Rapidly solidified non-equilibrium microstructure and phase transformation of plasma cladding Fe-based alloy coating

The rapidly solidified microstructural and compositional features, the precipitation and transformation of carbides during aging of Fe-based alloy coating prepared by plasma cladding have been investigated. The clad coating materials, whose powder mixture of Fe, Cr, Ni, B, Si and C with a weight ratio of 54.5:35:5:1:2:2.5, is processed using a non-transferred plasma arc. The clad coating adheres with low carbon steel in a good metallurgical bonding and the rate of dilution is 15-20%. Microstructural studies demonstrate that the coating possesses the metastable microstructure comprising the primary dendritic γ-austenite which is a non-equilibrium phase with an extended solid solution of alloying elements and interdendritic eutectic consisting of γ-austenite and (Cr,Fe)₇C₃ carbides. During the high temperature aging at 1253 K for 2 h, the fine spherical (Cr,Fe)₂₃C₆ carbide nucleates within (Cr,Fe)₇C₃ carbide and austenite matrix, and some martensite (α) also forms during cooling. The solidification and evolution sequence of the phase can be represented as follows: L → γ + L → γ + (γ + (Cr,Fe)₇C₃) → (γ + (Cr,Fe)₂₃C₆ + α). Due to the precipitation of (Cr,Fe)₂₃C₆ carbide and uniform distribution of carbide in the as-aged coating, the average hardness becomes higher than that of the as-clad coating.     

Influence of titanium addition on the microstructure of the novel ferrous-based stainless steel

The microstructural characteristics of the Fe-9Al-30Mn-1C-5Ti (wt.%) alloy were determined by scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray spectrometry. The microstructure of the alloy was essentially a mixture of (γ + TiC_x + (α + B2 + DO₃)) phases during solution treatment between 950 °C and 1150 °C. The TiC_x carbide had a face-center-cubic structure with a lattice parameter a of 0.432 nm. When the as-quenched alloy was subjected to aging treatment at temperatures of 450-850 °C, the following microstructural transformation occurred: (γ + TiC_x + κ + (α + DO₃)) → (γ + TiC_x + κ + (α + B2 + DO₃ + TiC_x)) → (γ + TiC_x + κ + κ′ + (α + B2 + DO₃)) → (γ + TiC_x + (α + B2 + DO₃)). Addition of Ti promotes the formation of the α phase at high temperatures.     

Isothermal section of the Ho-Co-Fe system at 773 K

The 773 K isothermal section of the phase diagram of the Ho-Co-Fe ternary system was investigated by using X-ray diffraction technique, metallographic analysis and scanning electron microscopy with energy dispersive analysis. The isothermal section of the ternary system consists of 6 three-phase regions, 16 two-phase regions and 11 single-phase regions. Three pairs of corresponding compounds of Ho-Co and Ho-Fe systems, i.e., Ho₂Co₁₇ and Ho₂Fe₁₇, HoCo₃ and HoFe₃, HoCo₂ and HoFe₂, form a continuous series of solid solution. At 773 K the compound Ho₆Fe_23−xCo_x was found to have a wide homogeneity range from 0 to 29 at.% Co. The maximum solid solubilities of Fe in Co, Ho₂Co₇, Ho₁₂Co₇ and Ho₃Co were determined to be about 10, 9, 2 and 5 at.% Fe, respectively. The maximum solid solubility of Co in Fe is found to be 78 at.% Co.     

Study of glass formation in the Sb2O3-PbO-MnO ternary system

Vitreous systems based on antimony oxide Sb₂O₃ have been investigated. The influence of MnO substitution on the mechanical and physical properties in the (80 − x)Sb₂O₃-20PbO-xMnO and (70 − x)Sb₂O₃-(30 − x)PbO-2xMnO systems has been studied. Vickers hardness, density, molar volume, Young modulus, glass temperature transition, infrared and UV transmission spectra depend on the MnO concentration. Crack analysis of the glass surface under indentor deformation shows the tenacity changes according to concentration of the MnO.     

