Comparison of dehydriding kinetics between pure LaNi5 and its substituted systems

The kinetic mechanisms of dehydriding reaction in La_0.8M_0.2Ni₅ and LaNi_4.5T_0.5 were comparatively investigated by the Chou model and the first order model, and the former was superior to the latter from the comparison of theoretical calculated results and experimental data. According to the characteristic time (t_c) in the Chou model, substituting La (t_c = 71.36 s) with Ce (t_c = 35.64 s), Nd (t_c = 30.82 s) and Pr (t_c = 28.86 s) increased the dehydriding reaction rate, but partial substitution of Ni (t_c = 71.36 s) with Co (t_c = 102.29 s), Fe (t_c = 116.70 s) and Cu (t_c = 120.62 s) decreased the hydrogen desorption reaction rate. The Chou model was also used to discuss the effect of different amount of Ni substituted with Fe and Co. The dehydriding reaction rates of La(Ni_1−xFe_x)₅ increased with x leveling from 0 to 0.20 but decreased with x increasing from 0.20 to 0.30, while that of LaNi_5−yCo_y decreased with increasing the amount of Co from 0 to 3.00. In addition, the Chou model was successfully applied to predicting the kinetic properties of LaNi_4.8Sn_0.2 at 40 °C and 60 °C, which exhibited an excellent agreement with the experimental data.     

Analysis of controlled-mechanism of grain growth in undercooled Fe-Cu alloy

An analysis of controlled-mechanism of grain growth in the undercooled Fe-4 at.% Cu immiscible alloy was presented. Grain growth behavior of the single-phase supersaturated granular grains prepared in Fe-Cu immiscible alloy melt was investigated by performing isothermal annealings at 500-800 °C. The thermo-kinetic model [Chen et al., Acta Mater. 57 (2009) 1466] applicable for nano-scale materials was extended to the system of micro-scale undercooled Fe-4 at.% Cu alloy. In comparison of pure kinetic model, pure thermodynamic model and the extended thermo-kinetic model, two characteristic annealing time (t₁ and t₂) were determined. The controlled-mechanism of grain growth in undercooled Fe-Cu alloy was proposed, including a mainly kinetic-controlled process (t ≤ t₁), a transition from kinetic-mechanism to thermodynamic-mechanism (t₁ < t < t₂) and purely thermodynamic-controlled process (t ≥ t₂).     

Tribological behaviour and residual stress of electrodeposited Ni/Cu multilayer films on stainless steel substrate

In the present study, [Ni (4.5 nm)/Cu (t_Cu = 2, 4 and 8 nm)] multilayers were pulse electrodeposited on stainless steel (AISI SS 304) substrate from sulphate based single bath technique. X-ray diffraction (XRD) was used to investigate the structure and stress of the Ni/Cu multilayer. The results from XRD analysis indicated that the deposited multilayers had a preferred crystal orientation of [111] and presence of satellite reflection suggested the formation of superlattice. The stress level within the deposited multilayers was found to be sensitive to the sublayer thickness. Sliding wear behaviour of electrodeposited Ni/Cu multilayer films has been investigated against a tungsten carbide (WC) ball as the counter body and compared with that of the constituents, Cu and Ni coatings. The wear tests were carried out by using a reciprocating ball-on-flat geometry at translation frequencies of 5 and 10 Hz, slip amplitude of 1 mm and at five different loads of 3, 5, 7, 9 and 11 N. Friction force was recorded on-line during the tests. At the end of the tests, the wear scars were examined by laser surface profilometry and scanning electron microscopy (SEM). Friction coefficient was found to be dependent on load and Cu layer thickness (t_Cu) and the values for multilayers were border between Ni and Cu. Among multilayers, sample with minimum t_Cu has shown the lowest friction coefficient and wear rate. With increasing t_Cu, the wear mechanism changes from pure abrasive wear at t_Cu = 2 nm, to particle entrapment at t_Cu = 4 nm to particle embedding at t_Cu = 8 nm. Detailed investigation of the wear scar morphology as well as wear rate measurement revealed that at low loads, (H/E) ratio and residual stress governed the wear rate and the principle wear mode was abrasive cutting. At intermediate loads, the role of residual stress became insignificant while wear was governed by (H/E) ratio and plastic deformation. However, at higher loads, plastic deformation played the major role.     

