Corrosion and corrosion fatigue of AISI 420C (X46Cr13) at 60 °C in CO2-saturated artificial geothermal brine

The lifetime reduction of cyclically loaded AISI 420C (X46Cr13, 1.4034) constantly exposed to highly corrosive CO₂-saturated hot thermal water is demonstrated in in situ-laboratory experiments (60 °C, brine: Stuttgart Aquifer, flowing CO₂: 30 L/h). S–N plots, micrographic-, phase-, fractographic- and surface analysis were applied to obtain sustainable information on the corrosion and corrosion fatigue behavior. Maximum number of cycles (here 12.5 × 10⁶ cycles to failure) is reached at σ_a = 173 MPa. Hydroxide and siderite layers were found on pits and crack surfaces. No typical fatigue limit exists and pit corrosion prior to crack initiation may be identified as failure cause.     

Square net distortion engineering in the ternary variants of titanium antimonide,Ti2−δMδSb (M = Zr,Hf)

The binary antimonide Ti₂Sb crystallizes in a unique structure type, which may be considered as a distorted variant of the La₂Sb structure type. The new ternary variants, Ti_2−δM_δSb (M = Zr, Hf) with δ < 0.85, were prepared by arc melting the elements in stoichiometric ratios. The ternaries crystallize in the body centered tetragonal space group I4/mmm, with lattice dimensions varying with δ and M, e.g. a = 3.977(1) Å and c = 15.011(2) Å for Ti_1.5Zr_0.5Sb (Z = 4). Single crystal structure investigations as well as powder X-ray profile refinements employing the Rietveld method and pair distribution function technique revealed, that with increasing δ the distortions lessen and finally disappear, as was predicted based on the Kleinke–Harbrecht structure map.     

Effects of stress ratio on fatigue crack propagation properties of submicron-thick free-standing copper films

The dominant mechanics and mechanisms of fatigue crack propagation in ca. 500 nm thick free-standing copper films were evaluated at the submicron level using fatigue crack propagation experiments at three stress ratios, R = 0.1, 0.5 and 0.8. Fatigue cracking initiated at the notch root and propagated stably under cyclic loading. The fatigue crack propagation rate (da/dN) vs. stress intensity factor range (ΔK) relation was dependent on the stress ratio R;da/dN, increases with increasing R. Plots of da/dN vs. the maximum stress intensity factor (K_max) exhibited coincident features in the high-K_max region (K_max ? 4.5 MPa m^1/2) irrespective of R, indicating that K_max is the dominant factor in fatigue crack propagation. In this region, the fatigue crack propagated in tensile fracture mode irrespective of the R value. The region ahead of the fatigue crack tip is plastically stretched by tensile deformation, causing necking deformation in the thickness direction and consequent chisel-point fracture. In contrast, in the low-K_max region (K_max < 4.5 MPa m^1/2), the da/dN vs. K_max function assumes higher values with decreasing R; in this region, the fracture mechanism depends on R. At the higher R value (R = 0.8), the fatigue crack propagates in the tensile fracture mode similar to that in the high-K_max region. On the other hand, at the lower R values (R = 0.1 and 0.5), a characteristic mechanism of fatigue crack propagation appears: within several grains, intrusions/extrusions form ahead of the crack tip along the Σ3 twin boundaries, and the fatigue crack propagates preferentially through the intrusions/extrusions.     

Preparation of Fe2B boride coating on low-carbon steel surfaces and its evaluation of hardness and corrosion resistance

Fe₂B coating was prepared on low-carbon steel by surface alloying. A series of experiments were carried out to examine some surface properties of boride coating. The surface heat treatment of coated low-carbon steel was performed at 700 °C, 800 °C and 900 °C for 2 h, 4 h, 6 h and 8 h under hydrogen atmosphere. The boride coating was revealed by XRD analysis and the microstructure of the boride coating was analyzed by scanning electron microscopy (SEM). Depending on the temperature and time of the process, the hardness of the borided low-carbon steel ranged from 99 to 1100 HV. The hardness showed a maximum (about 1100 HV) at 900 °C for 8 h. The corrosion resistance of the borided samples was evaluated by the Tafel polarization and electrochemical impedance spectroscopy (EIS). Shift in the corrosion potential (E_corr) towards the noble direction was observed, together with decrease in the corrosion current density (I_corr), increase in the charge transfer resistance (R_ct) and decrease in the capacitance (C_c), which indicated an improvement in corrosion resistance with increasing temperature and time of the treatment.     

