Search Results (13)

Nitrogen control in basic oxygen furnace (BOF) steelmaking is critical, as dissolved nitrogen concentrations exceeding 30–40 ppm detrimentally affect the mechanical properties and formability of low-carbon steel products; however, no prior study has applied a physics-informed machine learning model to nitrogen prediction at this process stage. A NitroPINN model was developed incorporating a multiplicative prediction structure that embeds Sievert’s law equilibrium, Wagner interaction coefficients, and Byrne–Belton surface blockage theory directly into the model. The model was trained and evaluated on 66 matched industrial heats from a top-blown 170-ton BOF converter, characterized by 16 physics-informed features, and benchmarked against ridge regression and a pure multilayer perceptron (MLP) under five-fold cross-validation. The NitroPINN achieved the lowest mean absolute error (MAE = 5.60 ppm) and mean absolute percentage error (MAPE = 27.2%) among the three models, whilst the learned equilibrium attainment factor η averaged 0.456 ± 0.028, consistent with sub-equilibrium nitrogen conditions imposed by intense CO flushing during oxygen blowing. All three models exhibited comparable overall accuracy, confirming that dataset size constitutes the principal performance bottleneck. The primary advantage of the NitroPINN lies in its physical interpretability, constraining predictions to metallurgically plausible ranges and providing a transparent decomposition into thermodynamic and kinetic contributions. Full article

Lotus-type porous metals, characterized by low densities, large surface areas, and directional properties, are contemporarily utilized as lightweight, catalytic, and energy-damping materials; heat sinks; etc. In this study, the effects of dimensionless working parameters on the morphology of lotus-type pores in metals during unidirectional solidification were extensively investigated via general algebraic expressions. The independent dimensionless parameters include metallurgical, transport, and geometrical parameters such as Sieverts’ law constant, a partition coefficient, the solidification rate, a mass transfer coefficient, the imposed mole fraction of a solute gas, the total pressure at the top free surface, hydrostatic pressure, a solute transport parameter, inter-pore spacing, and initial contact angle. This model accounts for transient gas pressure in the pore, affected by the solute transfer, gas, capillary, and hydrostatic pressures, and Sieverts’ laws at the bubble cap and top free surface. Solute transport across the cap accounts for solute convection at the cap and the amount of solute rejected by the solidification front into the pore. The shape of lotus-type pores can be described using a proposed fifth-degree polynomial approximation, which captures the major portions between the initial contact angle and the maximum radius at a contact angle of 90 degrees, obtained by conserving the total solute content in the system. The proposed polynomial approximation, along with its working parameters, offers profound insights into the formation and shape of lotus-type pores in metals. It systematically provides deep insights into mechanisms that may not be easily revealed with experimental studies. The prediction of a lotus-type pore shape is thus algebraically achieved in good agreement with the available experimental data and previous analytical results. Full article

The hydrogen/deuterium sorption properties of Ni₃₃Ti₃₉Nb₂₈ synthesized by the vacuum induction melting technique were measured between 400 and 495 °C for pressure lower than 3 bar. The Sieverts law is valid up to H(D)/M < 0.2 in its ideal form; the absolute values of the hydrogenation/deuteration enthalpy are ΔH(H₂) = 85 ± 5 kJ/mol and ΔH(D₂) = 84 ± 4 kJ/mol. From the kinetics of absorption, the diffusion coefficient was derived, and an Arrhenius dependence from the temperature was obtained, with E_a,d = 12 ± 1 kJ/mol for both hydrogen isotopes. The values of the alloy permeability, obtained by combining the solubility and the diffusion coefficient, were of the order of 10⁻⁹ mol m⁻¹ s⁻¹ Pa^−0.5, a value which is one order of magnitude lower than that of Ni₄₁Ti₄₂Nb₁₇, until now the best Ni-Ti-Nb alloy for hydrogen purification. In view of the simplicity of the technique here proposed to calculate the permeability, this method could be used for the preliminary screening of new alloys. Full article

