Nickel foam-supported Fe,Ni-Polyporphyrin microparticles: Efficient bifunctional catalysts for overall water splitting in alkaline media

Developing highly active, stable and sustainable electrocatalysts for overall water splitting is of great importance to generate renewable H₂ for fuel cells. Herein, we report the synthesis of electrocatalytically active, nickel foam-supported, spherical core-shell Fe-poly(tetraphenylporphyrin)/Ni-poly(tetraphenylporphyrin) microparticles (FeTPP@NiTPP/NF). We also show that FeTPP@NiTPP/NF exhibits efficient bifunctional electrocatalytic properties toward both the oxygen evolution reaction (OER) and the hydrogen evolution reaction (HER). Electrochemical tests in KOH solution (1 M) reveal that FeTPP@NiTPP/NF electrocatalyzes the OER with 100 mA cm⁻² at an overpotential of 302 mV and the HER with 10 mA cm⁻² at an overpotential of 170 mV. Notably also, its catalytic performance for OER is better than that of RuO₂, the benchmark OER catalyst. Although its catalytic activity for HER is slightly lower than that of Pt/C (the benchmark HER electrocatalyst), it shows greater stability than the latter during the reaction. The material also exhibits electrocatalytic activity for overall water splitting reaction at a current density of 10 mA cm⁻² with a cell voltage of 1.58 V, along with a good recovery property. Additionally, the work demonstrates a new synthetic strategy to an efficient, noble metal-free-coordinated covalent organic framework (COF)-based, bifunctional electrocatalyst for water splitting.     

Methodology for optimization of pouring variables using bottom pour for low masses of SS304 (<300 kg) in investment casting process (case study)

Bottom pour ladles with stopper rod systems are commonly used in the metal casting industry. However, stopper rod bottom-pouring systems have not yet been developed for the lower thermal masses of alloys typically used in the investment casting industry. Large thermal masses used with bottom pour systems are typically limited for ladles larger than 700 kg and to certain alloys with higher fluidity and longer solidification time like cast iron, aluminum alloys etc. In this study, bottom pour ladle designs and low thermal mass refractory systems have been developed and evaluated in production investment foundry trials with 300 kg pouring ladle. The ladles system and pouring practices used will be described along with the results from the pouring trials for SS304 that represents typical alloys used in Investment casting industries. Optimization of the variables used in an experimentation using Genetic algorithm is also explained.     

Thermal degradation of corn starch based biodegradable plastic plates and determination of kinetic parameters by isoconversional methods using thermogravimetric analyzer

Oil shortage and awareness of environment pollution leads to the extensive use of biodegradable starch-based materials against synthetic plastics. The accumulated wastes of these plastics takes more time for natural recycling and the process is complex. Therefore the best option of recycling would be to convert these polymers into a source of energy by pyrolysis. So to understand the pyrolytic behaviour, kinetics of such waste plastics is studied by using thermogravimetric analysis at different heating rates of 10 °C, 20 °C, 40 °C, 60 °C, 80 °C and 100 °C in nitrogen atmosphere followed by characterization of the pyrolysis products. The kinetic parameters are obtained for two major stages of decomposition in two different temperature ranges 250–620 °C and 620–855 °C by iso-conversional methods such as Friedman, Coats-Redfern, FWO and Kissinger methods. The regression coefficient data (>0.9) of kinetic plots obtained for different methods best fits to the kinetic equation. Empirical formula of the compound is determined by ultimate analysis is CH_2.214S_0.0018O_0.6910. Proximate analysis gives the idea of volatile component which is74.33%. The range of average value of activation energy is 120.7013 kJ/mol to 140.7707 kJ/mol for the biodegradable plastic plate with different conversion (0.1–0.6) and (0.1–0.3) respectively at two different temperatures. The pyrolysis products obtained using a semi-batch reactor are characterized to know their composition and other properties.     

Effects of ethylene-octene copolymer (POE) on the brittle to ductile transition of high-density polyethylene/POE blends

Three kinds of ethylene-octene copolymers (POE) were melt-blended with high-density polyethylene (PE-HD) in different proportions. Detailed characterizations were conducted to analyze their structural differences of POE and its effects in toughening PE-HD. The higher molecular weight POE can improve the toughness of PE-HD. 60:40 PE-HD/POE is elongated to break up to 700% while impact strength is 84.7 kJ/m² at −30°C, which is 21-fold of PE-HD. In the brittle to ductile transition (BDT) during impact, the fracture mechanism changes from the crazing mode to the shear yield-plastic deformation mode. The BDT temperature decreases as the POE molecular weight and its content increase. The interface strength in tension is estimated to access their effects. The Boltzmann-type models were successfully extended to describe the typical S-shaped curves in BDT of notched impact strength vs POE content or temperature. The supplementary decay model is suggested for the attenuation in toughening. Transition map in impact is proposed to select the use range of composition (c ) and temperature (T ) for high toughness. The curves are converted into 3D graph of T -c -impact strength for illustrating their coupling-separate effects, and further into the contour map of impact strength in T -c space for finding their partial equivalence.     

