Phase transformations in the Zn–Cd–Sb system

Phase equilibria of the Cd–Sb–Zn system have been investigated by metallographic examinations, DSC, XRD and WDS measurements. At 250 °C, the ternary diagram shows two three-phase fields, (Zn)+(Cd)+Zn₄Sb₃ and (Cd)+ Zn₄Sb₃+(Zn,Cd)Sb. Continuous solid solution has been found between ZnSb and CdSb. Solubility of Cd in Sb₃Zn₄ was determined to be about 43 at.%. A variant of the reaction scheme is proposed for the Cd–Sb–Zn system to understand phase relations observed at 250 °C.     

Thermodynamic studies on LaFeO3(s)

The enthalpy increments and the standard molar Gibbs energies in the formation of LaFeO₃(s) have been measured using a high-temperature Calvet micro-calorimeter and a solid oxide galvanic cell, respectively. The corresponding expression for enthalpy increments is given as:

H°(T)−H°(298.15 K)(J mol⁻¹)(±1.2%)=−36887.27+103.53 T(K)+25.997×10⁻³T²(K)+11.055×10⁵/T(K).

The heat capacity, the first differential of H°(T)−H°(298.15 K) with respect to temperature, is given as:

C_p,m°(T)(JK⁻¹mol⁻¹)=103.53+51.994×10⁻³T(K)−11.055×10⁵/T²(K).

From the measured e.m.f. of the cell, (−)Pt/(LaFeO₃(s)+La₂O₃(s)+Fe(s))//CSZ//(Ni(s)+NiO(s))/Pt(+), and the relevant Δ_fG_m°(T) values from the literature, the Δ_fG_m°(LaFeO₃, s, T) was calculated, and is given as:

Δ_fG_m°(LaFeO₃, s, T)(kJmol⁻¹)(±0.72)=−1319.2+0.2317T(K).

The calculated Δ_fH_m°(LaFeO₃, s, 298.15 K) and S°(298.15 K) values obtained using the second law method are −1334.7 kJ mol⁻¹ and 128.9 J K⁻¹ mol⁻¹, respectively.     

A substitution of nickel by antimony:: Crystal and electronic structure of the new antimonide Hf6Ni1−xSb2+x

The ternary antimonides Hf₆M_1−xSb_2+x (M=Fe, Co, Ni) were prepared by arc-melting of stoichiometric mixtures of Hf, HfSb₂ and M. According to the single crystal structure analyses, performed on Hf₆NiSb₂ and Hf₆Ni_0.76Sb_2.24, Hf₆M_1−xSb_2+x crystallizes in an ordered variant of the Fe₂P structure type with the M and Sb atoms occupying the two P positions on 1b and 2c of space group P

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2m, respectively (Zr₆CoAl₂ type). The 3d metal atoms M can partially be replaced by antimony, leading to significant, anisotropic changes in the lattice dimensions which are a=765.6(1) pm, c=362.10(7) pm, V=183.81(5)×10⁶pm³ for Hf₆NiSb₂, and a=760.5(1) pm, c=372.40(7) pm, V=186.53(5)×10⁶pm³ for Hf₆Ni_0.76Sb_2.24 as determined by single crystal data. Calculations of the electronic structure of Hf₆NiSb₂ using the Extended Hückel approximation show strong bonding Hf–Hf, Hf–Ni, and Hf–Sb interactions.     

Determination of phase equilibria in the Co-rich Co–Al–W ternary system with a diffusion-couple technique

Phase equilibria in the Co-rich Co–Al–W ternary system were determined with a unique diffusion-couple technique in which Co–27Al and Co–15W binary alloys (at. %) were first coupled for interdiffusion and then heat-treated for precipitation. After a diffusion process at 1300 °C for 20 h, concentration gradients of Al and W were formed in the γ-Co(A1) matrix in the vicinity of the coupled interface. After a heat treatment at 900 °C for 500 h the γ′-Co₃(Al,W)(L1₂) phase was formed with a coarsened shape in contact with the γ, CoAl(B2) and Co₃W(D0₁₉) phases. Additionally, it appeared with a submicron cuboidal shape within the γ matrix. After 2000 h, however, the coarsened γ′ phase became infrequent and the three phases of γ, CoAl and Co₃W came into frequent contact with each other. These results clearly demonstrate that the γ′ phase is metastable and the three phases of γ, CoAl and Co₃W are thermodynamically in equilibrium at 900 °C in the Co–Al–W ternary system.     