Binary intermetallic compounds, such as FePd₃, attract interests due to their physical, magnetic and catalytic properties. For a better understanding of their hydrogenation properties, both ordered FePd₃ and disordered Fe_0.25Pd_0.75 are studied by several in situ methods, such as thermal analysis, X-ray powder diffraction and neutron powder diffraction, at moderate hydrogen pressures up to 8.0 MPa. FePd₃ absorbs small amounts of hydrogen at room temperature and follows Sieverts’ law of hydrogen solubility in metals. [Pd₆] octahedral voids are filled up to 4.7(9)% in a statistical manner at 8.00(2) MPa, yielding the hydride FePd₃H_0.047(9). This is accompanied by decreasing long-range order of Fe and Pd atoms (site occupancy factor of Fe at Wyckoff position 1a decreasing from 0.875(3) to 0.794(4)). This trend is also observed during heating, while the ordered magnetic moment decreases up to the Curie temperature of 495(8) K. The temperature dependences of the magnetic moments of iron atoms in FePd₃ under isobaric conditions (p(D₂) = 8.2(2) MPa) are consistent with a 3D Ising or Heisenberg model (critical parameter β = 0.28(5)). The atomic and magnetic order and hydrogen content of FePd₃ show a complex interplay. Full article

Thermal analysis methods have been used in many reports to determine the activation energy for hydride decomposition (dehydrogenation). In our preceding work, we showed that the dehydrogenation rate of Mg-5Ni samples obeyed the first-order law, and the Kissinger equation could thus be used to determine the activation energy. In the present work, we obtained the activation energy for dehydrogenation by applying data from a volumetric method to the Kissinger equation. The quantity of hydrogen released from hydrogenated Mg-5Ni samples and the temperature of the reactor were measured as a function of time at different heating rates (Φ) in a Sieverts-type volumetric apparatus. The values of dH_d/dt, the dehydrogenation rate, were calculated as time elapsed and the temperature (T_m) with the highest dH_d/dt was obtained. The values of dH_d/dT, the rate of increase in released hydrogen quantity (H_d) to temperature (T) increase, were calculated according to time, and the temperature (T_m) with the highest dH_d/dT was also obtained. In addition, the values of dT/dt, the rate of increase in temperature to time (t) increase, were calculated according to time, and the temperature (T_m) with the highest dH_d/dt was obtained. Φ and T_m were then applied to the Kissinger equation to determine the activation energy for dehydrogenation of Mg-5Ni samples. Full article

Pd-membranes are interesting in multiple ultra-pure hydrogen production processes, although they can suffer inhibition by certain species or abrasion under fluidization conditions in membrane reactors, thus requiring additional protective layers to ensure long and stable operation. The ability to incorporate intermediate and palladium films with enough adherence on both external and internal surfaces of tubular porous supports becomes crucial to minimize their complexity and cost. This study addresses the incorporation of CeO₂ and Pd films onto the internal side of PSS tubes for applications in which further protection could be required. The membranes so prepared, with a Pd-thickness around 12–15 μm, show an excellent mechanical resistance and similar performance to those prepared on the external surface. A good fit to Sieverts’ law with an H₂-permeance of 4.571 × 10⁻³ mol m⁻² s⁻¹ Pa^−0.5 at 400 °C, activation energy around 15.031 kJ mol⁻¹, and complete ideal perm-selectivity was observed. The permeate fluxes reached in H₂ mixtures with N₂, He, or CO₂ decreased with dilution and temperature due to the inherent concentration-polarization. The presence of CO in mixtures provoked a higher decrease because of a further inhibition effect. However, the original flux was completely recovered after feeding again with pure hydrogen, maintaining stable operation for at least 1000 h. Full article

We developed a method to determine the activation energy for hydride decomposition using a Sieverts-type apparatus and the Kissinger equation, not using thermal analysis methods. The quantity of hydrogen released from the sample and the temperature of the reactor were first measured as a function of time at different heating rates (Φ) in a Sieverts-type apparatus. The dehydriding rates were calculated according to time and the temperature T_m (at which the dehydriding rate was the highest). Φ and T_m were then applied to the Kissinger equation. The dehydriding rate of Mg-5Ni samples obeyed a first-order law, and the Kissinger equation could thus be used to determine the activation energy. On a heating rate of 3 K/min, the decomposition rate of hydride was the highest at 590.0 K. From a plot of ln (Φ/T_m²) versus 1/T_m, the obtained activation energy for hydride decomposition was 174 kJ/mole. Full article