Effect of grinding-induced cyclic heating on the hardened layer generation in the plunge grinding of a cylindrical component

This paper discusses the effects of the grinding-induced cyclic heating on the properties of the hardened layer in a plunge cylindrical grinding process on the high strength steel EN26. It was found that a multi-pass grinding brings about a uniform and continuous hardened layer along the circumference of the cylindrical workpiece. An increase of the number of grinding passes, leads to a thicker layer of hardening, a larger compressive residual stress and a deeper plastic deformation zone. Within the plastic deformation zone, the martensitic grains are refined by the thermo-mechanical loading, giving rise to a hardness of 12.5% higher than that from a conventional martensitic transformation. The coupled effects of heat accumulation and wheel wear in the multi-pass grinding are the main causes for the thickening of the hardened layer. A too small infeed per workpiece revolution would result in insufficient grinding heat, and in turn, bring about an undesirable tempered hardened layer and a reduction of its hardness.     

A design of a robust discrete-time controller

In this paper, we proposed a robust discrete-time controller. This control system, which is derived from the idea of the normalized plant, does not include plant parameters. Thus, we obtain a control system independent of plant parameters and that has the same structure as a conventional optimal servo control system. Simulation and experimental results show that the proposed method is fairly robust to plant parameter variations and external disturbances.     

Convergence analysis of the alternating RGLS algorithm for the identification of the reduced complexity Volterra model

In this paper we provide a convergence analysis of the alternating RGLS (Recursive Generalized Least Square) algorithm used for the identification of the reduced complexity Volterra model describing stochastic non-linear systems. The reduced Volterra model used is the 3rd order SVD-PARAFC-Volterra model provided using the Singular Value Decomposition (SVD) and the Parallel Factor (PARAFAC) tensor decomposition of the quadratic and the cubic kernels respectively of the classical Volterra model. The Alternating RGLS (ARGLS) algorithm consists on the execution of the classical RGLS algorithm in alternating way. The ARGLS convergence was proved using the Ordinary Differential Equation (ODE) method. It is noted that the algorithm convergence canno׳t be ensured when the disturbance acting on the system to be identified has specific features. The ARGLS algorithm is tested in simulations on a numerical example by satisfying the determined convergence conditions. To raise the elegies of the proposed algorithm, we proceed to its comparison with the classical Alternating Recursive Least Squares (ARLS) presented in the literature. The comparison has been built on a non-linear satellite channel and a benchmark system CSTR (Continuous Stirred Tank Reactor). Moreover the efficiency of the proposed identification approach is proved on an experimental Communicating Two Tank system (CTTS).     

A dense and compact laser cladding layer with solid metallurgical bonding significantly improved corrosion resistance of Mg alloy for engineering applications

Although Mg alloy attracts great attention for engineering applications because of high specific strength and low density, low corrosion resistance limits its extensive use. In this study, Mg–Al–Zn–Mn alloy was treated via a laser cladding process to generate a dense and compact laser cladding layer with solid metallurgical bonding on the substrate for improving corrosion resistance, effectively hindering the corrosion pervasion into Mg alloy. The corrosion current density declined from 103 μA/cm² for Mg alloy to 13 μA/cm² for the laser cladding layer in NaCl aqueous solution. Moreover, the laser cladding layer was slightly corroded in comparison with Mg alloy in NaCl aqueous solution. Besides, the microhardness of the cladding layer reached a mean value of 170.5 HV, 3.1 times of Mg alloy (56.8 HV) due to the in situ formation of hardening intermetallic phases. Wear resistance of laser cladding layer was also obviously improved. These results demonstrated that the laser cladding layer obviously enhanced anticorrosion property of Mg alloy for engineering applications.     

Influence of the ZrB2 content on the anti-oxidation ability of ZrB2-SiC coatings in aerobic environments with broad temperature range

ZrB₂-SiC coatings with different ZrB₂ contents were prepared by liquid phase sintering. The oxidation processes of coatings were explained according to TG results of ZrB₂-SiC coatings and powders tested from 298 K to 1773 K. Results show that, increasing ZrB₂ content made the weight of the samples changed from weight-loss of 10.04% to weight-gain of 0.14%, while the fastest weight-loss regions were narrowed, whose inflection points reduced from 1310℃ to 1050℃. Increasing ZrB₂ content made the relative oxygen permeability of the ZrB₂-SiC/SiC coatings reduced from 40%–60% to -10%-5%. Increasing ZrB₂ content enhanced high-temperature stability of coatings, making final weight of samples changed from weight-loss of 0.16% to weight-gain of 0.11% after oxidation at 1773 K for 200 h. The peeling and dispersion of Zr-oxides formed Zr-B-Si-O compound glass layer, presenting enhanced stability, dispersion strengthening and pinning effect of Zr-oxides, which were responsible for the excellent anti-oxidation protective effect of coatings in a broad temperature region.