Synthesis,characterization and evaluation of cation-ordered LnBaCo2O5+δ as materials of oxygen permeation membranes and cathodes of SOFCs

LnBaCo₂O_5+δ (Ln = La, Pr, Nd, Sm, Gd, and Y) was synthesized via an EDTA–citrate complexing process. The particular Ln³⁺ dopant had a significant effect on the oxide’s phase structure/stability, oxygen content, electrical conductivity, oxygen permeability, and cathode performance. Stable, cation-ordered oxides with layered lattice structures were obtained with medium-sized Ln³⁺ ions over a wide range of oxygen partial pressures, a property essential for applications as oxygen separation membranes and solid oxide fuel cell (SOFC) cathodes. PrBaCo₂O_5+δ demonstrated the highest oxygen flux (∼5.09 × 10⁻⁷ mol cm⁻² s⁻¹ at 900 °C), but this value was still significantly lower than that of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3−δ perovskite (∼3.1 × 10⁻⁶ mol cm⁻² s⁻¹ at 900 °C). The observed difference was attributed to the much longer diffusion distance through a polycrystalline membrane with a layered lattice structure than through cubic perovskite because bulk diffusion was the rate-limiting step of permeation. An area-specific resistance of ∼0.213 Ω cm² was achieved at 600 °C with a PrBaCo₂O_5+δ cathode, suggesting that the layer-structured oxides were promising alternatives to ceramic membranes for SOFC cathodes.     

On the electronic transport properties of pyrrolo[1,2-a][1,10]phenanthroline derivatives in thin films

The temperature dependences of electrical conductivity, σ, and Seebeck coefficient, S, for six new synthesized pyrrolo[1,2-a][1,10]phenanthroline compounds, have been investigated. Thin film samples (d = 0.05–0.66 μm) deposited by an immersion method (with dimethylformamide as solvent) onto glass were used.The crystalline structure of as-prepared organic films was investigated by XRD. The sample surface was examined by means of AFM and optical microscopy techniques.The ln σ = f(10³/T) and S = f(10³/T) experimental curves are quite typical for polycrystalline semiconducting materials. The examined organic compounds show a p-type electrical conduction. The activation energy of electrical conduction ranged between 1.42 and 2.04 eV, while the ratio of charge carrier mobilities was in the range 0.76–0.90.The study of optical absorption evidenced direct bandgaps ranged between 4.06 and 4.11 eV, as well bandgaps of 2.69–3.58 eV for amorphous phases.Some relationships between materials parameters and molecular structure of the compounds are established. The model based on band gap representation is suitable for the explanation of charge transport in the studied compounds.     

A study on mechanochemical behavior of MoO3–Mg–C to synthesize molybdenum carbide

The influence of Mg value in the MoO₃–Mg–C mixture on the molybdenum carbide formation and the mechanism of reactions during mechanochemical process were investigated. In keeping with this aim, magnesium and carbon contents of the mixture were changed according to the following reaction: 2MoO₃ + (6 − x) Mg + (1 + x) C = (6 − x) MgO + Mo₂C + x CO. The value of x varied from 0 to 6. Differential thermal analysis (DTA) results for sample with stoichiometric ratio (x = 0) revealed that in the early stage, carbon reduced the MoO₃ to MoO₂ and subsequently highly exothermic magnesiothermic MoO₂ reduction occurred after magnesium melting. Also, it was indicated that the exothermic reaction temperature shifted to before magnesium melting in the 11 h-milled sample (x = 0) and all the exothermic reactions happened, simultaneously. According to the experimental findings, molybdenum carbide (Mo₂C) was synthesized in the mixture powder with stoichiometric ratio (x = 0) after 12 h milling process and the type of reactions was mechanically induced self-sustaining reaction (MSR). However, at lower Mg content in the MoO₃–Mg–C mixture (0 < x ≤ 2), the magnesiothermic reduction occurred in MSR mode and activated the carbothermal reaction. Further decrease in Mg value (2 < x ≤ 3) resulted in MSR mode magnesiothermic reaction and gradual carbothermal reduction. In samples with lower magnesium contents, partial molybdenum oxide reduction proceeded through a gradual mode magnesiothermic reaction.     

Modeling fluid flow in three-dimensional single crystal dendritic structures

Convection during directional solidification can cause defects such as freckles and misoriented grains. To gain a better understanding of conditions associated with the onset of convective instabilities, flow was investigated using three-dimensional (3D) computational fluid dynamics simulations in an experimentally obtained dendritic network. A serial-sectioned, 3D data set of directionally solidified nickel-base superalloy measuring 2.3 × 2.3 × 1.5 mm was used to determine the permeability for flow parallel and normal to the solidification direction as a function of solid fraction (f_S). Anisotropy of permeability varies significantly from 0.4 < f_S < 0.6. High flow velocity channels exhibit spacings commensurate with primary dendrite arms at the base of the mushy zone but rapidly increase by a factor of three to four towards dendrite tips. Permeability is strongly dependent on interfacial surface area, which reaches a maximum at f_S = 0.65. Results from the 3D simulation are also compared with empirical permeability models, and the microstructural origins of departures from these models are discussed.     

