Robust optimal operation of continuous catalytic reforming process under feedstock uncertainty

The continuous catalytic regenerative (CCR) reforming process is one of the most significant sources of hydrogen production in the petroleum refining process. However, the fluctuations in feedstock composition and flow rate could significantly affect both product distribution and energy consumption. In this study, a robust deviation criterion based multi-objective optimization approach is proposed to perform the optimal operation of CCR reformer under feedstock uncertainty, with simultaneous maximization of product yields and minimization of energy consumption. Minimax approach is adopted to handle these uncertain objectives, and the Latin hypercube sampling method is then used to calculate these robust deviation criteria. Multi-objective surrogate-based optimization methods are next introduced to effectively solve the robust operational problem with high computational cost. The level diagram method is finally utilized to assist in multi-criteria decision-making. Two robust operational optimization problems with different objectives are solved to demonstrate the effectiveness of the proposed method for robust optimal operation of the CCR reforming process under feedstock uncertainty.     

Ion migration behavior and its interaction with sintering environment in cation conductor during flash sintering

Flash sintering has been reported in various ceramics. Nevertheless, anion and cation conductors exhibit different flash-sintering behaviors, and the interaction mechanism between the conductive species and the sintering environment has remained unclear. Herein, we report the flash-sintering phenomena of a typical cation conductor, Na₃Zr₂(SiO₄)₂(PO₄) with anode region surrounded by air and NaNO₃ environments. The results prove that the ionic behavior and joule heating distribution can be controlled by changing the electrode environment. Four possible scenarios describing the ion migration behavior and interaction with the environment are proposed for providing a guidance for controlling the ion interaction behavior during flash sintering.     

Interface regulation effects on mechanical behavior of heterostructure Ti6Al4V/TiAl-based laminated composite sheets

Design of architectured composites with layered-ordered structure can solve the strength-toughness mismatch problem of structural materials. In the present study, heterostructure Ti6Al4V/TiAl laminated composite sheets with different thicknesses of interface layer and TiAl composite layer were successfully produced by hot-pressing technology. The effects of interface regulation and laminated structure on their mechanical properties, crack propagation, and fracture behavior were studied. The results indicated that compressive strength of the sheets increased with the decrease in interface thickness. Compressive strength of TiAl composite sheet with thicker composite layer reached 1481.55 MPa at the arrester orientation with sintering holding time of 40 min, which was 25.96% higher than that of the sheet obtained at 120 min. Analysis indicated that the interface area transferred stress through slip bands and through-interface cracks. Compressive strength at the divider orientation reached 1443.06 MPa, which was 45.78% higher than that of the sheet obtained at 120 min. In this case, the interface area transferred stress through slip bands and along-interface cracks. For TiAl composite sheets with thinner composite layer, compressive strength was further improved to 1631.01 MPa and 1594.66 MPa at the arrester and divider orientations with sintering holding time of 40 min, respectively. The ductile metal layer exerted a significant toughening effect. Both interface regulation and laminated structure transformation could enhance the hetero-deformation induced (HDI) strengthening and improve the comprehensive mechanical properties of the composite sheets.     

The structure,vacancy characteristics,and magnetic properties of GdMn1-xCrxO3 ceramics

To investigate the evolution of the structural and enhanced magnetic properties of GdMnO₃ systems induced by the substitution of Mn with Cr, polycrystalline GdMn_1-xCr_xO₃ samples were synthesized via solid-state reactions. XRD characterization shows that all GdMn_1-xCr_xO₃ compounds with single-phase structures crystallize well and that Cr³⁺ ions entering the lattice sites of GdMnO₃ induce structural distortion. SEM results indicate that the grain size of the synthesized samples (a few microns) decreases as the Cr substitution concentration increases. Positron annihilation lifetime spectroscopy reveals that vacancy-type defects occur in GdMn_1-xCr_xO₃ ceramics and that the vacancy size and concentration clearly change with the Cr content. The temperature and field dependence of the magnetization curves show that Cr substitution significantly influences the magnetic ordering of the gadolinium sublattice, improving the weak ferromagnetic transition temperature and magnetization of GdMn_1-xCr_xO₃. The enhanced magnetization of GdMn_1-xCr_xO₃ is closely related to the vacancy defect concentration.     

High energy storage and ultrafast discharge in NaNbO3-based lead-free dielectric capacitors via a relaxor strategy

Dielectric capacitors with decent energy storage and fast charge-discharge performances are essential in advanced pulsed power systems. In this study, novel ceramics (1-x)NaNbO₃-xBi(Ni_2/3Nb_1/3)O₃(xBNN, x = 0.05, 0.1, 0.15 and 0.20) with high energy storage capability, large power density and ultrafast discharge speed were designed and prepared. The impedance analysis proves that the introducing an appropriate amount of Bi(Ni_0·5Nb_0.5)O₃ boosts the insulation ability, thus obtaining a high breakdown strength (E_b) of 440 kV/cm in xBNN ceramics. A high energy storage density (W_total) of 4.09 J/cm³, recoverable energy storage density (W_rec) of 3.31 J/cm³, and efficiency (η) of 80.9% were attained in the 0.15BNN ceramics. Furthermore, frequency and temperature stability (fluctuations of W_rec ≤ 0.4% over 5–100 Hz and W_rec ≤ 12.3% over 20–120 °C) were also observed. The 0.15BNN ceramics exhibited a large power density (19 MW/cm³) and ultrafast discharge time (~37 ns) over the range of ambient temperature to 120 °C. These enhanced performances may be attributed to the improved breakdown strength and relaxor behavior through the incorporation of BNN. In conclusion, these findings indicate that 0.15BNN ceramics may serve as promising materials for pulsed power systems.     