Thermodynamic stability of barium thorate, BaThO3, from a Knudsen effusion study

The Gibbs energy of formation of barium thorate was determined using the Knudsen effusion forward collection technique. The evaporation process could be represented by the equation

BaThO₃(s)=ThO₂(s)+BaO(g)

The vapour pressure of BaO(g) over the two-phase mixture of BaThO₃(s) and ThO₂(s) was obtained from the rate of effusion of BaO(g) and could be represented as

ln(p/Pa) (±0.39)=−50526.5/T/K+26.95 (1770≤T/K≤2136)

The Gibbs energy of formation of BaThO₃(s) could be derived from this data and represented as

Δ_fG°(BaThO₃(s))/kJ mol⁻¹±8.0=−1801.75+0.276T/K

     

Characterization of the corrosion products of electrodeposited Zn, Zn–Co and Zn–Mn alloys coatings

The morphology, composition, phase composition and corrosion products of coatings of pure Zn (obtained from two types of electrolytic bath: an acidic bath (Zn_acid) and a cyanide-free alkaline bath (Zn_alkaline)) and of Zn–Mn and Zn–Co alloys on steel substrates were studied. To achieve this, diverse techniques were used, including polarization curves, atomic force microscopy (AFM), scanning electron microscopy (SEM), glow discharge spectroscopy (GDS), X-ray diffraction (XRD), and the salt spray test. In the salt spray test, the exposure time required for the coatings to exhibit red corrosion (associated with the oxidation of steel) decreased in the following order: Zn–Mn_(432h) > Zn–Co_(429h) > Zn_{alkaline(298h)} > Zn_acid(216h). The shorter exposure times required for corrosion of the pure Zn coatings are related to the coating composition and the crystallographic structure. Analysis of the corrosion products disclosed that Zn₅(OH)₈Cl₂·H₂O was a corrosion product of all of the coatings tested. However, the formation of oxides of manganese (MnO, Mn_0.98O₂, Mn₅O₈) in the Zn–Mn coating, and the formation of the hydroxide Zn₂Co₃(OH)₁₀·2H₂O in the Zn–Co coating, produced more compact and stable passive layers, with lower dissolution rates.     

In situ impedance spectroscopy study of the electrochemical corrosion of Ti and Ti–6Al–4V in simulated body fluid at 25 °C and 37 °C

The corrosion resistance of Ti and Ti–6Al–4V was investigated through electrochemical impedance spectroscopy, EIS, potentiodynamic polarisation curves and UV–Vis spectrophotometry. The tests were done in Hank solution at 25 °C and 37 °C. The EIS measurements were done at the open circuit potential at specific immersion times. An increase of the resistance as a function of the immersion time was observed, for Ti (at 25 °C and 37 °C), and for Ti–6Al–4V (at 25 °C), which was interpreted as the formation and growth of a passive film on the metallic surfaces.     

The phase equilibria of the Al–Ce–Ni system at 500 °C

The phase equilibria at 500 °C in the Al–Ce–Ni system in the composition region of 0–33.3 at.% Ce are investigated using XRD and SEM/EDX techniques applied to equilibrated alloys. The previously reported ternary phases and the variation of the lattice parameters versus the composition for different solid solution phases are investigated. It is confirmed that τ₂(Al₂CeNi) exists at 500 °C, while τ₃(Al₅Ce₂Ni₅) does not exist at 500 °C. A new compound τ₉ with composition of about Al₃₅Ce_16.5Ni_48.5 is found. The solubility of Ni in Al₁₁Ce₃ and αAl₃Ce is generally about 1 at.%, while the solubility of Ni in Al₂Ce is measured to be 2.7 at.%. The solubility of Ce in Al₃Ni, Al₃Ni₂, AlNi and AlNi₃ is all less than 1 at.%. The solubility of Al in CeNi₅, Ce₂Ni₇ and CeNi₃ is measured to be 30.4, 4.8 and 9.2 at.%, respectively, while there is no detectable solubility for Al in CeNi₂. A revised isothermal section at 500 °C in the Al–Ce–Ni system has been presented.     

The Yb–Zn–In system at 400 °C: Partial isothermal section with 0–33.3 at.% Yb

The phase relations in the ternary system Yb–Zn–In have been established for the partial isothermal section in the 0–33.3 at.% ytterbium concentration range at 400 °C, by researching of more than forty alloys. X-ray powder diffraction (XRPD), optical microscopy (OM) and scanning electron microscopy (SEM), complemented with energy dispersive X-ray spectroscopy (EDS), were used to study the microstructures, identify the phases and characterize their crystal structures and compositions. The phase equilibria of this Yb–Zn–In partial section at 400 °C are characterized by the presence of three extended homogeneity ranges, indium solubility in Yb₁₃Zn₅₈ and YbZn₂ and of zinc solubility in YbIn₂, and the existence of one ternary intermetallic compound, YbZn_1−xIn_1+x, x = 0.3. This new compound crystallizes in the UHg₂ structure type (space group P6/mmm), with a = 4.7933(5) Å, c = 3.6954(5) Å. The studied partial isothermal section has eight ternary phase fields at 400 °C.     