The concept of liquid metal membranes for hydrogen separation, based on gallium or indium, was recently introduced as an alternative to conventional palladium-based membranes. The potential of this class of gas separation materials was mainly attributed to the promise of higher hydrogen diffusivity. The postulated improvements are only beneficial to the flux if diffusion through the membrane is the rate-determining step in the permeation sequence. Whilst this is a valid assumption for hydrogen transport through palladium-based membranes, the relatively low adsorption energy of hydrogen on both liquid metals suggests that other phenomena may be relevant. In the current study, a microkinetic modeling approach is used to enable simulations based on a five-step permeation mechanism. The calculation results show that for the liquid metal membranes, the flux is limited by the dissociative adsorption over a large temperature range, and that the membrane flux is expected to be orders of magnitude lower compared to the membrane flux through pure palladium membranes. Even when accounting for the lower cost of the liquid metals compared to palladium, the latter still outperforms both gallium and indium in all realistic scenarios, in part due to the practical difficulties associated with making liquid metal thin films. Full article

Palladium and palladium alloy membranes are superior materials for hydrogen purification, removal, or reaction processes. Sieverts’ Law suggests that the flux of hydrogen through such membranes is proportional to the difference between the feed and permeate side partial pressures, each raised to the 0.5 power (n = 0.5). Sieverts’ Law is widely applied in analyzing the steady state hydrogen permeation through Pd-based membranes, even in some cases where the assumptions made in deriving Sieverts’ Law do not apply. Often permeation data are fit to the model allowing the pressure exponent (n) to vary. This study experimentally assessed the validity of Sieverts’ Law as hydrogen was separated from other gases and theoretically modelled the effects of pressure and temperature on the assumptions and hence the accuracy of the 0.5-power law even with pure hydrogen feed. Hydrogen fluxes through Pd and Pd-Ag alloy foils from feed mixtures (5–83% helium in hydrogen; 473–573 K; with and without a sweep gas) were measured to study the effect of concentration polarization (CP) on hydrogen permeance and the applicability of Sieverts’ Law under such conditions. Concentration polarization was found to dominate hydrogen transport under some experimental conditions, particularly when feed concentrations of hydrogen were low. All mixture feed experiments showed deviation from Sieverts’ Law. For example, the hydrogen flux through Pd foil was found to be proportional to the partial pressure difference (n ≈ 1) rather than being proportional to the difference in the square root of the partial pressures (n = 0.5), as suggested by Sieverts’ Law, indicating the high degree of concentration polarization. A theoretical model accounting for Langmuir adsorption with temperature dependent adsorption equilibrium coefficient was made and used to assess the effect of varying feed pressure from 1–136 atm at fixed temperature, and of varying temperature from 298 to 1273 K at fixed pressure. Adsorption effects, which dominate at high pressure and at low temperature, result in pressure exponents (n) values less than 0.5. With better understanding of the transport steps, a qualitative analysis of literature (n) values of 0.5, 0.5 < n < 1, and n > 1, was conducted suggesting the role of each condition or step on the hydrogen transport based on the empirically fit exponent value. Full article

This work focused on the computational fluid dynamics (CFD) modeling of H₂/N₂ separation in a membrane permeator module containing a supported dense Pd-based membrane that was prepared using electroless pore-plating (ELP-PP). An easy-to-implement model was developed based on a source–sink pair formulation of the species transport and continuity equations. The model also included the Darcy–Forcheimer formulation for modeling the porous stainless steel (PSS) membrane support and Sieverts’ law for computing the H₂ permeation flow through the dense palladium film. Two different reactor configurations were studied, which involved varying the hydrogen flow permeation direction (in–out or out–in). A wide range of experimental data was simulated by considering the impact of the operating conditions on the H₂ separation, such as the feed pressure and the H₂ concentration in the inlet stream. Simulations of the membrane permeator device showed an excellent agreement between the predicted and experimental data (measured as permeate and retentate flows and H₂ separation). Molar fraction profiles inside the permeator device for both configurations showed that concentration polarization near the membrane surface was not a limit for the hydrogen permeation but could be useful information for membrane reactor design, as it showed the optimal length of the reactor. Full article