Process Intensification of Living Cationic Polymerization of Isobutylene by a Flow Reaction System

Increasing the reaction temperature of the living cationic polymerization of isobutylene is crucial for industrial production due to the cost of refrigeration. The reaction temperature increase was achieved with an accelerated reaction rate using a flow reaction system. The polymerization conditions, including the flow reactor design, were based on the results of kinetic studies. Utilizing a milli‐scale flow reactor, polyisobutylene, which has a narrow molecular weight distribution, was obtained within a considerably short residence time at a high temperature. Furthermore, it was confirmed that the value of M_w/M_n correlates with the product of the Reynolds number and the angle of collision.     

Effects of Cu on the corrosion behavior and microstructure of Mg–Zn–Ca bulk metallic glass

For the purpose of developing biodegradable magnesium alloys with suitable properties for biomedical applications, Mg–Zn–Ca–Cu metallic glasses were prepared by copper mold injection methods. In the present work, the effect of Cu doping on mechanical properties, corrosion behavior, and glass-forming ability of Mg₆₆Zn₃₀Ca₄ alloy was studied. The experimental findings demonstrated that the incorporation of Cu decreases the corrosion resistance of alloys, but increases the microhardness and degradation rate slightly. However, the addition of a trace amount of Cu can make the samples have antibacterial properties. Therefore, Mg–Zn–Ca–Cu has great advantages in clinical implantation and is the potential implant material.     

Colossal dielectric response and relaxation behavior in novel system of Zr4+ and Nb5+ co-substituted CaCu3Ti4O12 ceramics

In this work, we developed a novel system of isovalent Zr⁴⁺ and donor Nb⁵⁺ co-doped CaCu₃Ti₄O₁₂ (CCTO) ceramics to enhance dielectric response. The influences of Zr⁴⁺ and Nb⁵⁺ co-substituting on the colossal dielectric response and relaxation behavior of the CCTO ceramics fabricated by a conventional solid-phase synthesis method were investigated methodically. Co-doping of Zr⁴⁺ and Nb⁵⁺ ions leads to a significant reduction in grain size for the CCTO ceramics sintered at 1060 °C for 10 h. XRD and Raman results of the CaCu₃Ti_3.8-xZr_xNb_0.2O₁₂ (CCTZNO) ceramics show a cubic perovskite structure with space group Im-3. The first principle calculation result exhibits a better thermodynamic stability of the CCTO structure co-doped with Zr⁴⁺ and Nb⁵⁺ ions than that of single-doped with Zr⁴⁺ or Nb⁵⁺ ion. Interestingly, the CCTZNO ceramics exhibit greatly improved dielectric constant (~10⁵) at a frequency range of 10²–10⁵ Hz and at a temperature range of 20–210 °C, indicating a giant dielectric response within broader frequency and temperature ranges. The dielectric properties of CCTZNO ceramics were analyzed from the viewpoints of defect-dipole effect and internal barrier layer capacitance (IBLC) model. Accordingly, the immensely enhanced dielectric response is primarily ascribed to the complex defect dipoles associated with oxygen vacancies by co-doping Zr⁴⁺ and Nb⁵⁺ ions into CCTO structure. In addition, the obvious dielectric relaxation behavior has been found in CCTZNO ceramics, and the relaxation process in middle frequency regions is attributed to the grain boundary response confirmed by complex impedance spectroscopy and electric modulus.     

Phase constitution,microstructure and mechanical properties of a Ni-based superalloy specially designed for additive manufacturing

In this study, a kind of Ni-based superalloy specially designed for additive manufacturing (AM) was investigated. Thermo-Calc simulation and differential scanning calorimetry (DSC) analysis were used to determine phases and their transformation temperature. Experimental specimens were prepared by laser metal deposition (LMD) and traditional casting method. Microstructure, phase constitution and mechanical properties of the alloy were characterized by scanning electron microscopy (SEM), transmission scanning electron microscopy (TEM), X-ray diffraction (XRD) and tensile tests. The results show that this alloy contains two basic phases, γ/γ', in addition to these phases, at least two secondary phases may be present, such as MC carbides and Laves phases. Furthermore, the as-deposited alloy has finer dendrite, its mean primary dendrite arm space (PDAS) is about 30-45 μm, and the average size of γ' particles is 100-150 nm. However, the dendrite size of the as-cast alloy is much larger and its PDAS is 300-500 μm with secondary and even third dendrite arms. Correspondingly, the alloy displays different tensile behavior with different processing methods, and the as-deposited specimen shows better ultimate tensile stress (1,085.7±51.7 MPa), yield stress (697±19.5 MPa) and elongation (25.8%±2.2%) than that of the as-cast specimen. The differences in mechanical properties of the alloy are due to the different morphology and size of dendrites, γ', and Laves phase, and the segregation of elements, etc. Such important information would be helpful for alloy application as well as new alloy development.