Search results for: nickel alloys

Authors: Bekim Berisha, Sebastian Hirsiger, Pavel Hora

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Advanced material models involving several sets of model parameters require a big experimental effort. As models are getting more and more complex like e.g. the so called “Homogeneous Anisotropic Hardening - HAH” model for description of the yielding behavior in the 2D/3D stress space, the number and complexity of the required experiments are also increasing continuously. In the context of sheet metal forming, these requirements are even more pronounced, because of the anisotropic behavior or sheet materials. In addition, some of the experiments are very difficult to perform e.g. the plane stress biaxial compression test. Accordingly, tensile tests in at least three directions, biaxial tests and tension-compression or shear-reverse shear experiments are performed to determine the parameters of the macroscopic models. Therefore, determination of the macroscopic model parameters based on virtual experiments is a very promising strategy to overcome these difficulties. For this purpose, in the framework of multiscale material modeling, a dislocation density based crystal plasticity model in combination with a FFT-based spectral solver is applied to perform virtual experiments. Modeling of the plastic behavior of metals based on crystal plasticity theory is a well-established methodology. However, in general, the computation time is very high and therefore, the computations are restricted to simplified microstructures as well as simple polycrystal models. In this study, a dislocation density based crystal plasticity model – including an implementation of the backstress – is used in a spectral solver framework to generate virtual experiments for three deep drawing materials, DC05-steel, AA6111-T4 and AA4045 aluminum alloys. For this purpose, uniaxial as well as multiaxial loading cases, including various pre-strain histories, has been computed and validated with real experiments. These investigations showed that crystal plasticity modeling in the framework of Representative Volume Elements (RVEs) can be used to replace most of the expensive real experiments. Further, model parameters of advanced macroscopic models like the HAH model can be determined from virtual experiments, even for multiaxial deformation histories. It was also found that crystal plasticity modeling can be used to model anisotropic hardening more accurately by considering the backstress, similar to well-established macroscopic kinematic hardening models. It can be concluded that an efficient coupling of crystal plasticity models and the spectral solver leads to a significant reduction of the amount of real experiments needed to calibrate macroscopic models. This advantage leads also to a significant reduction of computational effort needed for the optimization of metal forming process. Further, due to the time efficient spectral solver used in the computation of the RVE models, detailed modeling of the microstructure are possible.

Keywords: anisotropic hardening, crystal plasticity, micro structure, spectral solver

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Authors: D. Olszewska, J. Niewiedzial

