First-principles study of electronic structure and magnetic properties of orthorhombic CrGa2Sb2 and MnGa2Sb2

By the first-principles calculations, we present the results of electronic structure and magnetic properties on bulk CrGa₂Sb₂ and MnGa₂Sb₂ in an orthorhombic structure with the linear chains of transition-metal Cr and Mn atoms, using four different exchange correlation potentials: the local density approximation (LDA), the generalized gradient approximation (GGA), GGA + U, and the Tran-Blaha modified Becke-Johnson functional (mBJ). The electronic structure calculations from four exchange correlation potentials show that CrGa₂Sb₂ is a pseudogap (negative gap) material with very small density of states (DOS) at the Fermi level, while MnGa₂Sb₂ has notably higher DOS at the Fermi level compared to CrGa₂Sb₂, exhibiting stronger metallic conductivity, although the mBJ potential obtains lower DOS at the Fermi level than LDA and GGA for both CrGa₂Sb₂ and MnGa₂Sb₂. The GGA + U method with a small value (1 eV) of the on-site Coulomb interaction parameter U obtains lower DOS at the Fermi level compared to the large value of U. In agreement with the measurement data, the total energy calculations reveal that both CrGa₂Sb₂ and MnGa₂Sb₂ have a stable ferromagnetic ground state with lower energies relative to antiferromagnetic state. Based on the Heisenberg model, the magnetic exchange constants between the nearest-neighbor Cr–Cr and Mn–Mn along transition-metal linear chains are calculated to be 48.6 meV and 27.5 meV for CrGa₂Sb₂ and MnGa₂Sb₂, respectively. By the mean-field approximation method, we calculated the Curie temperature of two compounds to be above room-temperature.     

Magnetic and related properties of Ce5CoGe2, CeCoGe and CeCo2Ge2

Magnetic susceptibility, magnetization, specific heat, electrical resistivity and thermoelectric power of polycrystalline Ce₅CoGe₂, CeCoGe and CeCo₂Ge₂ were studied at temperatures down to 2 K and in magnetic fields up to 5 T. The novel phase Ce₅CoGe₂ was found to be a ferromagnet with the Curie temperature of about 11 K, which exhibits in the paramagnetic region some features of a dense Kondo system with strong crystal field effect. The re-investigated CeCoGe was found to order antiferromagnetically below 4.6 K, while CeCo₂Ge₂ is an intermediate-valence system, in agreement with previous reports. The thermoelectric power of the latter compound is large (up to 40 μV/K) and positive in the whole temperature range studied, while in the magnetically ordered systems Ce₅CoGe₂ and CeCoGe it is mostly negative and distinctly smaller (down to −1.5 and −11 μV/K, respectively).     

Synthesis and properties of CaCd2Sb2 and EuCd2Sb2

High density polycrystalline CaCd₂Sb₂ and EuCd₂Sb₂ intermetallics are synthesized by Spark Plasma Sintering and their thermoelectric properties are investigated. X-ray diffraction measurements reveal both materials have a structure in space group, containing a small amount of CdSb as a second phase. Thermoelectric measurements indicate both are p-type conductive materials. The figure of merit value of CaCd₂Sb₂ is 0.04 at 600 K and that of EuCd₂Sb₂ is 0.60 at 617 K. Theoretical calculations show that CaCd₂Sb₂ is a degenerate semiconductor with a band gap of 0.63 eV, while EuCd₂Sb₂ is metallic with DOS of 13.02 electrons/eV. For deeper understanding of the better thermoelectric properties of EuCd₂Sb₂, its low temperature magnetic, transport and heat capacity properties are investigated. Its Nèel temperature is 7.22 K, convinced by heat capacity anomaly at 7.13 K. Hall effect convinced that it is a p-type conductive material. It has high Hall coefficient, high carrier concentration and high carrier mobility of +1.426 cm³/C, 4.38 × 10¹⁸/cm³ and 182.40 cm²/Vs, respectively. They are all in the magnitude of good thermoelectric materials. The Eu 4f level around Fermi energy and antiferromagnetic order may count for the better thermoelectric properties of EuCd₂Sb₂ than that of CaCd₂Sb₂.     