The Al–R–Mg (R=Gd, Dy, Ho) systems. Part I: experimental investigation

Key experiments were carried out on the three Al–R–Mg (R=Gd,Dy,Ho) systems and the results obtained used for the thermodynamic optimisation reported in a separate paper in this issue [Caccasmani G, De Negri S, Saccone A, Ferro R. Intermetallics this issue.]. The samples were characterized by differential thermal analysis (DTA), X-ray powder diffraction (XRD), light optical microscopy (LOM), scanning electron microscopy (SEM) and quantitative electron probe microanalysis (EPMA). The isothermal sections at 400 °C are all characterized by extended homogeneity regions at a constant rare earth content. The extension of the (Mg,Al)R solid solution, cP2-CsCl type, varies with the R atomic number. Ternary compounds (τ) of Al₂(R,Mg) stoichiometry (hexagonal Laves phases with MgNi₂-type structure) have been found to exist at 400 °C in all the systems. Their temperatures of formation were detected by DTA measurements.     

Formation of AB2-intermetallics by diffusion in the Au–Sb–Bi system

Binary diffusion couples, in which one single-phased product layer is growing between pure elements, were employed to study the diffusion properties of Au₂Bi- and AuSb₂-intermetallics at 230 and 330 °C. The position of the Kirkendall-marker plane inside the reaction zones revealed that in this temperature range the minority element is the faster diffuser in the Laves-phase Au₂Bi as well as in AuSb₂. The concept of integrated diffusion coefficient is used to describe the growth kinetics of the intermetallic compounds. The integrated diffusion coefficient in an intermetallic is related to the tracer diffusivities of the components and the thermodynamic stability of the phases involved in the interaction. The tracer diffusion coefficients were deduced from the interdiffusion experiments. The isothermal cross-section through the ternary phase diagram Au–Sb–Bi at 230 °C was constructed by means of the diffusion couple technique. No ternary phases are found in this system. Both intermetallic compounds Au₂Bi and AuSb₂ are in equilibrium with the (Sb,Bi)-solid solution. The solubility of Sb in the Laves-phase Au₂Bi was found to be negligible. Up to about 10.5 at.% of Bi can be dissolved in the AuSb₂-phase, the Bi-atoms substituting Sb in the cubic lattice of AuSb₂.     

Kinetics and mechanism of the nickel electrode—I. Acid solutions containing a high concentration of chloride and nickel ions

The kinetics of the Ni electrode in acid solutions with a high chloride ion concentration has been investigated in the range of 25–75°C. Dissolution occurs uniformly only at low anodic potentials. When the latter exceeds a critical value, E_crit, net localized metal corrosion takes place. The plot at E < E_crit corresponds to a curve approaching two limiting slopes, namely, at (

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. The cathodic Tafel slope is . These results, including their pH dependence, are explained with a reaction mechanism involving the participation of adsorbed hydroxo-species.     

On the four-phase reactions in the Ti–Ni–Al system

Two four-phase reactions of transition type in the Ti–Ni–Al system were studied on several alloys, which were annealed at carefully set temperatures and quenched. The phase constitution was established by XRD and EPMA analyses. Due to sluggish reaction kinetics, the transition temperatures were defined by annealing and quenching techniques as no DTA signals could be received. For the reaction NiAl + TiNiAl  TiNiAl₂ + TiNi₂Al, the transition temperature was found to be 925 °C ± 15 °C and for the reaction TiNiAl + Ti₃NiAl₈  TiAl₂ + TiNiAl₂, the transition temperature was found to be 990 °C ± 15 °C. Furthermore we confirmed the three-phase field TiNi₂Al + Ti₃Al + Laves phase (TiNiAl), as reported at 900 °C by Huneau et al. in 1999.     

A contribution to the Al–Ni–Cr phase diagram

The Al–Ni–Cr phase diagram was specified at 1000 °C and partially at 900 °C. The results concerning the region below 60 at.% Al agreed qualitatively with the literature data. The binary Al–Cr phases μ and γ dissolve up to 1 and 3 at.% Ni, respectively, and Al₃Ni₂ up to 2.5 at.% Cr. Two ternary phases were revealed: hexagonal ζ (a ≈ 1.77, c ≈ 1.24 nm) in a wide range between Al₈₁Ni₃Cr₁₆, Al_76.5Ni₃Cr_20.5, Al_76.5Ni₉Cr_14.5 and Al_71.5Ni₉Cr_19.5, and high-temperature orthorhombic (a ≈ 1.26, b ≈ 3.48, c ≈ 2.02 nm) around Al_76.5Ni_2.0Cr_21.5.     

