When Ln = rare earth or Y, single-phase materials are formed only in the case of LnFe_0.75Mo_0.25O₃ and these possess an orthorhombic structure. All the phases tested are extrinsic semiconductors in the range of 25–350°C, with E_a ranging from 0.1 to 0.4 eV. Resistivity of the Ln(Fe, Mo)O₃ series of oxides increases from Ln = La to Ln = Lu. Ni-containing compounds are p type, while those containing Fe or Co in the B sites are n type.     

Determination of tungsten with iron(III) after reduction with mercury in thiocyanate medium

Tungsten(V) is formed by shaking for 2 min sodium tungstate solution in 0.4 M potassium thiocyanate-4M hydrochloric acid medium, with mercury. It is titrated with standard iron(III) solution. The thiocyanate present stabilizes W(V) to aerial oxidation and also acts as indicator. The W(V) can also be titrated potentiometrically in 7M hydrochloric acid, a tungsten wire electrode being used. Fe, Ni, Cr, Zr, Bi, Sb, Ce, Al, Pb, Ca and U do not interfere. Cu, V and As can be tolerated up to 5 mg. Co, Mo, Re, Nb and Mn interfere, but not in the potentiometric determination. The method is direct, simple, rapid, accurate and reproducible.     

Emission of secondary ions from 3d, 4d, and 5d transition metals under chloro-trifluoro-methane CClF3 as reactant gas

Surface interactions of CClF₃ with polycrystalline samples of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Rh, Pd, Ag, Ta, W, Re, Ir, and Pt were investigated by means of moderate dynamic SIMS. As observed with other reactant gases these transition metals in most cases appear to be discernible into “dissociative” and (partial) “molecular” adsorbents. Small signals of oxidic secondary ions which are detectable for residual gas conditions vanished under the action of CClF₃. However, due to strong polarization by either of the halogens, the emission of Me²⁺ ions is enhanced for Ti, V, and Nb.     

Reactivity of main-group—transition-metal bonds : VI. the kinetics of iodination of tetracarbonyl(trimethylstannyl)cobalt and pentacarbonyl(trimethylstannyl)rhenium

The kinetics of the iodine cleavage of the SnCo bond in [Me₃SnCo(CO)₄ ] and of the SnRe bond in [Me₃SnRe(CO)₅] have been measured. The order of rates of cleavage of the SnM bond in the compounds [Me₃SnM(CO)_x(cp)_y] (M = Mn, Re, x = 5, y = 0;M = Co, x = 4, y = 0; M = Cr, Mo, W, x = 3, y = 1; M = Fe, x = 2, y = 1; cp = η-cyclopentadienyl) indicates that the main factors determining reactivity towards iodine are the size of the metal atom (M) and the shielding of it by the other ligands.     

The application of discontinuous,countercurrent, liquid-liquid extraction to the study of the distribution of metal ions between hydrochloric acid and methyl isobutyl ketone

Summary The extraction of the elements Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb and Bi from hydrochloric acid into methyl isobutyl ketone has been studied as a function of hydrochloric acid concentration. The results are presented in graphical form. The data were obtained by studying the distribution patterns of the elements after equilibration on a Craig countercurrent liquid-liquid extraction apparatus.

---

Zusammenfassung Die Extraktion der Elemente Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb und Bi mit Methylisobutylketon aus salzsaurer Lösung als Funktion der Säurekonzentration wurde studiert. Die Ergebnisse wurden aus den Spitzen der Verteilungskurven nach Einstellung des Gleichgewichts in einem diskontinuierlichen Gegenstrom-flüssig-flüssig-Extraktionsapparat berechnet.

---

Résumé On a étudié l'extraction des éléments Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Ga, As, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, La, W, Re, Os, Ir, Pt, Au, Hg, Tl, Pb et Bi en solution chlorhydrique par la méthylisobutylcétone. On présente les résultats sous forme graphique. Les données ont été obtenues en étudiant les diagrammes de distribution des éléments après équilibrage sur un appareil Craig à extraction à contre-courant liquide-liquide.

     

Zirconium titanate ceramic pigments: Crystal structure, optical spectroscopy and technological properties

Srilankite-type zirconium titanate, a promising structure for ceramic pigments, was synthesized at 1400 °C following three main doping strategies: (a) ZrTi_1−xA_xO₄, (b) ZrTi_1−x−yA_xB_yO₄ and (c) Zr_1−xC_xTiO₄ where A=Co, Cr, Fe, Mn, Ni or V (chromophores), B=Sb or W (counterions) and C=Pr (chromophore); x=y=0.05. Powders were characterized by XRD with Rietveld refinements and DRS in the UV-visible-NIR range; technological properties were appraised in several ceramic matrices (frits, glazes and body). Zirconium titanate can be usefully coloured with first row transition elements, giving green and greenish yellow (Co and Ni); orange-buff (Cr and V); tan-brown hues (Mn and Fe). In industrial-like synthesis conditions, a disordered structure as (Zr,Ti)O₂, with both Zr and Ti randomly distributed in the octahedral site, is achieved. Doping with chromophores and counterions induces unit cell dimensions variation and causes an oversaturation in zirconium oxide. Optical spectroscopy reveals the occurrence of Co²⁺, Cr³⁺, Fe³⁺, Mn²⁺, Mn³⁺, Ni²⁺, V³⁺ and V⁴⁺. The zirconium titanate pigments fulfil current technological requirements for low-temperature applications, but exhibit a limited chemico-physical stability for higher firing temperature and in chemically aggressive media.     