Resistivity, thermopower, and thermal conductivity of nickel doped compounds Cr1−xNixSb2 at low temperatures

Substitutional compounds Cr_1−xNi_xSb₂ (0 ≤ x ≤ 0.1) were synthesized, and the effect of Ni substitution on transport and thermoelectric properties of Cr_1−xNi_xSb₂ were investigated at the temperatures from 7 to 310 K. The results indicated that the magnitudes of the resistivity and thermopower of Cr_1−xNi_xSb₂ decreased greatly with increasing Ni content at low temperatures, owing to an increase in electron concentration caused by Ni substitution for Cr. Experiments also showed that the low-temperature lattice thermal conductivity of Cr_1−xNi_xSb₂ decreased substantially with increasing Ni content due to an enhancement of phonon scattering by the increased number of Ni atoms. As a result, the figure of merit, ZT, of lightly doped Cr_0.99Ni_0.01Sb₂ was improved at T > ∼230 K. Specifically, the ZT of Cr_0.99Ni_0.01Sb₂ at 310 K was approximately ∼29% larger than that of CrSb₂, indicating that thermoelectric properties of CrSb₂ can be improved by an appropriate substitution of Ni for Cr.     

The effects of niobium and nickel on the corrosion resistance of the zinc phosphate layers

In this investigation the viability of nickel substitution by niobium in zinc phosphate (PZn) baths has been studied. Samples of carbon steel (SAE 1010) were phosphated in two baths, one containing nickel (PZn + Ni) and the other with niobium substituting nickel (PZn + Nb). Potentiodynamic polarization curves (anodic and cathodic, separately) and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion resistance of the phosphated carbon steels in a 0.5 mol L^− 1 NaCl electrolyte. The phosphate layers obtained were analysed by X-ray diffraction and it was found that they are composed of Zn₃(PO₄)₂.4H₂O (hopeite) and Zn₂Fe(PO₄)₂.4H₂O (phosphophylite). Surface observation by scanning electron microscopy (SEM) showed that the PZn + Ni layer is deposited as needle-like crystals, whereas the PZn + Nb layer shows a granular morphology. The electrochemical results showed that the PZn + Nb coating was more effective in the corrosion protection of the carbon steel substrate than the PZn + Ni layer. The results also suggested that nickel can be replaced by niobium in zinc phosphate baths with advantageous corrosion properties of the layer formed.     

Effects of Tl-filling into the voids and Rh substitution for Co on the thermoelectric properties of CoSb3

In order to enhance the thermoelectric (TE) properties of CoSb₃, we tried to reduce the lattice thermal conductivity (κ_lat) by filling Tl into the voids and substitution of Rh for Co. We prepared polycrystalline samples of Tl_x(Co_1−yRh_y)₄Sb₁₂ (x = 0, 0.05, 0.10, 0.15, 0.20 and y = 0.1, 0.2) and examined their TE properties from room temperature to 750 K. All the samples indicated negative values of the Seebeck coefficient (S). Both the electrical resistivity and the absolute values of the S decreased with increasing the Tl-filling ratio. The Tl-filling and Rh substitution reduced the κ_lat, due to the rattling and the alloy scattering effects. The minimum value of the κ_lat was 1.54 W m⁻¹ K⁻¹ at 550 K obtained for Tl_0.20(Co_0.8Rh_0.2)₄Sb₁₂. Tl_0.20(Co_0.8Rh_0.2)₄Sb₁₂ exhibited the best TE performance; the maximum value for the dimensionless figure of merit ZT was 0.58 at around 600 K.     

Phase equilibria and thermodynamic calculation of the Co–Ta binary system

Experimental investigation and thermodynamic evaluation of the Co–Ta binary phase diagram was carried out. Equilibrium compositions obtained in two-phase alloys and diffusion couples were measured by electron probe microanalyzer (EPMA). A very narrow λ₃(C36) + λ₂(C15) two-phase region is confirmed to be present around 26.5 at.% Ta at temperatures between 950 °C and 1448 °C. Equilibrium relationships above 1500 °C among the liquid, Laves (λ₁(C14), λ₂ and λ₃, whose stoichiometry is described by Co₂Ta), μ(D8_b) and CoTa₂(C16) phases were investigated by microstructural examination in as-cast Co-(24–60 at.%)Ta alloys. The solvus temperature of the γ′ Co₃Ta (L1₂) phase precipitated in the 5.8 at.%Ta γ(Co) and the peritectoid temperature of the Co₇Ta₂ phase in an 8.5 at.%Ta alloy were determined to be 1013 °C and 1033 °C, respectively, by differential scanning calorimeter (DSC). Fine precipitates of the γ′ phase precipitated in the γ (A1) matrix were observed by transmission electron microscope (TEM). Analyzing the present experimental results synthetically, the γ′ Co₃Ta phase was identified to be a metastable phase, of which the γ/γ′ transition temperature of the stoichiometric Co₃Ta alloy was estimated to be 2000 °C. Thermodynamic assessment of the Co–Ta binary system was carried out based on the present results as well as on experimental data in the literature. Calculated results of not only stable but also metastable equilibria were found to be in good agreement with the revised phase diagram. The evaluated stability of the metastable γ′ Co₃Ta coincides with the enthalpy of formation (ΔH(γ'Co₃Ta) = −23.44 kJ/mol) calculated by the ab initio method.     

