Structure-dependent activity and stability of Al2O3 supported Rh catalysts for the steam reforming of n-dodecane

Steam reforming of liquid hydrocarbon fuels is an appealing way for the production of hydrogen. In this work, the Rh/Al₂O₃ catalysts with nanorod (NR), nanofiber (NF) and sponge-shaped (SP) alumina supports were successfully designed for the steam reforming of n-dodecane as a surrogate compound for diesel/jet fuels. The catalysts before and after reaction were well characterized by using ICP, XRD, N₂ adsorption, TEM, HAADF-STEM, H₂-TPR, CO chemisorption, NH₃-TPD, CO₂-TPD, XPS, Al²⁷ NMR and TG. The results confirmed that the dispersion and surface structure of Rh species is quite dependent on the enclosed various morphologies. Rh/Al₂O₃-NR possesses highly dispersed, uniform and accessible Rh particles with the highest percentage of surface electron deficient Rh⁰ active species, which due to the unique properties of Al₂O₃ nanorod including high crystallinity, relatively large alumina particle size, thermal stability, and large pore volume and size. As a consequent, Rh/Al₂O₃-NR catalyst exhibited superior catalytic activity towards steam reforming reactions and hydrogen production rate over other two catalysts. Especially, Rh/Al₂O₃-NR catalyst showed the highest hydrogen production rate of 87,600 mmol g_fuel^?1 g_Rh^?1min^?1 among any Rh-based catalysts and other noble metal-based catalysts to date. After long-term reaction, a significant deactivation occurred on Rh/Al₂O₃–NF and Rh/Al₂O₃-SP catalysts, due to aggregation and sintering of Rh metal particles, coke deposition and poor hydrothermal stability of nanofibrous structure. In contrast, the Rh/Al₂O₃-NR catalyst shows excellent reforming stability with negligible coke formation. No significantly sintering and aggregation of the Rh particles is observed after long-term reaction. Such great catalyst stability can be explained by the role of hydrothermal stable nanorod alumina support, which not only provides a unique environment for the stabilization of uniform and small-size Rh particles but also affords strong surface basic sites.     

Investigation of the changes in physical properties of PES/PVC fabrics after aging

The aim of this work was to investigate the physical and mechanical performance of architectural polyester (PES)–poly(vinyl chloride) (PVC) membranes exposed to different artificial aging conditions. Two commercially available architectural membranes were chosen as research objects. The durability of the PES/PVC fabrics was evaluated by the loss in mechanical performance, scanning electron microscopy, and X-ray diffraction analysis in order to understand the effect of the degradation agents on the surface of the membranes. The mechanical performance of the PES/PVC membranes was unchanged. Scanning electron microscopy images of the tested materials showed initial cracks after aging. The X-ray fluorescence analysis showed that at the time of aging, the amount of Cl and Si decreased slightly, while Ti decreased by half, and Ca by volume increased twice. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47523.     

Blends of Bio-Based Poly(Limonene Carbonate) with Commodity Polymers

In this study, blends of the bio-based poly(limonene carbonate) (PLimC) with different commodity polymers are investigated in order to explore the potential of PLimC toward generating more sustainable polymer materials by reducing the amount of petro- or food-based polymers. PLimC is employed as minority component in the blends. Next to the morphology and thermal properties of the blends the impact of PLimC on the mechanical properties of the matrix polymers is studied. The interplay of incompatibility and zero-shear melt viscosity contrast determines the blend morphology, leading for all blends to a dispersed droplet morphology for PLimC. Blends with polymers of similar structure to PLimC (i.e., aliphatic/aromatic polyester) show the best performance with respect to mechanical properties, whereas blends with polystyrene or poly(methyl methacrylate) are too brittle and polyamide 12 blends show very low elongations at break. In blends with Ecoflex (poly(butylene adipate-co-terephthalate)) and Arnitel EM400 (copoly(ether ester)) with poly(butylene terephthalate) hard and polytetrahydrofuran soft segments) a threefold increase in E-modulus can be achieved, while keeping the elongation at break at reasonable high values of ≈200%, making these blends highly interesting for applications.     