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In some types of Li-ion batteries carbon in the form of graphite is used. Unfortunately, carbon materials, in particular graphite, have very good electrochemical properties, but increase their volume during charge/discharge cycles, which may even lead to an explosion of the cell. The cell element may be replaced by a composite material consisting of lithium-titanium oxide Li4Ti5O12 (LTO) modified with copper and nickel ions and carbon derived from sucrose. This way you can improve the conductivity of the material. LTO is appropriate only for applications which do not require high energy density because of its high operating voltage (ca. 1.5 V vs. Li/Li+). Specific capacity of Li4Ti5O12 is high enough for utilization in Li-ion batteries (theoretical capacity 175 mAh·g-1) but it is lower than capacity of graphite anodes. Materials based on Li4Ti5O12 do not change their volume during charging/discharging cycles, however, LTO has low conductivity. Another positive aspect of the use of sucrose in the carbon composite material is to eliminate the addition of carbon black from the anode of the battery. Therefore, the proposed materials contribute significantly to environmental protection and safety of selected lithium cells. New anode materials in order to obtain Li3.8Cu0.1Ni0.1Ti5O12 have been prepared by solid state synthesis using three-way: i) stoichiometric composition of Li2CO3, TiO2, CuO, NiO (A- Li3.8Cu0.1Ni0.1Ti5O12); ii) stoichiometric composition of Li2CO3, TiO2, Cu(NO3)2, Ni(NO3)2 (B-Li3.8Cu0.1Ni0.1Ti5O12); and iii) stoichiometric composition of Li2CO3, TiO2, CuO, NiO calcined with 10% of saccharose (Li3.8Cu0.1Ni0.1Ti5O12-C). Structure of materials was studied by X-ray diffraction (XRD). The electrochemical properties were performed using appropriately prepared cell Li|Li+|Li3.8Cu0.1Ni0.1Ti5O12 for cyclic voltammetry and discharge/charge measurements. The cells were periodically charged and discharged in the voltage range from 1.3 to 2.0 V applying constant charge/discharge current in order to determine the specific capacity of each electrode. Measurements at various values of the charge/discharge current (from C/10 to 5C) were carried out. Cyclic voltammetry investigation was carried out by applying to the cells a voltage linearly changing over time at a rate of 0.1 mV·s-1 (in the range from 2.0 to 1.3 V and from 1.3 to 2.0 V). The XRD method analyzes show that composite powders were obtained containing, in addition to the main phase, 4.78% and 4% TiO2 in A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12, respectively. However, Li3.8Cu0.1Ni0.1O12-C material is three-phase: 63.84% of the main phase, 17.49 TiO2 and 18.67 Li2TiO3. Voltammograms of electrodes containing materials A-Li3.8Cu0.1Ni0.1O12 and B-Li3.8Cu0.1Ni0.1O12 are correct and repeatable. Peak cathode occurs for both samples at a potential approx. 1.52±0.01 V relative to a lithium electrode, while the anodic peak at potential approx. 1.65±0.05 V relative to a lithium electrode. Voltammogram of Li3.8Cu0.1Ni0.1Ti5O12-C (especially for the first measurement cycle) is not correct. There are large variations in values of specific current, which are not characteristic for materials LTO. From the point of view of safety and environmentally friendly production of Li-ion cells eliminating soot and applying Li3.8Cu0.1Ni0.1Ti5O12-C as an active material of an anode in lithium-ion batteries seems to be a good alternative to currently used materials.

Keywords: anode, Li-ion batteries, Li₄O₅O₁₂, spinel

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Authors: Natia Jalagonia, Jimsher Maisuradze, Karlo Barbakadze, Tinatin Kuchukhidze

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At present intensive scientific researches of ceramics, cermets and metal alloys have been conducted for improving materials physical-mechanical characteristics. In purpose of increasing impact strength of ceramics based on alumina, simple method of graphene homogenization was developed. Homogeneous distribution of graphene (homogenization) in pressing composite became possible through the connection of functional groups of graphene oxide (-OH, -COOH, -O-O- and others) and alumina superficial OH groups with aluminum organic compounds. These two components connect with each other with -O-Al–O- bonds, and by their thermal treatment (300–500°C), graphene and alumina phase are transformed. Thus, choosing of aluminum organic compounds for modification is stipulated by the following opinion: aluminum organic compounds fragments fixed on graphene and alumina finally are transformed into an integral part of the matrix. By using of other elements as modifier on the matrix surface (Al2O3) other phases are transformed, which change sharply physical-mechanical properties of ceramic composites, for this reason, effect caused by the inclusion of graphene will be unknown. Fixing graphene fragments on alumina surface by alumoorganic compounds result in new type graphene-alumina complex, in which these two components are connected by C-O-Al bonds. Part of carbon atoms in graphene oxide are in sp3 hybrid state, so functional groups (-OH, -COOH) are located on both sides of graphene oxide layer. Aluminum organic compound reacts with graphene oxide at the room temperature, and modified graphene oxide is obtained: R2Al-O-[graphene]–COOAlR2. Remaining Al–C bonds also reacts rapidly with surface OH groups of alumina. In a result of these process, pressing powdery composite [Al2O3]-O-Al-O-[graphene]–COO–Al–O–[Al2O3] is obtained. For the purpose, graphene oxide suspension in dry toluene have added alumoorganic compound Al(iC4H9)3 in toluene with equimolecular ratio. Obtained suspension has put in the flask and removed solution in a rotary evaporate presence nitrogen atmosphere. Obtained powdery have been researched and used to consolidation of ceramic materials based on alumina. Ceramic composites are obtained in high temperature vacuum furnace with different temperature and pressure conditions. Received ceramics do not have open pores and their density reaches 99.5 % of TD. During the work, the following devices have been used: High temperature vacuum furnace OXY-GON Industries Inc (USA), device of spark-plasma synthesis, induction furnace, Electronic Scanning Microscopes Nikon Eclipse LV 150, Optical Microscope NMM-800TRF, Planetary mill Pulverisette 7 premium line, Shimadzu Dynamic Ultra Micro Hardness Tester DUH-211S, Analysette 12 Dynasizer and others.