Structural characterization and oxygen nonstoichiometry of ceria-zirconia (Ce1−xZrxO2−δ) solid solutions

The oxygen nonstoichiometry and crystalline structure of ceria-zirconia Ce_1?xZr_xO_2?δ (CZO) (x = 0.05, 0.1, 0.2, 0.5, and 0.8) solid solutions, commercially used as oxygen storage materials, have been examined using thermogravimetry, X-ray diffraction, and Raman spectroscopy. In this study detailed data describing oxygen vacancy concentrations, obtained at intermediate to high pO₂, are interpreted with the aid of point defect equilibria relationships. For cubic CZO (x ? 0.2), the ease of reducibility dramatically increased with increasing Zr content, as reflected by an ultimate >40% decrease in reduction enthalpy, with a corresponding shift in onset of reduction to higher pO₂. The impact of pre-existing oxygen vacancies on the larger reduction enthalpy found for Y doped CZO, as compared with this study, is discussed, as is evidence that Zr increases the electron migration energy in ceria by 50%. The reducibility of tetragonal CZO (x > 0.2) was found to increase following redox cycling. This enhanced reducibility is believed to be related to ordering and is partially negated by a high temperature (1000 °C) heat treatment.     

Estimation of residual corrosion rates of steel under cathodic protection in soils via voltammetry

Steel coupons were buried in soil for 2 months under cathodic protection. Their residual corrosion rates were deduced from voltammetry and weight loss measurements. In aerated soils, the current density due to O₂ reduction, j_K,O2, was modelled with a mixed activation–diffusion controlled kinetic. The anodic part j_A of the current density j, computed as j_A = j − j_K,O2, obeyed Tafel law. Its extrapolation to the protection potential gave a corrosion rate (∼7 μm yr⁻¹) consistent with that obtained from weight loss measurements. With a deficient protection, corrosion rates remained at ∼80 μm yr⁻¹, a value given by both methods.     

Characterization and dielectric behavior of V2O5-doped 0.9Mg0.95Co0.05TiO3–0.1Ca0.6La0.8/3TiO3 ceramic system at microwave frequency

The microwave dielectric properties and the microstructures of Mg_0.95Co_0.05TiO₃–Ca_0.6La_0.8/3TiO₃ ceramics, prepared by a mixed oxide route, have been investigated. With small amount of V₂O₅ additions, the sintering temperatures of 0.9Mg_0.95Co_0.05TiO₃–0.1Ca_0.6La_0.8/3TiO₃ ceramics can be lowered to 1250 °C. The microwave dielectric properties are found strongly correlated with the sintering temperature as well as the amount of V₂O₅ additions. The Q × f value of 0.9Mg_0.95Co_0.05TiO₃–0.1Ca_0.6La_0.8/3TiO₃ increased with increasing temperature to 1250 °C and decreased thereafter. The decrease in Q × f value was coincident with the abnormal grain growth. A maximum Q × f value of 58,000 (GHz) associated with a dielectric constant (?_r) of 21.7 and a temperature coefficient (τ_f) of ?10 ppm/°C, was achieved for 0.25 wt.% V₂O₅-doped samples at 1250 °C. Moreover, a cross-coupled compact hairpin filter with designed center frequency of 2.0 GHz is designed and fabricated using the proposed dielectric ceramic to study its performance. It also showed a substantial reduction in both insertion loss and size in comparison with other dielectrics FR4 and alumina.     

Spin-glass-like behaviour in the ternary U3Fe4+xAl12−x uranium–iron aluminide

The U₃Fe_4+xAl_12?x (0 < x < 0.5) intermetallic was prepared by arc melting, followed by annealing at 850 °C. This compound crystallizes in the hexagonal Gd₃Ru₄Al₁₂-type structure (e.g. P6₃/mmc), with room temperature parameters a = 8.7516(3) Å and c = 9.2653(4) Å for x = 0. The structure is characterized by planar layers of M3Al4 (M = Gd, U), containing M atoms in a triangular arrangement and forming a distorted Kagomé net. Magnetic measurements revealed a spin-glass-type behaviour with a freezing temperature, T_f = 7.9 K. The magnitude of the frequency shift of the freezing temperature is ≈0.03 and a Vogel–Fulcher law is followed with values typical for a spin-glass. ⁵⁷Fe Mössbauer data show that there is no freezing of the iron magnetic moments directions below T_f, indicating that the origin of the spin-glass-like behaviour is related to topological frustration of the uranium moments.     