Effect of Ta seed layer on crystalline structure and magnetic properties in an exchange-biased Co/IrMn system

Ta-seeded and un-seeded layers of a top-configuration Co/IrMn system were deposited onto glass substrate by DC sputtering. Three sets of deposition conditions for Co(50 Å)/IrMn(t_IrMn Å) and Co(t_Co Å)/IrMn(90 Å), where t_IrMn = 15, 30, 60, 90, 110, and 150 Å, and t_Co = 15, 25, 50, 75, 100, 125, and 150  Å, were: condition (a) substrate temperature (T_s) was kept at room temperature (RT). Condition (b) T_s set to RT, with in-plane magnetic field, H = 500 Oe. In condition (c), condition (b) was followed by post-deposition annealing in the magnetic field at T_A = 250 °C for 1 h, then field cooled to RT. X-ray diffraction (XRD) patterns and grazing incidence scans revealed maximum IrMn (1 1 1) texture to occur for post-deposition annealed Ta seed layer samples. The IrMn (1 1 1) texture-effect significantly influences magnetic properties, including exchange-biasing field (H_ex), interfacial energy (J_k), and coercivity (H_c). The Ta seed layer also significantly influences magnetic properties. Adding a Ta seed layer to the Co/IrMn system increases H_ex, because of the IrMn (1 1 1) texture. For Ta-seeded Co/IrMn under condition (c), H_ex tended to saturate for t_IrMn ≥ 90 Å. Under conditions (a) and (b), H_ex decreased with increasing t_IrMn for t_IrMn ≥ 90 Å. H_ex values for all un-seeded Co/IrMn systems increased with t_IrMn. J_k versus t_IrMn plot is proportional only to H_ex in the Ta-seeded and un-seeded layers of a top-configuration Co/IrMn system, due to the interfacial energy formula, t_Co is fixed, and saturation magnetization (M_s) of the Co layer is constant. Results for the Ta-seeded system showed a strong relationship between H_c and t_IrMn, due to coupling-decoupling interactions between Co spin, and IrMn layers close to the Co/IrMn interface. The H_ex versus t_Co result shows that the H_ex is proportional to (1/t_Co). The H_ex values with the Ta seed layer are almost slightly larger than those without a Ta seed-layer. The dependence of J_k on t_Co is similar to the trend in M_s on t_Co, J_k tends to saturate slowly as t_Co increases. Surface pinning occurred in all systems, revealing an inverse relation between H_c and t_Co. Removing the Ta seed-layer weakens IrMn (1 1 1) texturing, reducing H_ex. The maximum observed H_ex and J_k values were 205 Oe and 0.11 erg/cm², respectively.     

Analysis of grain growth process in melt spun Fe-B alloys under the initial saturated grain boundary segregation condition

A grain growth process in the melt spun low-solid-solubility Fe-B alloys was analyzed under the initial saturated grain boundary (GB) segregation condition. Applying melt spinning technique, single-phase supersaturated nanograins were prepared. Grain growth behavior of the single-phase supersaturated nanograins was investigated by performing isothermal annealing at 700 °C. Combined with the effect of GB segregation on the initial GB excess amount, the thermo-kinetic model [Chen et al., Acta Mater. 57 (2009) 1466] was extended to describe the initial GB segregation condition of nanoscale Fe-B alloys. In comparison of pure kinetic model, pure thermodynamic model and the extended thermo-kinetic model, an initial saturated GB segregation condition was determined. The controlled-mechanism of grain growth under initial saturated GB segregation condition was proposed using two characteristic annealing times (t₁ and t₂), which included a mainly kinetic-controlled process (t ≤ t₁), a transition from kinetic-mechanism to thermodynamic-mechanism (t₁ < t < t₂) and pure thermodynamic-controlled process (t ≥ t₂).     

Influence of pressure and surface roughness on the heat transfer efficiency during water spray quenching of 6082 aluminum alloy

The heat flux (q) and heat transfer coefficient (h) at the interface between hot aluminum surface and spray water were determined by using an inverse heat conduction method. Good agreements between numerically calculated temperatures with the inverse identified h and experimentally measurements demonstrate that the method is valid for solving the q and h of spray quenching process. The estimated heat flux consists of three main stages of transition boiling, nucleate boiling and single-phase cooling. The results show that both the heat flux and heat transfer coefficient increase with the increasing of spray pressure. When the surface temperature is lower than 170 °C, the q, h and the maximum heat transfer coefficient (h_max) decrease and then increase as surface roughness increases. However, when the surface temperature is higher than 170 °C, the influence of surface is insignificant. This phenomenon may be attributed to the variation of nucleation site density with surface roughness.     