Microstructural evolution and mechanical properties of as-cast and directionally-solidified Nb-15Si-22Ti-2Al-2Hf-2V-(2, 14) Cr alloys at room and high temperatures

Arc-melting (AC) and directional solidification (DS) techniques were used to prepare Nb-15Si-22Ti-2Al-2Hf-2V-(2, 14) Cr alloys (hereafter referred as to 2Cr and 14Cr alloys, respectively), and the microstructural evolution and mechanical properties, including Vickers hardness, room temperature fracture toughness and high temperature strength, of the two AC and DS alloys were compared. The results showed that with heat-treatment at 1350 °C for 50 h, the AC-2Cr alloy composed of Nb solid solution (Nb_SS) and α-Nb₅Si₃ silicide, while Laves C15-Cr₂Nb phase arose in the 14Cr alloy. With two-phase Nb_SS/α-Nb₅Si₃ microstructure, the AC-2Cr alloy showed excellent room-temperature fracture toughness (K_Q: 14.2 MPa m^1/2) and 0.2% yield strength at 1250 °C (σ_0.2: 315 MPa) and 1350 °C (σ_0.2: 294 MPa), better than the AC-14Cr alloy with tri-phase Nb_SS/α-Nb₅Si₃/C15-Cr₂Nb microstructure (K_Q: 9.4 MPa m^1/2, σ_0.2: 189 MPa at 1250 °C and 87 MPa at 1350 °C). The DS technique was found not to change the phase constituent of each alloy, but it made the microstructure slightly orient to the growth direction, resulting in a significant improvement in room-temperature fracture toughness (by ∼43%) and high-temperature yield strength σ_0.2 (by ∼55%), as compared with the AC samples.     

Thermal barrier coating bonded by (Al2O3–Y2O3)/(Y2O3-stabilized ZrO2) laminated composite coating prepared by two-step cyclic spray pyrolysis

Thermal barrier coating bonded by (Al₂O₃–Y₂O₃)/(Y₂O₃-stabilized ZrO₂) (YSZ) laminated coating has been developed on Ni-based superalloy by two-step cyclic pyrolysis. It is demonstrated, from cyclic oxidation tests at 1100 °C, that YSZ top coat and alloy substrate can be bonded together effectively by the (Al₂O₃–Y₂O₃)/YSZ laminated coating, showing good resistance to oxidation, cracking, spallation and buckling. These beneficial effects can be attributed to the sealing effect of the designed multi-sealed compact bond coat with α-Al₂O₃ layers, the decrease of thermal stresses, the increase of fracture toughness in such bond coat and no interdiffusion between the substrate and bond coat.     

Impact of oxyfuel atmospheres H2O/CO2/O2 and H2O/CO2 on the oxidation of ferritic–martensitic and austenitic steels

In future power plant technologies, oxyfuel, steels are subjected to steam rich and carbon dioxide rich combustion gases. The effect of simulated combustion gases H₂O/CO₂/O₂ (30/69/1 mol%) and H₂O/CO₂ (30/70 mol%) on the corrosion behavior of low alloyed steels, 9–12% chromium steels and an austenitic steel were studied. It was discovered that the formation of protective chromium rich oxides is hampered due to the carburization of the base material and the formation of chromium rich carbides. The kinetics of corrosion and carburization are quantified. The effect of temperature and the effect of gas pressure are analyzed statistically.     

Oxidation behavior and phase transition of ZrB2–SiCw–ZrO2f ceramic

The oxidation behavior and phase transition of ZrB₂–SiC_w–ZrO_2f ceramic had been investigated by in situ high-temperature XRD, XPS, SEM, EDS and TEM measurements. The initial oxidation temperature of most ZrB₂ was 1000 °C and no significant oxidation of SiC was found up to 1200 °C. The oxidation products formed at lower temperatures would penetrate into the pores and flaws on the surface, which was beneficial to crack healing. In order to improve the oxidation resistance of this system, it should be focused on decreasing the oxygen diffusivity and the volume expansion caused by phase transition.     