Keywords: graphene oxide, alumo-organic, ceramic

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Authors: Dorottya Guban, Irina Borbath, Istvan Bakos, Peter Nemeth, Andras Tompos

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One of the greatest challenges of the implementation of polymer electrolyte membrane fuel cells (PEMFCs) is to find active and durable electrocatalysts. The cell performance is always limited by the oxygen reduction reaction (ORR) on the cathode since it is at least 6 orders of magnitude slower than the hydrogen oxidation on the anode. Therefore high loading of Pt is required. Catalyst corrosion is also more significant on the cathode, especially in case of mobile applications, where rapid changes of loading have to be tolerated. Pt-Sn bulk alloys and SnO2-decorated Pt3Sn nanostructures are among the most studied bimetallic systems for fuel cell applications. Exclusive formation of supported Sn-Pt alloy phases with different Pt/Sn ratios can be achieved by using controlled surface reactions (CSRs) between hydrogen adsorbed on Pt sites and tetraethyl tin. In this contribution our results for commercial and a home-made 20 wt.% Pt/C catalysts modified by tin anchoring via CSRs are presented. The parent Pt/C catalysts were synthesized by modified NaBH4-assisted ethylene-glycol reduction method using ethanol as a solvent, which resulted either in dispersed and highly stable Pt nanoparticles or evenly distributed raspberry-like agglomerates according to the chosen synthesis parameters. The 20 wt.% Pt/C catalysts prepared that way showed improved electrocatalytic performance in the ORR and stability in comparison to the commercial 20 wt.% Pt/C catalysts. Then, in order to obtain Sn-Pt/C catalysts with Pt/Sn= 3 ratio, the Pt/C catalysts were modified with tetraethyl tin (SnEt4) using three and five consecutive tin anchoring periods. According to in situ XPS studies in case of catalysts with highly dispersed Pt nanoparticles, pre-treatment in hydrogen even at 170°C resulted in complete reduction of the ionic tin to Sn0. No evidence of the presence of SnO2 phase was found by means of the XRD and EDS analysis. These results demonstrate that the method of CSRs is a powerful tool to create Pt-Sn bimetallic nanoparticles exclusively, without tin deposition onto the carbon support. On the contrary, the XPS results revealed that the tin-modified catalysts with raspberry-like Pt agglomerates always contained a fraction of non-reducible tin oxide. At the same time, they showed increased activity and long-term stability in the ORR than Pt/C, which was assigned to the presence of SnO2 in close proximity/contact with Pt-Sn alloy phase. It has been demonstrated that the content and dispersion of the fcc Pt3Sn phase within the electrocatalysts can be controlled by tuning the reaction conditions of CSRs. The bimetallic catalysts displayed an outstanding performance in the ORR. The preparation of a highly dispersed 20Pt/C catalyst permits to decrease the Pt content without relevant decline in the electrocatalytic performance of the catalysts.

Keywords: anode catalyst, cathode catalyst, controlled surface reactions, oxygen reduction reaction, PtSn/C electrocatalyst