Influence of metal ions on the formation of artificial zinc rusts

The artificial rust particles were prepared from ZnCl₂ solutions dissolving Al(III), Fe(III), Fe(II), Ni(II), Co(II) and Mg(II) at different atomic ratios from 0 to 0.3 in metal/Zn. With increasing metal/Zn the crystal phases of the products turned following as ZnO → a mixture of ZnO and Zn₅(OH)₈Cl₂ · H₂O (ZHC) → ZHC. Al(III) most facilitated the formation of ZHC but Mg(II) and Fe(III) produced no ZHC. The morphology of the formed particles varied following as agglomerate → fine → rod → sheet → irregular with the increase of metal/Zn. The sheet and irregularly shaped particles were identified as ZHC and the other particles as ZnO.     

Effect of underpotential deposition of lead on polarization behavior of nickel in acidic perchlorate solutions at room temperature

The effect of Pb²⁺ on polarization behavior of nickel has been investigated in 0.1 M NaClO₄ + 10⁻² M HClO₄ + x M PbO solutions (x = 0, 10⁻⁵, 10⁻⁴, 10⁻³) at room temperature. The cyclic voltammogram has suggested that Pb²⁺ degrades the stability of the passive film on Ni. The corrosion potential of Ni shifted to the more noble direction and the anodic current peak of Ni dissolution decreased with increasing Pb²⁺ concentration in solution, indicating that Pb²⁺ suppresses significantly the anodic dissolution. The underpotential deposition (UPD) of lead on Ni in the potential range more noble than −0.215 V (SHE) corresponding to the equilibrium potential of the Pb²⁺ (10⁻³ M)/Pb electrode was confirmed by XPS and GDOES analyses. The anodic Tafel slope, b⁺, of Ni dissolution changed from b⁺ = 40 mV decade⁻¹ in the absence of Pb²⁺ to b⁺ = 17 mV decade⁻¹ in the presence of 10⁻⁴ or 10⁻³ M Pb²⁺, which was ascribed to the increase in active sites of Ni surface emerged as a result of electrodesorption of Pb adatoms. The roles of Pb adatoms in active dissolution and active/passive transition of Ni were discussed from the above results.     

Crystal structure change in the dehydrogenation process of the Li-Mg-N-H system

The Li-Mg-N-H system has the property of reversible reaction with hydrogen between hydrogenation and dehydrogenation (Mg₃N₂ + 4Li₃N + 12H₂ ↔ 3Mg(NH₂)₂ + 12LiH). At the several dehydrogenation stages of p-c isotherm measurement at 523 K, the structural change was investigated using the synchrotron X-ray diffraction. There are two regions in p-c isotherm of the Li-Mg-N-H system, i.e. plateau and sloping region. In the plateau region, Mg(NH₂)₂ and Li₃Mg₃(NH₂)(NH)₄ coexist. In the sloping region, the intermediate phase Li_3+3yMg₃(NH₂)_1−y(NH)_4+2y changes continuously from Li₃Mg₃(NH₂)(NH)₄ to Li₂Mg(NH)₂. The chemical composition of the intermediate phase was estimated from the amount of desorbed hydrogen by p-c isotherm and the atomic ratio of Mg and N by Rietveld analysis. The crystal structure of the intermediate phase, Li_3+3yMg₃(NH₂)_1−y(NH)_4+2y (space group: I222), was determined. Because all these intermediate structures are similar to anti-CaF₂-type, it is deduced that the dehydrogenation process are caused by the diffusion of Li⁺ to cation sites of Mg(NH₂)₂. The analysis of structural change clarified the dehydrogenation process that is accomplished by the diffusion of Li⁺ and Mg²⁺ without N atom diffusion.     