Barium- and strontium-enriched (Ba0.5Sr0.5)1+xCo0.8Fe0.2O3−δ oxides as high-performance cathodes for intermediate-temperature solid-oxide fuel cells

(Ba_0.5Sr_0.5)_1+xCo_0.8Fe_0.2O_3−δ, or BSCF(1 + x), (0 ⩽ x ⩽ 0.3) oxides were synthesized and investigated as cathodes for intermediate-temperature solid-oxide fuel cells. The A-site cation excess in BSCF(1 + x) resulted in a lattice expansion and the creation of more active sites for oxygen reduction reaction due to the lowered valence states of the B-site ions and the increased oxygen vacancy concentration, which improved the oxygen adsorption process. On the other hand, the A-site excess could also result in higher resistances for oxygen adsorption (due to the formation of BaO and/or SrO impurities), and oxygen-ion transfer (by facilitating the solid-phase reaction between the cathode and the electrolyte). By taking all these factors into account, we found BSCF1.03 to be the optimal composition, which lead to a peak power density of 1026.2 ± 12.7 mW cm⁻² at 650 °C for a single cell.     

Swelling of poly(3-alkylthiophene) films exposed to solvent vapors and humidity: Evaluation of solubility parameters

White light interferometry was used to determine the swelling of poly(3-alkylthiophene)s (P3ATs), with different head-to-tail regioregularity, exposed to different volatile compounds (VCs): humidity, cyclohexanone, tetrahydrofuran and chloroform. Film expansion increases always from regioregular R-P3DDT, R-P3HT to regiorandom P3BT, P3DDT. Regular solution approach was used to determine Flory–Huggins interaction parameter between P3ATs and VCs. Solubility parameters δ_P ∼ 16.9 ± 0.8, 15.3 ± 0.4, 13.1 ± 0.3, and 12.5 ± 0.2 MPa^1/2 evaluated for P3DDT, P3BT, R-P3HT, and R-P3DDT, respectively, were confirmed by the values extrapolated from surface tension data. Evaluated δ_P values should allow an easier strategy for P3AT solution processing aimed at optimized film structure of P3AT polymers and their blends.     

Electro/magnetic shielding effectiveness of soft magnetic Fe80Nb6B14 amorphous alloy

Application of the Fe₈₀Nb₆B₁₄ amorphous alloy to electromagnetic shielding was examined in detail using different experimental techniques. For shields made of the optimized (annealing at 700 K/1 h) amorphous ribbons the shielding effectiveness b was measured versus frequency f and shield thickness h. It was shown that for h = 200 μm in the frequency range 2 MHz < f < 15 MHz (the near-zone, electric field) b decreases from 55 dB to 20 dB. In the frequency range 0.2 kHz < f < 10 kHz (the near-zone, magnetic field) b > 20 dB. The best shielding effectiveness, i.e. b > 100 dB was obtained for electromagnetic field in the frequency range 200 MHz < f < 1000 MHz (the far-zone).     

Electrochemical corrosion behaviors of straight WC–Co alloys: Exclusive variation in grain sizes and aggressive media

The electrochemical corrosion behaviors of straight WC–10Co cemented carbides with grain sizes of 1.2, 2.6, 6.1 and 8.2 μm, were comparatively investigated in the solutions of NaOH (pH = 13), Na₂SO₄ (pH = 7) and H₂SO₄ (pH = 1) respectively. To insure a sole variable of WC grain sizes, specific magnetic saturation values of the alloys are adjusted to be identical. The results show a good linear dependence for R_ct (charge transfer resistance) and I_corr (corrosion current density) against the grain sizes. A high sensitivity of the grain sizes to both R_ct and I_corr are identified in NaOH and H₂SO₄. In the solutions of NaOH and Na₂SO₄, the alloys with smaller WC grain sizes exhibit better corrosion resistances, while the alloys with larger WC grain sizes exhibit better corrosion resistances in H₂SO₄. Additionally, in terms of the corrosiveness, NaOH is the weakest and H₂SO₄ is the most aggressive for all the alloys. The corrosion mechanisms were discussed in light of the SEM surface observation, X-ray photoelectron spectroscope analysis and the electrical equivalent circuits for electrochemical impedance spectroscopy.     