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Authors: Hamda M. Al-Ali

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From addressing fundamental questions about the history of the solar system to exploring other planets for any signs of life have always been the core of human space exploration. This triggered humans to explore whether other planets such as Mars could support human life on them. Therefore, many planned space missions to other planets have been designed and conducted to examine the feasibility of human survival on them. However, space missions are expensive and consume a large number of various resources to be successful. To overcome these problems, material efficiency shall be maximized through the use of reusable launch vehicles (RLV) rather than disposable and expendable ones. Material efficiency is defined as a way to achieve service requirements using fewer materials to reduce CO2 emissions from industrial processes. Materials such as aluminum-lithium alloys, steel, Kevlar, and reinforced carbon-carbon composites used in the manufacturing of spacecrafts could be reused in closed-loop cycles directly or by adding a protective coat. Material efficiency is a fundamental principle of a circular economy. The circular economy aims to cutback waste and reduce pollution through maximizing material efficiency so that businesses can succeed and endure. Five strategies have been proposed to improve material efficiency in the space industry, which includes waste minimization, introduce Key Performance Indicators (KPIs) to measure material efficiency, and introduce policies and legislations to improve material efficiency in the space sector. Another strategy to boost material efficiency is through maximizing resource and energy efficiency through material reusability. Furthermore, the environmental effects associated with the rapid growth in the number of space missions include black carbon emissions that lead to climate change. The levels of emissions must be tracked and tackled to ensure the safe utilization of space in the future. The aim of this research paper is to examine and suggest effective methods used to improve material efficiency in space missions so that space and Earth become more environmentally and economically sustainable. The objectives used to fulfill this aim are to identify the materials used in space missions that are suitable to be reused in closed-loop cycles considering material efficiency indicators and circular economy concepts. An explanation of how spacecraft materials could be re-used as well as propose strategies to maximize material efficiency in order to make RLVs possible so that access to space becomes affordable and reliable is provided. Also, the economic viability of the RLVs is examined to show the extent to which the use of RLVs has on the reduction of space mission costs. The environmental and economic implications of the increase in the number of space missions as a result of the use of RLVs are also discussed. These research questions are studied through detailed critical analysis of the literature, such as published reports, books, scientific articles, and journals. A combination of keywords such as material efficiency, circular economy, RLVs, and spacecraft materials were used to search for appropriate literature.

Keywords: access to space, circular economy, material efficiency, reusable launch vehicles, spacecraft materials

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Authors: Nihad Chakri, Btissam El Amrani, Faouzi Berrada, Halima Jounaid, Fouad Amraoui

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Public baths or hammams play an essential role in the Moroccan urban and peri-urban fabric, constituting part of the cultural heritage. Urbanization in Morocco has led to a significant increase in the number of these traditional hammams: between 6,000 and 15,000 units (to be updated) operate with a traditional heating system. Numerous studies on energy consumption indicate that a hammam consumes between 60 and 120m3 of water and one to two tons of wood per day. On average, one ton of wood costs 650 Moroccan dirhams (approximately 60 Euros), resulting in a daily fuel cost of around 1300 Moroccan dirhams (about 120 Euros). These high consumptions result in significant environmental nuisances generated by: Wastewater: in the case of hammams located on the outskirts of Casablanca, such as our study area, the Municipality of Dar Bouazza, most of these waters are directly discharged into the receiving environment without prior treatment because they are not connected to the sanitation network. Emissions of black smoke and ashes produced by the often incomplete combustion of wood. Reducing the liquid and gas emissions generated by these hammams thus poses an environmental and sustainable development challenge that needs to be addressed. In this context, we initiated the Eco-hammam project with the objective of implementing innovative and locally adapted solutions to limit the negative impacts of hammams on the environment and reduce water and wood energy consumption. This involves treating and reusing wastewater through a compact system with heat recovery and using alternative energy sources to increase and enhance the energy efficiency of these traditional hammams. To achieve this, on-site surveys of hammams in the Dar Bouazza Municipality and the application of statistical approaches to the results of the physico-chemical and bacteriological characterization of incoming and outgoing water from these units were conducted. This allowed us to establish an environmental diagnosis of these entities. In conclusion, the analysis of well water used by Dar Bouazza's hammams revealed the presence of certain parameters that could be hazardous to public health, such as total germs, total coliforms, sulfite-reducing spores, chromium, nickel, and nitrates. Therefore, this work primarily focuses on prospecting upstream of our study area to verify if other sources of pollution influence the quality of well water.