Formation, fast oxidation and thermodynamic data of Fe(II) hydroxychlorides

Iron(II) hydroxide and hydroxychloride precipitates were obtained by mixing FeCl₂ · 4H₂O and NaOH aqueous solutions with various concentration ratios R′ = [Cl⁻]/[OH⁻] = 2 [FeCl₂]/[NaOH] at [NaOH] = 0.4 mol L⁻¹. They were analysed by Infrared spectroscopy after 24 h of ageing at room temperature. Fe(OH)₂ was obtained alone only for the smallest values of R′, typically R′ ? 1.16. β-Fe₂(OH)₃Cl formed as soon as R′ ? 1.40 and was obtained alone for R′ ? 2.25. The initial precipitates were oxidised by addition of a small amount of hydrogen peroxide (5 mL of an aqueous solution containing approximately 30 vol% H₂O₂) instead of O₂. The action of H₂O₂ on Fe(OH)₂ gave rise to δ-FeOOH as already reported. Its action on Fe(II) hydroxychlorides gave rise to akaganéite β-FeO_1−2x(OH)_1+xCl_x. A transformation of the two-phase system found at R′ = 1.5 after long ageing times (6 months) was observed and β-Fe₂(OH)₃Cl remained alone. This slow transformation of Fe(OH)₂ into β-Fe₂(OH)₃Cl may explain why β-Fe₂(OH)₃Cl was only reported as a corrosion product on iron archaeological artefacts. Finally, the respective domains of stability of Fe(OH)₂ and β-Fe₂(OH)₃Cl were demarcated and an estimation of the standard Gibbs free energy of formation of β-Fe₂(OH)₃Cl could be given: .     

Thermodynamic stability of Co–Al–W L12 γ′

Co-based superalloys in the Co–Al–W system exhibit coherent L1₂ Co₃(Al,W) γ′ precipitates in an face-centered cubic Co γ matrix, analogous to Ni₃Al in Ni-based systems. Unlike Ni₃Al, however, experimental observations of Co₃(Al,W) suggest that it is not a stable phase at 1173 K. Here, we perform an extensive series of density functional theory (DFT) calculations of the γ′ Co₃(Al,W) phase stability, including point defect energetics and finite-temperature contributions. We first confirm and extend previous DFT calculations of the metastability of L1₂ Co₃(Al_0.5W_0.5) γ′ at 0 K with respect to hexagonal close-packed Co, B2 CoAl and D0₁₉ Co₃W using the special quasi-random structure (SQS) approach to describe the Al/W solid solution, employing several exchange/correlation functionals, structures with varying degrees of disorder, and newly developed larger SQSs. We expand the validity of this conclusion by considering the formation of antisite and vacancy point defects, predicting defect formation energies similar in magnitude to Ni₃Al. However, in contrast to the Ni₃Al system, we find that substituting Co on Al sites is thermodynamically favorable at 0 K, consistent with experimental observation of Co excess and Al deficiency in γ′ with respect to the Co₃(Al_0.5W_0.5) composition. Lastly, we consider vibrational, electronic and magnetic contributions to the free energy, finding that they promote the stability of γ′, making the phase thermodynamically competitive with the convex hull at elevated temperature. Surprisingly, this is due to the relatively small finite-temperature contributions of one of the γ′ decomposition products, B2 CoAl, effectively destabilizing the Co, CoAl and Co₃W three-phase mixture, thus stabilizing the γ′ phase.     