Precise control of multilayered structures of Nb-O-N thin films by the use of reactive gas pulsing process in DC magnetron sputtering

Multilayered niobium oxynitride films were deposited onto (100) Si using DC magnetron sputtering with a reactive gas pulsing process. The argon and nitrogen flows were kept constant during sputtering of a pure niobium target and the oxygen flow was pulsed during deposition. Pulse durations of T = 10, 40 and 100 s and duty cycles α = t_ON / T of 0.3, 0.6 and 0.9 were chosen (t_ON = injection time of high oxygen flow). A mounting triangle was used as the pulse shape for the oxygen injection.During thin film deposition the cathode voltage, U_cath, the O₂ and N₂ partial pressures, p(O₂) and p(N₂), were recorded. A delay of both parameters (U_cath, p(O₂)) was observed after each pulse, for the return to the values during t_OFF = T − t_ON (off-time of oxygen injection with high flow).High resolution scanning electron microscopy revealed a multilayered structure for coatings deposited with T = 40 and 100 s. Transmission electron microscopy was used to verify that also the coatings with T = 10 s possess a multilayered structure with a period of λ = 10 nm. Despite this low period small crystallites (< 7 nm) were present in these layers. The indentation hardness and the Youngs modulus were in the range of 8.3-16.5 GPa and 154-180 GPa, respectively.     

Dependence of magnetic properties on the film thickness and Pt atomic fraction of post-annealed Fe1−xPtx-C granular films on MgO(1 0 0) and SiO2/Si(1 0 0) substrates

The Fe_1−xPt_x-C granular films with different Pt atomic fractions (0.09 ≤ x ≤ 0.52) and film thicknesses (5 nm ≤ t ≤ 100 nm) were deposited on MgO(1 0 0) and SiO₂/Si(1 0 0) substrates by facing-target sputtering and post-annealing. With the increasing x, the ordered L1₀ FePt grains form. All of the films are ferromagnetic, and the easy axis is in the film plane. With the decrease of t, the films turn from hard ferromagnetic to soft ferromagnetic. The maximum coercivity of the 100-nm thick Fe_1−xPt_x-C granular films measured at a 10-kOe field is 3.7 kOe at x = 0.48. The coercivity of the Fe_0.56Pt_0.44-C granular films increases, and the magnetization measured at a 10-kOe field decreases with the increasing t. The reversal mechanism of the 100-nm thick Fe_1−xPt_x-C granular films turns from the domain wall motion to the Stoner-Wohlfarth rotation mode as x increases. However, the reversal mechanism of the Fe₅₆Pt₄₄-C granular films with different t approaches the Stoner-Wohlfarth rotation mode, and is film-thickness independent.     

A study of the film formation kinetics on zinc in different acidic corrosion inhibitor solutions by quartz crystal microbalance

Chromates conversion coatings provide very effective corrosion protection for many metals. However, the high toxicity of chromate leads to an increasing interest in using non-toxic alternatives such as molybdates, silicates, rare earth metal ions and etc. In this work, quartz crystal microbalance (QCM) was applied as an in-situ technique to follow the film formation process on zinc (plated on gold) in acidic solutions containing an inorganic inhibitor, i.e. potassium chromate, sodium silicate, sodium molybdate or cerium nitrate. Using an equation derived in this work, the interfacial mass change during the film formation process under different conditions was calculated, indicating three different film formation mechanisms. In the presence of K₂CrO₄ or Na₂SiO₃, the film growth follows a mix-parabolic law, showing a process controlled by both ion diffusion and surface reaction. The apparent kinetic equations are 0.4t = −17.4 + 20Δm_f + (Δm_f)² and 0.1t = 19.0 + 8.4Δm_f + 10(Δm_f)² respectively (t and Δm are in seconds and μg/cm²). In solutions containing Na₂MoO₄, a logarithmic law of Δm_f = −24.7 + 6.6 ln t was observed. Changing the inhibitor to Ce(NO₃)₃, the film growth was found to obey an asymptote law that could be fit into the equation of Δm_f = 55.1(1 − exp(−2.6 × 10⁻³t)).     

Ferroelectric relaxor behavior and dielectric spectroscopic study of 0.99(Bi0.5Na0.5TiO3)-0.01(SrNb2O6) solid solution

0.99(Bi_0.5Na_0.5TiO₃)-0.01(SrNb₂O₆) was prepared by simple solid state reaction route. Material stabilized in rhombohedral perovskite phase with lattice constants a = 3.9060 Å, α = 89.86° and a_h = 5.4852 Å, c_h = 6.7335 Å for hexagonal unit cells. Density of material was found 5.52 g_m/cm³ (92.9% of theoretical one) in the sample sintered at 950 °C. The temperature dependent dielectric constant exhibits a broad peak at 538 K (?_m = 2270) at 1 kHz that shows frequency dependent shifts toward higher temperature - typical relaxor behavior. Modified Curie-Weiss law was used to fit the dielectric data that exhibits almost complete diffuse phase transition characteristics. The dielectric relaxation obeys the Vogel-Fulcher relationship with the freezing temperature 412.4 K. Significant dielectric dispersion is observed in low frequency regime in both components of dielectric response and a small dielectric relaxation peak is observed. Cole-Cole plots indicate polydispersive nature of the dielectric relaxation; the relaxation distribution increases with increase in temperature.     