Keywords: public baths, hammams, cultural heritage, urbanization, water consumption, wood consumption, environmental nuisances, wastewater, environmental challenge, sustainable development, Eco-hammam project, innovative solutions, local adaptation, negative impacts, water conservation, wastewater treatment, heat recovery, alternative energy sources, on-site surveys, Dar Bouazza Municipality, statistical approaches, physico-chemical characterization, bacteriological characterization, environmental diagnosis, well water analysis, public health, pollution sources, well water quality

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Authors: O. Bilbao, I. Loizaga, F. A. Girot, A. Torregaray

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The current energetical situation and the high competitiveness in industrial sectors as the automotive one have become the development of new manufacturing processes with less energy and raw material consumption a real necessity. As consequence, new forming processes related with high temperature hot forging in closed dies have emerged in the last years as new solutions to expand the possibilities of hot forging and iron casting in the automotive industry. These technologies are mid-way between hot forging and semi-solid metal processes, working at temperatures higher than the hot forging but below the solidus temperature or the semi solid range, where no liquid phase is expected. This represents an advantage comparing with semi-solid forming processes as thixoforging, by the reason that no so high temperatures need to be reached in the case of high melting point alloys as steels, reducing the manufacturing costs and the difficulties associated to semi-solid processing of them. Comparing with hot forging, this kind of technologies allow the production of parts with as forged properties and more complex and near-net shapes (thinner sidewalls), enhancing the possibility of designing lightweight components. From the process viewpoint, the forging forces are significantly decreased, and a significant reduction of the raw material, energy consumption, and the forging steps have been demonstrated. Despite the mentioned advantages, from the material behavior point of view, the expansion of these technologies has shown the necessity of developing new material flow behavior models in the process working temperature range to make the simulation or the prediction of these new forming processes feasible. Moreover, the knowledge of the material flow behavior at the working temperature range also allows the design of the new closed dies concept required. In this work, the flow behavior characterization in the mentioned temperature range of the widely used in automotive commercial components 42CrMo4 steel has been studied. For that, hot compression tests have been carried out in a thermomechanical tester in a temperature range that covers the material behavior from the hot forging until the NDT (Nil Ductility Temperature) temperature (1250 ºC, 1275 ºC, 1300 ºC, 1325 ºC, 1350ºC, and 1375 ºC). As for the strain rates, three different orders of magnitudes have been considered (0,1 s-1, 1s-1, and 10s-1). Then, results obtained from the hot compression tests have been treated in order to adapt or re-write the Spittel model, widely used in automotive commercial softwares as FORGE® that restrict the current existing models up to 1250ºC. Finally, the obtained new flow behavior model has been validated by the process simulation in a commercial automotive component and the comparison of the results of the simulation with the already made experimental tests in a laboratory cellule of the new technology. So as a conclusion of the study, a new flow behavior model for the 42CrMo4 steel in the new working temperature range and the new process simulation in its application in automotive commercial components has been achieved and will be shown.

Keywords: 42CrMo4 high temperature flow behavior, high temperature hot forging in closed dies, simulation of automotive commercial components, spittel flow behavior model

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Authors: Masood Otarod, Ronald M. Supkowski