Morphological study of thin films: Simulation and experimental insights using horizontal visibility graph

We studied the morphological nature of various thin films such as silicon carbide (SiC), diamond (C), germanium (Ge), and gallium nitride (GaN) on silicon substrate Si(100) using the pulsed laser deposition (PLD) method and Monte Carlo simulation. We, for the first time, systematically employed the visibility algorithm graph to meticulously study the morphological features of various PLD grown thin films. These thin-film morphologies are investigated using random distribution, Gaussian distribution, patterned heights, etc. The nature of the interfacial height of individual surfaces is examined by a horizontal visibility graph (HVG). It demonstrates that the continuous interfacial height of the silicon carbide, diamond, germanium, and gallium nitride films are attributed to random distribution and Gaussian distribution in thin films. However, discrete peaks are obtained in the brush and step-like morphology of germanium thin films. Further, we have experimentally verified the morphological nature of simulated silicon carbide, diamond, germanium, and gallium nitride thin films were grown on Si(100) substrate by pulsed laser deposition (PLD) at elevated temperature. Various characterization techniques have been used to study the morphological, and electrical properties which confirmed the different nature of the deposited films on the Silicon substrate. Decent hysteresis behavior has been confirmed by current-voltage (IV) measurement in all the four deposited films. The highest current has been measured for GaN at ～60 nA and the lowest current in SiC at ～30 nA level which is quite low comparing with the expected signal level (μA). The HVG technique is suitable to understand surface features of thin films which are substantially advantageous for the energy devices, detectors, optoelectronic devices operating at high temperatures.     

Material encapsulation in poly(methyl methacrylate) shell: A review

Material encapsulation is a relatively new technique for coating a micro/nanosize particle or droplet with polymeric or inorganic shell. Encapsulation technology has many applications in various fields including drug delivery, cosmetic, agriculture, thermal energy storage, textile, and self-healing polymers. Poly(methyl methacrylate) (PMMA) is widely used as shell material in encapsulation due to its high chemical stability, biocompatibility, nontoxicity, and good mechanical properties. The main approach for micro/nanoencapsulation of materials using PMMA as shell comprises emulsion-based techniques such as emulsion polymerization and solvent evaporation from oil-in-water emulsion. In the present review, we first focus on the encapsulation techniques of liquid materials with PMMA shell by analyzing the effective processing parameters influencing the preparation of PMMA micro/nanocapsules. We then describe the morphology of PMMA capsules in emulsion systems according to thermodynamic relations. The techniques to investigation of mechanical properties of capsule shell and the release mechanisms of core material from PMMA capsules were also investigated. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48039.     

Evaluation of hydrodynamic behavior of the perforated gas distributor of industrial gas phase polymerization reactor using CFD-PBM coupled model

A 2D computational fluid dynamics (Eulerian–Eulerian) multiphase flow model coupled with a population balance model (CFD-PBM) was implemented to investigate the fluidization structure in terms of entrance region in an industrial-scale gas phase fluidized bed reactor. The simulation results were compared with the industrial data, and good agreement was observed. Two cases including perforated distributor and complete sparger were applied to examine the flow structure through the bed. The parametric sensitivity analysis of time step, number of node, drag coefficient, and specularity coefficient was carried out. It was found that the results were more sensitive to the drag model. The results showed that the entrance configuration has significant effect on the flow structure. While the dead zones are created in both corners of the distributors, the perforated distributor generates more startup bubbles, heterogeneous flow field, and better gas–solid interaction above the entrance region due to jet formation.     

Upscaled DEM-CFD model for vibrated fluidized bed based on particle-scale similarities

Simulation based on discrete element method (DEM) coupled with computational fluid dynamics (CFD), coupled DEM-CFD, is a powerful tool for investigating the details of dense particle–fluid interaction problems such as in fluidized beds and pneumatic conveyers. The addition of a mechanical vibration to a system can drastically alter the particle and fluid flows; however, their detailed mechanisms are not well understood. In this study, a DEM-CFD model based on a non-inertial frame of reference is developed to achieve a better understanding of the influence of vibration in a vibrated fluidized bed. Because the high computational cost of DEM-CFD calculations is still a major problem, an upscaled coarse-graining model is also employed. To realize similar behaviors with enlarged model particles, non-dimensional parameters at the particle scale were deduced from the governing equations. The suitability and limitations of the proposed model were examined for a density segregation problem of a binary system. To reduce the computational costs, we show that the ratio between the bed width and model particle size can be reduced to a minimum value of 100; to obtain similar segregation behaviors, the ratio between the bed height and model particle size is considered unchanged.     