Design and synthesis of a novel class of inhibitors for mild steel corrosion in acidic and carbon dioxide-saturated saline media

p-(9-(2-Methylisoxazolidin-5-yl)nonyloxy)benzaldehyde I, prepared using a cycloaddition protocol, was elaborated into its cinnamaldehyde derivative II which upon quarternization with propargyl chloride afforded III bearing an interesting blend of structural traits suitable for imparting inhibition of mild steel corrosion. Novel compounds I–III showed efficient inhibition against mild steel corrosion in CO₂–0.5 M NaCl (40 °C, 1 atm; 120 °C, 10 bar), 1, 4, 7.7 M HCl, and 0.5 M H₂SO₄ at 60 °C as determined by gravimetry and electrochemical methods. The presence of carbonaceous surface and nitrogen, as revealed by XPS study, indicated the formation of a film covering the metal surface, which imparted corrosion inhibition.     

Effects of La content on the glass transition and crystallization process of Al–Ni–La amorphous alloys

Effects of La content on the glass transition and crystallization process of Al_94−xNi₆La_x (x = 3–9) amorphous alloys were investigated by X-ray diffraction and differential scanning calorimeter. The results show that the thermal stability increases with increasing the La content. The crystallization changes from a two-stage process without glass transition at x = 3–6 to a three-stage one with obvious glass transition at x = 7–9. The first crystallization process results in precipitation of single fcc-Al at x = 3–5, fcc-Al plus metastable phase(s) at x = 6 and 7, and single metastable phase at x = 8 and 9. The first crystallization process at x = 4 and 5 is the growth of quenched-in nuclei, whereas that at x = 6, 7 and 9 is the diffusion-controlled growth with a decreasing, constant and increasing nucleation rate, respectively. The activation energy for the first crystallization process is larger in the eutectic reaction than that in the primary reaction, and is the highest when the number of the products is the most.     

Corrosion of ultra-high-purity Mg in 3.5% NaCl solution saturated with Mg(OH)2

Corrosion was evaluated for ultra-high-purity magnesium (Mg) immersed in 3.5% NaCl solution saturated with Mg(OH)₂. The intrinsic corrosion rate measured with weight loss, P_W = 0.25 ± 0.07 mm y⁻¹, was slightly smaller than that for high-purity Mg. Some specimens had somewhat higher corrosion rates attributed to localised corrosion. The average corrosion rate measured from hydrogen evolution, P_AH, was lower than that measured with weight loss, P_W, attributed to dissolution of some hydrogen in the Mg specimen. The amount of dissolution under electrochemical control was a small amount of the total dissolution. A new hydride dissolution mechanism is suggested.     

The fatigue behavior of I-phase containing as-cast Mg–Zn–Y–Zr alloy

The fatigue behavior of as-cast Mg–12%Zn–1.2%Y–0.4%Zr alloy has been investigated. The S–N curve showed that the fatigue strength at 10⁷ cycles was 45 MPa. Scanning electron microscopy observations on the surfaces of the failed and unfailed specimens (after up to 1 × 10⁷ cycles) suggested that the slip bands could act as preferential sites for non-propagating fatigue crack initiation, and the I-phase could effectively retard fatigue crack propagation (FCP). The macro fracture morphology clearly indicated that the overall fracture surface was composed of three regions, i.e. a fatigue crack initiation region (Region 1), a steady crack propagation region (Region 2) and a tearing region (Region 3). High-magnification fractographs showed that only porosities can act as the crack initiation sites for all specimens. Moreover, for specimens with fatigue lifetimes lower than 2 × 10⁵ cycles, the cracks mostly initiated at the subsurface or surface of the specimen. However, when the fatigue lifetime was equal to or higher than 2 × 10⁵ cycles, the fatigue crack initiation sites transferred to the interior of the specimen. The maximum stress intensity factors corresponding to the transition sites between Regions 1, 2 and 3 were 2 and 4.2 MPa m^1/2, respectively. When the maximum stress intensity factor K_max was lower than 4.2 MPa m^1/2, in the steady crack propagation region, due to the retarding effect of I-phase/α-Mg matrix interfaces, the fatigue cracks tended to pass the I-phase/α-Mg matrix eutectic pockets directly and propagated through the grain cells, resulting in the formation of many flat facets on the fracture surface. However, when the maximum stress intensity factor was higher than 4.2 MPa m^1/2, in the sudden failure region, the rigid bonding of I-phase/α-Mg matrix interfaces was destroyed and the cracks preferentially propagated along the interfaces, which resulted in the fracture surface being almost completely composed of cracked I-phase/α-Mg matrix eutectic pockets. Based on microstructural observation and the fracture characteristics of the two regions, it is suggested that with an increase in crack tip driving force, the FCP mode changes from transgranular propagation to intergranular propagation.