Experimental investigation of the Ce-Cu phase diagram

The binary Ce-Cu system has been re-investigated via the selected eighteen key alloys by means of the differential scanning calorimetry (DSC), X-ray diffraction (XRD), and scanning electron microscopy (SEM) with energy dispersive X-ray analysis techniques. Five intermetallic compounds, Cu₆Ce, Cu₅Ce, Cu₄Ce, Cu₂Ce, and CuCe, have been confirmed. Cu₆Ce and Cu₂Ce melt congruently at 947 °C and 810 °C, respectively. Cu₅Ce, Cu₄Ce, and CuCe are formed through peritectic reactions, L + Cu₆Ce ↔ Cu₅Ce at 799 °C, L + Cu₅Ce ↔ Cu₄Ce at 792 °C, and L + Cu₂Ce ↔ CuCe at 492 °C, respectively. Three eutectic reactions, L ↔ (Cu) + Cu₆Ce at 879 °C, L ↔ Cu₄Ce + Cu₂Ce at 753 °C, and L ↔ CuCe + (γCe) at 407 °C, have been observed. One catatectic reaction, (δCe) ↔ L + (γCe) at 702 °C, was determined. According to the present experimental results, the Ce-Cu phase diagram is revised.     

Experimental determination of phase equilibrium in the Fe–Co–Sb ternary system

Phase stability and phase transformation were studied in the Fe–Co–Sb ternary system for the three sections: CoSb–Fe_0.56Sb_0.44, 30 at.% of Sb and 75 at.% of Sb. In the first section, we find a continuous solid solution without any secondary phase. The unit cell volume increases as a function of X_Fe/(X_Fe + X_Co). At 30 at.% of Sb, the B8 and the bcc-A₂ phases are obtained across the whole Fe–Co section. On the CoSb₃ side (75 at.% of Sb), Fe atoms cannot completely substitute for Co atoms in the skutterudite structure. Below 5 at.% of substitution of Fe for Co in CoSb₃, only the D0₂ phase is present while for high concentration of Fe, marcasite and Sb phases coexist.     

One-step synthesis and properties of monolithic photoluminescent ruby colored cuprous oxide antimony oxide glass nanocomposites

Cuprous oxide (Cu₂O) antimony glass (K₂O-B₂O₃-Sb₂O₃) monolithic nanocomposites having brilliant yellow to ruby red color have been synthesized by a single-step melt-quench technique involving in situ thermochemical reduction of Cu²⁺ (CuO) by the reducing glass matrix without using any external reducing agent. The X-ray diffraction (XRD), infrared transmission and reflection spectra, and selected area electron diffraction analysis support the reduction of Cu²⁺ to Cu⁺ with the formation of Cu₂O nanoclusters along with Cu_ySb_2−x(O,OH)_6-7 (y ≤ 2, x ≤ 1) nanocrystalline phases while Cu⁰ nanoclusters are formed at very high Cu concentration. The UV-vis spectra of the yellow and orange colored nanocomposites show size-controlled band gap shift of the semiconductor (Cu₂O) nanocrystallites embedded in the glasses while the red nanocomposite exhibits surface plasmon resonance band at 529 nm due to metallic Cu. Transmission electron microscopic image advocates the formation of nanocystallites (5-42 nm). Photoluminescence emission studies show broad red emission band around 626 nm under various excitation wavelengths from 210 to 270 nm.     

Investigation of the HCl (g) attack on pre-oxidized pure Fe, Cr, Ni and commercial 304 steel at 400 °C

The paper presents the results from an investigation studying the ability of pre-oxidized metals and alloys to withstand chlorine attack in the form of gaseous HCl. The materials under investigation were pure Fe (s), Cr (s), Ni (s), and a commercial 18Cr-10Ni-Fe (304) alloy. The samples were pre-oxidized in different well defined environments, dry 10 vol.% O₂ (g) + N₂ (bal.), 10 vol.% O₂ (g) + 5 vol.% H₂O (g) + N₂ (bal.) and 10 vol.% O₂ (g) + 250 vppm SO₂ (g) + N₂ (bal.) for 24 h at 400 °C using a horizontal tube furnace. Afterwards the oxide films were characterized by GI-XRD, FEG-SEM, XPS and ToF-SIMS. The samples were then exposed further in 10 vol.% O₂ (g) + 500 vppm HCl (g) + x (x = 5 vol.% H₂O (g), 250 vppm SO₂ (g)) + N₂ (bal.). The exposure time was 100 h and after the exposures during the cool down process the reaction chamber was flushed with dry 10 vol.% O₂ (g) + N₂ (bal.). The corroded samples were then examined by the same techniques mentioned before. HCl (g) showed mainly to be aggressive toward the Fe (s) samples that form a relatively thick and porous oxide scale consisting of layered Fe₂O₃ (s)/Fe₃O₄ (s) during pre-oxidation, and the aggressiveness did not depend on the pre-oxidation conditions. All the other materials formed thin and dense oxides (20-100 nm) during pre-oxidation, and they did not suffer accelerated oxidation caused by HCl (g) during the subsequent exposure. The only exception was Ni (s) that had been pre-oxidized in an atmosphere containing SO₂ (g), in this case Ni sulphides and sulphates were formed during pre-oxidation which in turn caused accelerated oxidation to Ni when subsequently exposed to HCl (g). HCl (g) readily reacts with NiSO₄ (s) and Ni₃S₂ (s) and forms NiCl₂ (s) and SO₃ (g).     