Evaluation of metastable pitting on titanium by charge integration of current transients

The metastable pitting of titanium has been studied under potentiostatic control in solutions containing chloride ions. An approach based on the charge integration of current transients was proposed for a quantitative determination of metastable pitting. A pit density (d_mpit) was defined as the number of metastable pits per unit area per unit time (cm⁻² h⁻¹) with a typical size, instead of a size distribution. The calculated d_mpit of titanium at 0.5 V_SCE in 0.6 M NaCl was about 1.0 × 10³ cm⁻² h⁻¹ with a typical radius of 0.12 μm. An exponential potential dependence of d_mpit was obtained through the integration approach.     

Nanoindentation characteristics of Zr69.5Al7.5 − xGaxCu12Ni11 glasses and their nanocomposites

This work deals with the indentation behavior of Zr_69.5Al_7.5 − xGa_xCu₁₂Ni₁₁ (x = 0, 1.5, 7.5 at.%) alloys. A comparison between their nanohardness and reduced elastic modulus values of the as-synthesized glassy phase with their nanocomposites has been made. The indentation characteristics of a novel Ga substituted glass composition corresponding to x = 7.5 have shown significant improvement in regard to hardness and elastic modulus. The evidence of pile up has been observed in case of as-synthesized glassy ribbons. The load (P) versus depth (h) curves for as-synthesized melt-spun ribbons displayed the presence of displacement burst, which are known as pop-ins. The amount of energy per unit volume required for the shear band formation in glassy state has been estimated based on the pop-ins observed in P-h curve. This seems to decrease with Ga addition. Based on transmission electron microscopic observations of indented glassy specimen, the possibility of nanocrystallization has been ruled out.     

Prevention of passive film breakdown and corrosion of iron in 0.1 M KClO4 with and without Cl by covering with an ultrathin two-dimensional polymer coating and healing treatment in 0.1 M NaNO3

A two-dimensional polymer coating, the self-assembled monolayer of 16-hydroxy hexadecanoate ion HO(CH₂)₁₅ modified with 1,2-bis(triethoxysilyl)ethane (C₂H₅O)₃Si(CH₂)₂Si(OC₂H₅)₃ and octadecyltriethoxysilane C₁₈H₃₇Si(OC₂H₅)₃ was prepared on the passivated iron electrode and further, the passive film was healed by additional treatment in 0.1 M NaNO₃. This electrode was immersed in oxygenated 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ to 1 × 10⁻² M of Cl⁻. Protection of passive film against breakdown by covering the electrode with the polymer coating was examined by monitoring the open-circuit potential during immersion in the solutions for many hours to determine the time for passive film breakdown, t_bd. Repeated polarization measurements were carried out during immersion in these solutions for obtaining the protective efficiency, P. The t_bd value of the passivated, polymer-coated and healed electrode in 0.1 M KClO₄ solutions with and without Cl⁻ increased with a decrease in the concentration of Cl⁻. No breakdown occurred on the electrode during immersion in 0.1 M KClO₄ solutions with and without 1 × 10⁻⁴ of Cl⁻ for 360 h. The P values were extremely high, more than 99.9% before t_bd, indicating complete protection of iron from corrosion. The effect of healing treatment in 0.1 M NaNO₃ on passive film breakdown was investigated by electron-probe microanalysis.     

Extruded tellurite glass optical fiber preforms

The extrusion behavior of tellurite glass in the supercooled liquid region was investigated. Good extrusion formability was observed under low strain rates at various temperatures in the glass transformation region investigated. Tube and holey fiber (HF) preforms were fabricated from tellurite glass billets using a laboratory press. In particular, the results for three-spoke HF design and round tube preforms with composition 75TeO₂·20ZnO·5Na₂O (TZN) are presented. The extruded preforms with precise geometrical features, an excellent surface quality and no crystallization were achieved in the temperatures range from 344 to 360 °C and at ram speeds ranging from 0.002 to 0.01 mm/s. Discrete shear bands were observed in the preforms, increasing in number and/or becoming better defined with increasing load and ram speed. Fewer shear bands were present when increasing the extrusion temperature from 344 to 360 °C. Thus, subsequent extrudates were successfully fabricated free of shear bands, providing good optical homogeneity that yielded solid and holey fibers that could provide much improved optical performance.     