Antiferromagnetic ordering below 1.7 K in PrIr2Ge2

We present our investigations on magnetic and transport properties of polycrystalline PrIr₂Ge₂ which forms in CaBe₂Ge₂-type primitive tetragonal structure (space group P4/nmm). The ac magnetic susceptibility data exhibit two well pronounced peaks at 2.08 K and 0.76 K due to the onset of magnetic order. The specific heat also exhibits a sharp λ-type anomaly at 1.7 K confirming the onset of bulk antiferromagnetic order. The temperature dependence of magnetic part of entropy suggests a quasi-triplet ground state in this compound. The onset of magnetic order is also confirmed by the electrical resistivity data.     

Corrosion behaviour of Y2O3-ZrO2 coatings on IN713LC in a LiCl-Li2O molten salt

Hot corrosion studies were performed on superalloy specimens. The IN713LC superalloy were sprayed with an aluminized NiCrAlY-bond coat and then with an yttria-zirconia top coat. The bare superalloy reveals an obvious weight loss due to spalling of the scales by the rapid scale growth and thermal stress. The top coatings showed a much better hot corrosion resistance in the presence of LiCl-3 wt.% Li₂O molten salt when compared with those of the bare superalloy and the aluminized bond coatings. These coatings have been found to be beneficial for increasing hot corrosion resistance of structural materials for lithium molten salts.     

Molecular modeling of the inhibition mechanism of 1-(2-aminoethyl)-2-alkyl-imidazoline

Inhibition mechanism of five 1-(2-aminoethyl)-2-alkyl-imidazoline derivatives for carbon steel against CO2 corrosion was studied by molecular modeling. Molecular reactivity derived from quantum chemical calculation is insensitive to alkyl length. Inhibitor molecules can be adsorbed preferentially on metal surface with imidazoline ring attached on the surface. And with increase of alkyl length, interaction between inhibitor molecule and metal surface is enhanced to enable more stable adsorption of inhibitor molecules, which will form more compact self-assembly membrane with higher inhibition efficiency. The efficiency order of the inhibitors obtained by theoretical analysis was verified by experimental results.     

Corrosion characteristics of LiBH4 film exposed to a CO2/H2O/O2/N2 mixture

LiBH₄ films were prepared by pulsed laser deposition using a LiB target in a background pressure of hydrogen. The corrosion characteristics of LiBH₄ films were measured by exposing them to a gas mixture of CO₂/H₂O/O₂/N₂ at ambient temperature for 1–24 h. Scanning electron microscopy images show some cracks on the surface of corrosion films, which could act as easy paths for H₂O and CO₂ to further react with Li⁺ and B³⁺. The X-ray photoelectron spectroscopy results and theoretical analysis show that LiBH₄ tends to react with H₂O and CO₂ to form Li₂B₄O₇, Li₂CO₃ and LiOH during the corrosion process.     

Initiation and growth of iron metal dusting in CO-H2-H2O gas mixtures

The initiation and growth of iron metal dusting in CO-H₂-H₂O gas mixtures at 700 °C were investigated by surface observations of very early stages of the reaction. At first, iron was supersaturated with dissolved carbon and its surface became facetted. The nucleation of graphite and cementite depended on the surface crystallographic orientation. A fine grain structure at ground surfaces and a high carbon activity accelerated cementite nucleation. Further carburisation resulted in the formation of particulate areas mixed with deposited graphite, which accelerated the spallation of cementite and the protrusion of round particles. In some areas, large graphite mounds and bulk graphite were formed on the surface. Filamentous carbon was found in particulate areas and surrounding the graphite mounds. Based on these observations, a possible process of iron metal dusting was discussed.     