Emission of secondary ions from 3d, 4d, and 5d transition metals under chloro-trifluoro-methane CClF3 as reactant gas

Surface interactions of CClF₃ with polycrystalline samples of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Nb, Mo, Rh, Pd, Ag, Ta, W, Re, Ir, and Pt were investigated by means of moderate dynamic SIMS. As observed with other reactant gases these transition metals in most cases appear to be discernible into “dissociative” and (partial) “molecular” adsorbents. Small signals of oxidic secondary ions which are detectable for residual gas conditions vanished under the action of CClF₃. However, due to strong polarization by either of the halogens, the emission of Me²⁺ ions is enhanced for Ti, V, and Nb. Received: 6 August 1997 / Revised: 22 December 1997 / Accepted: 29 December 1997     

Properties of boron,boride, and indium nanomaterials: The melting temperatures of spherical nanoparticles,nanowires, and nanofilms

High-temperature synthesis of boron nanowires with a fixed structure, spherical nanoparticles, cylindrical nanowires, and nanofilms of indium created a basis for theoretical studies of the nanochemistry of the boron family. The melting temperatures of these nanomaterials were studied as depending on their structural properties and electronic structure, as well as T _m trends in M _x B _y nanoborides, where M = Ti, Zr, or Hf; V, Nb, or Ta; Cr, Mo, or W; Fe, Co, or Ni.     

The syntheses and coordination properties of M(CO)3X(DAB) (M = Mn,Re; X = Cl,Br, I; DAB = 1,4-diazabutadiene)

M(CO)₅X (M = Mn, Re; X = Cl, Br, I) reacts with DAB (1,4-diazabutadiene = R₁N=C(R₂)C(R₂)′=NR′₁) to give M(CO)₃X(DAB). The ¹H, ¹³C NMR and IR spectra indicate that the facial isomer is formed exclusively. A comparison of the ¹³C NMR spectra of M(CO)₃X(DAB) (M = Mn, Re; X = Cl, Br, I; DAB = glyoxalbis-t-butylimine, glyoxyalbisisopropylimine) and the related M(CO)₄DAB complexes (M = Cr, Mo, W) with Fe(CO)₃DAB complexes shows that the charge density on the ligands is comparable in both types of d⁶ metal complexes but is slightly different in the Fe-d⁸ complexes. The effect of the DAB substituents on the carbonyl stretching frequencies is in agreement with the A′(cis) > A″ (cis) > A′(trans) band ordering.Mn(CO)₃Cl(t-BuNCHCHNt-Bu) reacts with AgBF₄ under a CO atmosphere yielding [Mn(CO)₄(t-BuNCHCHN-t-Bu)]BF₄. The cationic complex is isoelectronic with M(CO)₄(t-BuNCHCHNt-Bu) (M = Cr, Mo, W).     

Crystal structure, optical properties and colouring performance of karrooite MgTi2O5 ceramic pigments

Karrooite, MgTi₂O₅, is a promising ceramic pigment due to its high refractoriness and refractive indices, as well as its ability to host transition metal ions in two crystallographically distinct octahedral sites. The colouring performance was investigated combining X-ray powder diffraction with UV-vis-NIR spectroscopy on karrooite doped with V, Cr, Mn, Fe, Co or Ni (M) according to the formula Mg_1−xTi_2−xM_2xO₅, with x=0.02 and 0.05. Transition metals solubility in the karrooite lattice is not complete and a second phase is always present (geikielite or rutile). Structural data proved that incorporation of different chromophore ions into the karrooite structure affects unit cell parameters, bond length distances and angles, site occupancies and therefore cation order-disorder. Optical spectra exhibit broad absorbance bands of Co(II), Cr(IV), Fe(III), Mn(II), Mn(III), Ni(II), V(IV) with distinct contributions by cations in the M₁ and M₂ sites. Karrooite pigments have colours ranging from orange to brown-tan (Cr, Fe, Mn, V) to green (Co) and yellow (Ni) that are stable in low-temperature (<1050 °C) ceramic glazes and glassy coatings.     