Hydrogen promotion as a clean energy vector could provide an efficient strategy for realizing real decarbonization of the current energy system. Purification steps are usually required in most H₂-production processes, providing the use of Pd-based membranes, particularly those supported on porous stainless steel (PSS), important advantages against other alternatives. In this work, new composite membranes were prepared by modifying PSS supports with graphite, as an intermediate layer, before incorporating a palladium film by electroless pore-plating. Fully dense Pd layers were reached, with an estimated thickness of around 17 μm. Permeation measurements were carried out in two different modes: H₂ permeation from the inner to the outer side of the membrane (in–out) and in the opposite way (out–in). H₂ permeances between 3.24 × 10⁻⁴ and 4.33 × 10⁻⁴ mol m⁻² s⁻¹ Pa^−0.5 with α_H2/N2 ≥ 10,000 were reached at 350–450 °C when permeating from the outer to the inner surface. Despite a general linear trend between permeating H₂ fluxes and pressures, the predicted intercept in (0,0) by the Sieverts’ law was missed due to the partial Pd infiltration inside the pores. H₂-permeances progressively decreased up to around 33% for binary H₂–N₂ mixtures containing 40 vol% N₂ due to concentration–polarization phenomena. Finally, the good performance of these membranes was maintained after reversing the direction of the permeate flux. This fact practically demonstrates an adequate mechanical resistance despite generating tensile stress on the Pd layer during operation, which is not accomplished in other Pd membranes. Full article

An investigation has been made concerning the solubility of nitrogen in liquid binary alloys (Ni-V and Ni-Ta) and ternary alloys (Ni-Cr-V and Ni-Cr-Ta) by sampling method. The experiments were carried out in the temperature range from 1773 K to 1873 K and under the nitrogen partial pressure up to 1.0 bar. A technique involving induction melting and a rapid quench device has been used in this study. It has been found that Sieverts’ law successfully describes the nitrogen dissolution in all these liquid alloys up to 1.0 bar of nitrogen gas partial pressure. The additions of vanadium, tantalum and chromium significantly increase the nitrogen solubility, especially vanadium-alloying addition. Furthermore, we have determined the interaction parameters, enthalpies and entropies of nitrogen dissolution in these liquid alloys. Full article

The influence of hydrogen on the mechanical properties of four, medium-strength, commercial, quenched-and-temped steels has been studied using the linearly increasing stress test (LIST) combined with cathodic hydrogen charging. The relationship was established between the equivalent hydrogen pressure and the hydrogen charging overpotential during cathodic hydrogen charging, though the use of electrochemical permeation experiments and thermal desorption spectroscopy. The cathodic hydrogen charging conditions were equivalent to testing in gaseous hydrogen at hydrogen fugacities of over a thousand bar. Under these hydrogen-charging conditions, there was no effect of hydrogen up to the yield stress. There was an influence of hydrogen on the final fracture, which occurred at the same stress as for the steels tested in air. The influence of hydrogen was on the details of the final fracture. In some cases, brittle fractures initiated by hydrogen, or DHF: Decohesive hydrogen fracture, initiated the final fracture of the specimen, which was largely by ductile micro-void coalescence (MVC), but did include some brittle fisheye fractures. Each fisheye was surrounded by MVC. This corresponds to MF: Mixed fracture, wherein a hydrogen microfracture mechanism (i.e., that producing the fisheyes) competed with the ductile MVC fracture. The fisheyes were associated with alumina oxide inclusion, which indicated that these features would be less for a cleaner steel. There was no subcritical crack growth. There was essentially no influence of hydrogen on ductility for the hydrogen conditions studied. At applied stress amplitudes above the threshold stress, fatigue initiation, for low cycle fatigue, occurred at a lower number of cycles with increasing hydrogen fugacity and increasing stress amplitude. This was caused by a decrease in the fatigue initiation period, and by an increase in the crack growth rate. In the presence of hydrogen, there was flat transgranular fracture with vague striations with some intergranular fracture at lower stresses. Mechanical overload occurred when the fatigue crack reached the critical length. There was no significant influence of hydrogen on the final fracture. Full article