Phase Equilibrium of the Fe-Cr-Ni-Al Quaternary System at 900 °C

The 900 °C isothermal sections of the Fe-Cr-Ni-Al quaternary with Fe fixed at 70 at.% and that with Ni fixed at 60 at.% have been determined by scanning electron microcopy coupled with energy dispersive spectroscopy and x-ray diffraction. Only one three-phase region marked as α-Fe + β-(Fe,Ni)Al + γ-Fe has been found in the 70Fe-Cr-Ni-Al section. With regard to the Fe-Cr-60Ni-Al section, there are three three-phase regions, i.e., α-Cr + γ-Ni + γ′-Ni₃Al, γ-Ni + γ′-Ni₃Al + β-(Fe,Ni)Al and α-Cr + β-(Fe,Ni)Al + γ′-Ni₃Al and one four-phase region, namely α-Cr + β-(Fe,Ni)Al + γ-Ni + γ′-Ni₃Al. No quaternary compound is found in the present work.     

The influence of Sc/Lu ratio on the phase transformation and luminescence of cerium-doped lutetium scandium orthoborate solid solutions

The dependence of structural characteristics of cerium-doped lutetium scandium orthoborate (Lu_1−xSc_x)BO₃:Ce solid solutions on Sc/Lu ratio was investigated. It was found that the calcite phase of LuBO₃ can be stabilized up to 1550 °C at least when the n(Sc)/n(Lu + Sc) ratio was ≥10 at.%. The closed correlations between Sc³⁺ or Ce³⁺ molar ratio in the host and luminescence mechanism were discussed in detail. Based on the requirements of steady phase structure, better luminescence efficiency and higher density, the reasonable n(Sc)/n(Lu + Sc) and n(Ce)/n(RE) ratio should be in the range of 30-50 at.% and 0.3-0.5 at.%, respectively. A modified composition, (Lu_0.5Sc_0.5)_0.995Ce_0.005BO₃ solid solution, was selected to grow single crystal. Its X-ray excited luminescence intensity can be as high as about 27% of LYSO:Ce standard crystal and the effective lifetime is round 20.1 ns. Hence, the cerium-doped lutetium scandium orthoborate crystal is a promising scintillator for X-ray detection or γ-ray detection.     

Enthalpy of formation of selected mixed oxides in a CaO-SrO-Bi2O3-Nb2O5 system

The heats of drop-solution in 3Na₂O + 4MoO₃ melt at 973 K and 1073 K for calcium and strontium carbonates, Bi₂O₃, Nb₂O₅ and several stoichiometric mixed oxides in CaO-Nb₂O₅, SrO-Nb₂O₅ and Bi₂O₃-Nb₂O₅ systems were measured using a Setaram Multi HTC-96 calorimeter. The values of enthalpy of formation from constituent binary oxides at 298 K, Δ_oxH, were derived for the mixed oxides under investigation: Δ_oxH(CaNb₂O₆) = −132.0 ± 23.8 kJ mol⁻¹, Δ_oxH(Ca₂Nb₂O₇) = −208.0 ± 31.9 kJ mol⁻¹, Δ_oxH(SrNb₂O₆) = −167.9 ± 19.1 kJ mol⁻¹, Δ_oxH(Sr₂Nb₂O₇) = −289.2 ± 37.5 kJ mol⁻¹ and Δ_oxH(BiNbO₄) = −41.9 ± 11.1 kJ mol⁻¹. Additionally, the values Δ_oxH for other mixed oxides with different stoichiometries were estimated on the basis of these experimental results.