Quaternäre Magnesium-Iridiumboride Mg2Xlr5B2 mit X = Be,Al, Si,P, Ti,V, Cr,Mn, Fe,Co, Ni,Cu, Zn,Ga, Ge,As – eine Besetzungsvariante des Ti3Co5B2-Typs

Quaternary Magnesium Iridium Borides Mg₂XIr₅B₂ with X = Be, Al, Si, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As – a Substitution Variant of the Ti₃Co₅B₂ Type of Structure The compounds Mg₂XIr₅B₂ with X = Be, Al, Si, P, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge and As crystallize tetragonally with Z = 2 in the space group P4/mbm. The lattice constants are in the range a = 9.199 Å, c = 2.880 Å for Mg₂BeIr₅B₂ und a = 9.406 Å, c = 2.953 Å for Mg₂TiIr₅B₂ (further lattice constants are given in Table 1). X-ray structure determinations carried out with single crystals of the Si-and the P-compounds showed that a substitution variant of the Ti₃Co₅B₂ type of structure is formed. According to X-ray powder photographs the other compounds are isotypic. In the compounds with X = P and As the X-siteset is only occupied at about 70% and 80% respectively.     

Polarographic determination of cadmium, lead, nickel, thallium and uranium(VI) in isoquinoline formate

Summary The polarographic behaviour of Cd, Pb, Ni, Tl and U(VI) has been described in 0.1 M isoquinoline formate as base electrolyte. In all cases well defined reversible waves were obtained and determinations are possible in the presence of Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg and Cu.

---

Polarographische Bestimmung von Cadmium, Blei, Nickel, Thallium und Uran(VI) in Isochinolinformiat

Zusammenfassung Das polarographische Verhalten von Cd, Pb, Ni, Th. und U(VI) in 0,1 M Isochinolinformiatlösung wird beschrieben, Bestimmungsmöglichkeiten werden aufgezeigt. In allen Fällen werden gut definierte reversible Stufen erhalten. Folgende Elemente stören nicht: Mo, Co, Zn, Mn, Te, In, Se, Fe, Cr, V, Th, Zr, As, Sb, Ag, Hg, Cu.

     

Electrometric titrations of Cr(VI), Mn(IV), V(V), Co(III) and U(VI) with a standard iron(II) solution in alkaline media containing hexitols

Direct and indirect potentiometric, bipotentiometric and biamperometric titrations with a standard iron(II) solution are described for some inorganic compounds in alkaline media containing hexitols (mannitol, dulcitol and sorbitol). The optimal conditions for titrations based on the Cr(VI) → Cr(III), Mn(IV) → Mn(III) → Mn(II), V(V) → V(IV), Co(III) → Co(II) and U(VI) → U(IV) systems are discussed. Of the hexitols studied, sorbitol has the greatest effect on the value of the redox potential of the Fe(III)/Fe(II) system; the E_f° value is about —1.10 V vs. SCE.     

Solvent extraction of metal xanthates

The solvent extraction of metal xanthates is reviewed with emphasis on the characteristics and analytical uses of ethyl xanthate complexes. Elements reviewed include As, Sb, Bi, Cd, Co, Cu. Cr, Ga, Au, In, Fe, Pb, Mn, Hg, Mo, Ni, Pd, Pt, Re, Ag, Se, Te, Tc, Tl, Sn, U, V and Zn.     

An integrated approach to the complete chemical analysis of magnesium or sodium diuranate (yellow cake) sample

A procedure for the complete chemical analysis of magnesium or sodium diuranate (yellow cake) sample is reported. Uranium is determined gravimetrically after peroxide precipitation. Optimum parameters, such as pH, quantity of hydrogen peroxide, volume of sample, temperature and complexing agent for quantitave precipitation of uranium, and effective separation of other elements were studied. Aluminum, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, and Zn were determined by flame atomic absorption spectrometer and B, Mo, SO₄, REEs and Y by inductively coupled plasma atomic emission spectrometer in the filtrates of hydroxide and peroxide precipitation separation. The proposed method is accurate and the precision is characterized by an RSD of ~0.2% for U; 2 to 6% for Mg, Na, K, Ca, Fe, SiO₂, Al, Cd, Co, Cr, Fe, Mn, Ni, Pb, and Zn and 3 to7% for REEs, Y, Mo and B     

Rare earth transition metal sulfides,LnMS3

Ternary rare earth transition metal sulfides LnMS₃ with Ln = La, Nd, and Gd, and M = V and Cr; as well as Ln = La and M = Mn, Fe, Co, and Ni have been prepared and characterized. The vanadium and chromium sulfides crystallize in a monoclinic layer structure isotypic with LaCrS₃, while the other LnMS₃ sulfides crystallize in a hexagonal structure. Chemical shifts of the metal K-absorption edge and XPS binding energies of core levels indicate that the transition metal is trivalent in the V and Cr sulfides, while it is divalent in the Mn, Fe, Co, and Ni sulfides. Electrical and magnetic properties of the sulfides are discussed in terms of their structures and the electronic configurations of the transition metal ions.