Studying local liquid velocity in liquid–solid packed bed using the newly developed X-ray DIR technique

Combination of X-ray Digital Industrial Radiography (DIR) and Particle Tracking Velocimetry (PTV) techniques for local liquid velocity measurement (V_LL) has been newly developed and successfully applied for trickle bed reactor (TBR). The technique was validated against newly developed fiber optical probe technique. This work attempts to highlight the applicability of this newly developed technique on a liquid–solid packed bed reactor. In this work, liquid was represented by water and solids were represented by EPS beads. The EPS beads were chosen because of its low density property. Three superficial liquid velocities (V_SL) were applied to the system. The experiment was replicated four times. The digital industrial radiography (DIR) consists of a complementary metal oxide semiconductor (CMOS) digital detector and X-ray source. Results of this work suggest that the technique has been successfully applied and comparable with previous work that has been done in the literature. It also suggests that there will be a maximum measurable interstitial liquid velocity when it travel inside the packed bed. The measured V_LL can have a maximum range that is between 4 and 4.7 times that of its V_SL. For V_SL=0.42±±2%, the V_LL-Max is in between 1.7 cm/s and 1.9 cm/s, V_SL=0.84±±2%, the V_LL-Max is in between 3.6 cm/s and 4.0 cm/s, and for V_SL=1.11±±2%, the V_LL-Max is in between 4.3 cm/s and 4.8 cm/s.     

Simulation of thermal barrier coating spallation induced by the initiation/growth/coalescence of internal crack and interfacial crack based on a real image model

In the furnace cycle test, the growth of oxide film leads to the propagation and coalescence of multiple cracks near the interface, which should be responsible for the spallation of thermal barrier coatings (TBCs). A TBC model with real interface morphology is created, and the near-interface large pore is retained. The purpose of this work is to clarify the mechanism of TBC spallation caused by successive initiation, propagation, and linkage of cracks near the interface during thermal cycle. The dynamic growth of thermally grown oxide (TGO) is carried out by applying a stress-free strain. The crack nucleation and arbitrary path propagation in YSZ and TGO are simulated by the extended finite element method (XFEM). The debonding along the YSZ/TGO/BC interface is evaluated using a surface-based cohesive behavior. The large-scale pore in YSZ near the interface can initiate a new crack. The ceramic crack can propagate to the YSZ/TGO interface, which will accelerate the interfacial damage and debonding. For the TGO/BC interface, the normal compressive stress and small shear stress at the valley hinder the further crack propagation. The growth of YSZ crack and the formation of through-TGO crack are the main causes of TBC delamination. The accelerated BC oxidation increases the lateral growth strain of TGO, which will promote crack propagation and coalescence. The optimization design proposed in this work can provide another option for developing TBC with high durability.     

Additive manufacturing of bipolar plates for hydrogen production in proton exchange membrane water electrolysis cells

Water electrolysis is a process that can produce hydrogen in a clean way when renewable energy sources are used. This allows managing large renewable surpluses and transferring this energy to other sectors, such as industry or transport. Among the electrolytic technologies to produce hydrogen, proton exchange membrane (PEM) electrolysis is a promising alternative. One of the main components of PEM electrolysis cells are the bipolar plates, which are machined with a series of flow distribution channels, largely responsible for their performance and durability. In this work, AISI 316L stainless steel bipolar plates have been built by additive manufacturing (AM), using laser powder bed fusion (PBF-L) technology. These bipolar plates were subjected to ex-situ corrosion tests and assembled in an electrolysis cell to evaluate the polarization curve. Furthermore, the obtained results were compared with bipolar plates manufactured by conventional machining processes (MEC). The obtained experimental results are very similar for both manufacturing methods. This demonstrates the viability of the PBF-L technology to produce metal bipolar plates for PEM electrolyzers and opens the possibilities to design new and more complex flow distribution channels and to test these designs in initial phases before scaling them to larger surfaces.