Copper corrosion inhibition in O2-saturated H2SO4 solutions

Corrosion inhibition of copper in O₂-saturated 0.50 M H₂SO₄ solutions by four selected amino acids, namely glycine (Gly), alanine (Ala), valine (Val), or tyrosine (Tyr), was studied using Tafel polarization, linear polarization, impedance, and electrochemical frequency modulation (EFM) at 30 °C. Protection efficiencies of almost 98% and 91% were obtained with 50 mM Tyr and Gly, respectively. On the other hand, Ala and Val reached only about 75%. Corrosion rates determined by the Tafel extrapolation method were in good agreement with those obtained by EFM and an independent chemical (i.e., non-electrochemical) method. The chemical method of confirmation of the corrosion rates involved determination of the dissolved Cu²⁺, using ICP-AES (inductively coupled plasma atomic emission spectrometry) method of chemical analysis. Nyquist plots exhibited a high frequency depressed semicircle followed by a straight line portion (Warburg diffusion tail) in the low-frequency region. The impedance data were interpreted according to two suitable equivalent circuits. The kinetics of dissolved O₂ reduction and hydrogen evolution reactions on copper surface were also studied in O₂-saturated 0.50 M H₂SO₄ solutions using polarization measurements combined with the rotating disc electrode (RDE). The Koutecky-Levich plot indicated that the dissolved O₂ reduction at the copper electrode was an apparent 4-electron process.     

Kinetics of H2O2 reaction with oxide films on carbon steel

The nature of carbon steel surfaces in 0.01 M borate solutions (pH 10.6) have been characterized using a range of electrochemical techniques and ex situ analyses such as Raman and Auger spectroscopy. Their subsequent behaviour on exposure to 10⁻³ M H₂O₂-containing solutions has also been studied. The anodically oxidized carbon steel surfaces have been characterized according to three regions: (I) the potential range <−0.5 V (vs SCE), when the surface is active and covered by Fe^II/Fe^III oxide/hydroxide; (II) the potential range −0.5 V to 0.0 V when the surface is passivated by an outer layer of Fe^III oxide/hydroxide over the inner layer of Fe^II/Fe^III oxide/hydroxide; and (III) potentials >0 V when further growth of the underlying layer appears to lead to minor film breakdown/restructuring. The addition of H₂O₂ to films grown in the passive region or above (II and III) leads initially to a degradation of the outer layer allowing increased growth of the inner layer. Subsequently, the outer passivating layer is repaired and passivity re-established. These changes appear to be confirmed by Raman spectroscopy.     

Oxidation of Fe–10Cr in O2 and in O2 + H2O environment at 600 °C: A microstructural investigation

Oxidation of Fe–10Cr in dry and wet O₂ was studied at 600 °C for up to 168 h. Oxide microstructure was investigated by STEM/EDX, FIB/SEM and TEM. Oxidation in dry O₂ gives a Cr-rich protective (Fe_1−xCr_x)₂O₃ scale. The same protective oxide initially forms in O₂ + H₂O environment, but after an incubation period scale breakdown is triggered by CrO₂(OH)₂ evaporation that depletes the substrate in Cr and converts (Fe_1−xCr_x)₂O₃ to FeCr spinel oxide. Internal oxidation occurs after breakaway. Alternating external and internal oxidation result in the inward-growing scale showing a characteristic banded morphology.     

Magnetoresistivity of DyNi2B2C thin film

We present high-resolution resistivity and magnetoresistivity measurements on a DyNi₂B₂C thin film obtained by laser ablation. The measurements are interpreted in the framework of the theory developed by Yamada and Takada (YT) in the early 1970s (Yamada H., Takada S. Prog Theor Phys 1973;49:1401) for the magnetoresistivity of the antiferromagnetic materials and permit identification of the magnetic field H_c2 that destroys the magnetic ordering. So, we obtain a H–T phase diagram where the antiferromagnetic and paramagnetic states are unambiguously determined and that we compare with data in the literature. Finally, in the paramagnetic state we have found a linear dependence between magnetoresistivity and the square of the magnetization.     