Thermochemistry of holmium bismuthides

Thermodynamic properties of Ho–Bi intermediate phases (HoBi and Ho₅Bi₃) have been studied by means of calorimetric and tensimetric techniques. The heats of formation at T=298 K were determined by high temperature direct synthesis calorimetry and the molar heat capacity of HoBi was measured by differential scanning calorimetry (DSC) in the temperature range 330–920 K. The equilibrium vapour pressures over the two-phase region HoBi+Ho₅Bi₃ were measured by Knudsen Effusion–Mass Spectrometry in the temperature range 1357–1631 K. These data were analyzed by the second-law method to obtain the enthalpy changes for the atomization processes and, thereafter, the heats of formation for the two compounds. From the calorimetric measurements the heats of formation at 298 K were determined to be −93±3 and −112±4 kJ/mol atoms, respectively for the Ho₅Bi₃ and HoBi compounds, consistent with

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and obtained from the tensimetric measurements.     

Thermochemistry of ytterbium silicides

The results of the investigation of the high temperature decomposition reactions in vacuum under equilibrium conditions of ytterbium silicides in the whole composition range are reported. By means of the Knudsen Effusion–Mass Spectrometry (KE–MS) and the Knudsen Effusion–Weight Loss (KE–WL) techniques, the Yb(g) vapour pressures in equilibrium over the various high temperature and low temperature biphasic regions were measured in the temperature range 781–1395 K and the reaction enthalpies for the respective decompositions were derived. From this set of experimental data we derived for the first time the heats of formation of all the six known Si–Yb intermediate phases. The following values Δ_fH°₂₉₈ are recommended: Si₃Yb₅=−48.3±3.6, Si₄Yb₅=−53.2±4.6, SiYb=−51.1±5.1, Si₄Yb₃=−48.0±3.1, Si₅Yb₃=−41.3±2.6, Si_1.74Yb=−37.4±0.9, all in kJ/mol atoms.     

Pressure–composition isotherms in the Mg2Ni–H2 system

A relatively pure Mg₂Ni intermetallic compound was prepared by partial melting and sintering. Absorption and desorption pressure–composition isotherms for the Mg₂Ni–H₂ system were obtained. The relationships between the equilibrium plateau pressure (P_eq) and the temperature were

and

The procedure to obtain the pressure–composition isotherms was explained and a method to calculate the composition for pressure–composition isotherms (“the summation method”) was also suggested.     

Isothermal section at 1673 K of the Mo–Ru–Si diagram and crystallographic structures of ternary phases

Efforts to improve the high temperature behavior of MoSi₂ in oxidizing environments led to the investigation of the Mo–Ru–Si phase diagram. The isothermal section at 1673 K was determined by X-ray diffraction, optical and scanning electron microscopies and EPMA. Five new silicides were identified and their crystallographic structure was characterized using conventional and synchrotron X-ray as well as neutron powder diffraction. Mo₁₅Ru₃₅Si₅₀, denoted α-phase, is of FeSi-type structure, space group P2₁3, a=4.7535 (5) Å, D_x=7.90 g. cm⁻³, Bragg R=7.13. Mo₆₀Ru₃₀Si₁₀ is the ordered extension of the Mo₇₀Ru₃₀ σ-phase with space group P4₂/mnm, a=9.45940(8) Å, c=4.94273(5) Å, D_x=6.14 g. cm⁻³, Bragg R=5.75.     

Thermodynamic study of CVD–ZrO2 phase diagrams

Chemical vapor deposition (CVD) of zirconium oxide (ZrO₂) from zirconium acetylacetonate Zr(acac)₄ has been thermodynamically investigated using the Gibbs’ free energy minimization method and the FACTSAGE program. Thermodynamic data Cp°, ΔH° and S° for Zr(acac)₄ have been estimated using the Meghreblian–Crawford–Parr and Benson methods because they are not available in the literature. The effect of deposition parameters, such as temperature and pressure, on the extension of the region where pure ZrO₂ can be deposited was analyzed. The results are presented as calculated CVD stability diagrams. The phase diagrams showed two zones, one of them corresponds to pure monoclinic phase of ZrO₂ and the other one corresponds to a mix of monoclinic phase of ZrO₂ and graphite carbon.