Comparison of extrusion strains produced by cosine and conical dies

Visioplastic analysis is used to compare strain fields produced in cylindrical aluminum billets extruded at elevated temperature through axially symmetric dies that have either a cosine or a conical profile. The visioplastic method consists of computing strain rates from changes experienced in a flow function as a billet passes through the extrusion die. The flow function is constructed using a grid that is stamped on an axial plane of the billet before extrusion. After the partially extruded billet is removed from the die numerical methods are used to determine the strain rates from the deformed grid. The state of strain over the extrusion region is computed using transformation and then integration of the strain rates. Results show that, unlike the conical die, the cosine die does not produce strains of reversed sign in the die entry region. The consequent benefits of using cosine dies for extrusion of powder metals are discussed.     

Competition between interfacial and interlayer exchange couplings in Co/Cr2O3/Fe trilayers

The temperature dependence of competition between interlayer and interfacial couplings is observed at different temperatures in Co (3 nm)/Cr₂O₃ (t)/Fe (10 nm) trilayers with t = 3 nm, 6 nm, 15 nm and 25 nm, respectively. The interlayer coupling enhances and the interfacial coupling weakens with increasing temperature. The balanceable temperature between interfacial and interlayer couplings shifts to low temperatures with increasing spacer thickness. Furthermore, the competition between interfacial and interlayer couplings greatly affects the magnetotransport properties of the trilayers. The negative magnetoresistance and the minimum resistance corresponding to balanceable temperature are found in trilayers.     

Moderate temperature and high-speed synthesis of α-Al2O3 films by laser chemical vapor deposition using Nd:YAG laser

Al₂O₃ films were prepared at deposition temperatures (T_dep) from 980 to 1230 K by laser chemical vapor deposition (LCVD) using the continuous wave of a Nd:YAG laser with laser power (P_L) up to 260 W. γ-Al₂O₃ films were obtained at T_dep < 1100 K, whereas α-Al₂O₃ films were obtained at T_dep > 1100 K. γ-Al₂O₃ films were morphologically characterized by a cone-like structure, while α-Al₂O₃ films had hexagonal faceted grains. The highest deposition rate (R_dep) of γ-Al₂O₃ film was 570 μm h^− 1, while that of α-Al₂O₃ film was 250 μm h^− 1. α-Al₂O₃ films in a single phase were obtained at 170 K lower in T_dep and 100 times higher in R_dep than those by conventional thermal CVD.     

Structure and electrical properties of MnO2-doped Sr2−xCaxNaNb5O15 lead-free piezoelectric ceramics

Lead-free piezoelectric ceramics Sr_2−xCa_xNaNb₅O₁₅ + y wt% MnO₂have been prepared by the conventional solid state reaction method. Our results reveal that Ca²⁺and Mn ions have entered into the Sr₂NaNb₅O₁₅ lattices to form a solid solution with tungsten-bronze structure. The substitution of Ca²⁺ induces a decrease in piezoelectric coefficient d₃₃, electromechanical coupling factors k_p and k_t, while, the addition of Mn ions decreases the sintering temperature and effectively promotes the densification of the ceramics. The effect of substitution of Ca²⁺and Mn ions on the structure, electrical properties and diffused phase changing were investigated systematically. For the ceramic with x = 0.05 and y = 0.5, the piezoelectric, dielectric and ferroelectric properties become optimum, giving a piezoelectric coefficient d₃₃ = 190 pC/N, electromechanical coupling factors k_p = 13.4% and k_t = 36.5%, ?_r = 2123, loss tangent tan δ = 0.038, remanent polarization P_r = 4.76 μC/cm², coercive field E_c = 12.68 kV/cm, and Curie temperature T_c = 260 °C.     

Physical modeling of equal channel angular pressing using plasticine

We report here the results of our physical modeling study of the equal channel angular pressing process using two-colour constituent plasticine workpieces in a metallic die. The workpieces, usually called billets, are made up of discs as well as spherical balls. They are deformed repeatedly with and without changing the orientation between successive passes. Both square and round dies with inner channel intersection angle of 90° are used. The flow patterns are revealed by sectioning the billet after a requisite number of passes. Thorough mixing of the two constituents with a drastic reduction in the section size of each constituent of the plasticine workpiece was observed after 15 passes. The initial shape of the constituents of the billet does not affect the final flow pattern of the microstructure. Material accumulation of the two colour constituents of plasticine was observed in some regions of the billet along the central region at a low and intermediate number of passes.