Oxidation, carburisation and metal dusting of 304 stainless steel in CO/CO2 and CO/H2/H2O gas mixtures

The oxidation and carburisation behaviour of 304 stainless steel was studied during thermal cycling in CO/CO₂ at 700 °C, and also in CO/H₂/H₂O at 680 °C. Thermal cycling caused repeated scale separation which accelerated chromium depletion from the alloy subsurface regions. The CO/CO₂ gas, with a_C=7 and , caused internal precipitation of oxides and carbides, some surface damage, but no dusting. In contrast, the CO/H₂/H₂O gas, with a_C = 19 and caused rapid graphite deposition and metal dusting. This was accompanied by internal oxidation and carburisation. The internal oxide was identified as spinel, which forms in the short term, but not at long reaction time. Its formation produced a significant volume expansion, which disrupted the material and resulted in surface damage in both gas atmospheres. In CO/H₂/H₂O, however, direct graphite deposition and metal disintegration into dust was the main reaction. The very different reaction morphologies produced by the two gas mixtures are discussed in terms of competing gas-alloy reaction steps.     

2-Mercaptobenzothiazole monolayers on zinc and silver surfaces for anticorrosion

Anticorrosive behaviors of 2-mercaptobenzothiazole (MBT) self-assembled monolayers (SAMs) on silver and zinc electrodes were comparatively studied by means of electrochemical impedance spectroscopy (EIS). The promising inhibition effect of the MBT for silver and zinc from corrosion had been confirmed. The adsorption geometries of MBT monolayers on zinc and silver electrodes were observed by surface enhanced Raman scattering (SERS) technique. The SERS spectra implied that monolayers of MBT could be self-assembled on Ag surface through S¹⁰ and N³ atoms and the molecular plane should be tilted with respect to the surface. On Zn surface, MBT molecules formed monolayers via both S atoms and the other moieties of the molecule away from the surface. From the in situ electrochemical SERS results it can be found that MBT monolayers on both Ag and Zn surfaces experienced the changes of adsorption fashions as the potential shifting to more negative direction.     

Rotating magnetocaloric effect in HoAl2 single crystal

In this paper we theoretically discuss the rotating magnetocaloric effect in HoAl₂ single crystal. In order to do that, we use a model Hamiltonian of interacting magnetic moments including a term to account for the crystal electric field. Our theoretical calculations of the entropy changes are in a reasonable agreement with the available experimental data. Moreover, we predict the existence of an anomalous rotating magnetocaloric effect for some directions of the magnetic field rotation.     

Characterization and properties of the MgF2/ZrO2 composite coatings on magnesium prepared by micro-arc oxidation

Through micro-arc oxidation, the MgF₂/ZrO₂ composite coatings were prepared on magnesium at the different applied voltages (in the range of 400-550 V) in a zirconate electrolytic solution. The morphologies, phase components, microhardness, bond strengths, and corrosion resistances of the composite coatings were investigated. The effect of the applied voltages on the characteristics and properties of the composite coatings and the basic formation mechanism of the coatings were also discussed. The results indicate that the composite coatings are relatively dense and uniform in thickness, and predominantly composed of MgF₂, tetragonal ZrO₂ (t-ZrO₂) and monoclinic ZrO₂ (m-ZrO₂). The composite coatings exhibit a gradient distribution in phase component from the surface to the inner part. It is found that the applied voltage plays an important role in the characteristics and properties of the composite coatings. With the increase of the applied voltage, the thickness and the t-ZrO₂ content of the composite coatings increase, while the m-ZrO₂ content decreases and no significant variation is observed in the MgF₂ content. Moreover, the surface microhardness and bond strength of the coatings increases with the applied voltage increasing. The microhardness values display a gradient distribution in the cross sections of the coatings, and the maximum microhardness value and its corresponding position in the cross sections are related to the applied voltage. In addition, the corrosion resistances of the composite coatings on magnesium surface are obviously superior to the magnesium substrate in the NaCl solutions, and the effect is more remarkable at higher voltage.