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This abstract discusses a method that reduces the general dispersion model in cylindrical coordinates to a second order linear ordinary differential equation with constant coefficients so that it can be utilized to conduct kinetic studies in packed bed tubular catalytic reactors at a broad range of Reynolds numbers. The model was tested by 13CO isotope transient tracing of the CO adsorption of Boudouard reaction in a differential reactor at an average Reynolds number of 0.2 over Pd-Al2O3 catalyst. Detailed experimental results have provided evidence for the validity of the theoretical framing of the model and the estimated parameters are consistent with the literature. The solution of the general dispersion model requires the knowledge of the radial distribution of axial velocity. This is not always known. Hence, up until now, the implementation of the dispersion model has been largely restricted to the plug-flow regime. But, ideal plug-flow is impossible to achieve and flow regimes approximating plug-flow leave much room for debate as to the validity of the results. The reduction of the general dispersion model transpires as a result of the application of a factorization theorem. Factorization theorem is derived from the observation that a cross section of a catalytic bed consists of a solid phase across which the reaction takes place and a void or porous phase across which no significant measure of reaction occurs. The disparity in flow and the heterogeneity of the catalytic bed cause the concentration of reacting compounds to fluctuate radially. These variabilities signify the existence of radial positions at which the radial gradient of concentration is zero. Succinctly, factorization theorem states that a concentration function of axial and radial coordinates in a catalytic bed is factorable as the product of the mean radial cup-mixing function and a contingent dimensionless function. The concentration of adsorbed compounds are also factorable since they are piecewise continuous functions and suffer the same variability but in the reverse order of the concentration of mobile phase compounds. Factorability is a property of packed beds which transforms the general dispersion model to an equation in terms of the measurable mean radial cup-mixing concentration of the mobile phase compounds and mean cross-sectional concentration of adsorbed species. The reduced model does not require the knowledge of the radial distribution of the axial velocity. Instead, it is characterized by new transport parameters so denoted by Ωc, Ωa, Ωc, and which are respectively denominated convection coefficient cofactor, axial dispersion coefficient cofactor, and radial dispersion coefficient cofactor. These cofactors adjust the dispersion equation as compensation for the unavailability of the radial distribution of the axial velocity. Together with the rest of the kinetic parameters they can be determined from experimental data via an optimization procedure. Our data showed that the estimated parameters Ωc, Ωa Ωr, are monotonically correlated with the Reynolds number. This is expected to be the case based on the theoretical construct of the model. Computer generated simulations of methanation reaction on nickel provide additional support for the utility of the newly conceptualized dispersion model.

Keywords: factorization, general dispersion model, isotope transient kinetic, partial differential equations

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Authors: Alexia Wu, Joel Ribis, Jean-Christophe Brachet, Emmanuel Clouet, Benoit Arnal, Elodie Rouesne, Stéphane Urvoy, Justine Roubaud, Yves Serruys, Frederic Lepretre

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To enhance the safety of Light Water Reactor, accident tolerant fuel (ATF) claddings materials are under development. In the framework of CEA-AREVA-EDF collaborative program on ATF cladding materials, CEA has engaged specific studies on chromium coated zirconium alloys. Especially for Loss-of-Coolant-Accident situations, chromium coated claddings have shown some additional 'coping' time before achieving full embrittlement of the oxidized cladding, when compared to uncoated references – both tested in steam environment up to 1300°C. Nevertheless, the behavior of chromium coatings and the stability of the Zr-Cr interface under neutron irradiation remain unknown. Two main points are addressed: 1. Bulk Cr behavior under irradiation: Due to its BCC crystallographic structure, Cr is prone to Ductile-to-Brittle-Transition at quite high temperature. Irradiation could be responsible for a significant additional DBTT shift towards higher temperatures. 2. Zircaloy/Cr interface behavior under irradiation: Preliminary TEM examinations of un-irradiated samples revealed a singular Zircaloy-4/Cr interface with nanometric intermetallic phase layers. Such particular interfaces highlight questions of how they would behave under irradiation - intermetallic zirconium phases are known to be more or less stable under irradiations. Another concern is a potential enhancement of chromium diffusion into the zirconium-alpha based substrate. The purpose of this study is then to determine the behavior of such coatings after ion irradiations, as a surrogate to neutron irradiation. Ion irradiations were performed at the Jannus-Saclay facility (France). 20 MeV Kr8+ ions at 400°C with a flux of 2.8x1011 ions.cm-2.s-1 were used to irradiate chromium coatings of 1-2 µm thick on Zircaloy-4 sheets substrate. At the interface, the calculated damage is close to 10 dpa (SRIM, Quick Calculation Damage mode). Thin foil samples were prepared with FIB for both as-received and irradiated coated samples. Transmission Electron Microscopy (TEM) and in-situ tensile tests in a Scanning Electron Microscope are being used to characterize the un-irradiated and irradiated materials. High Resolution TEM highlights a great complexity of the interface before irradiation since it is formed of an alternation of intermetallic phases – C14 and C15. The interfaces formed by these intermetallic phases with chromium and zirconium show semi-coherency. Chemical analysis performed before irradiation shows some iron enrichment at the interface. The chromium coating bulk microstructures and properties are also studied before and after irradiation. On-going in-situ tensile tests focus on the capacity of chromium coatings to sustain some plastic deformation when tested up to 350°C. The stability of the Cr/Zr interface is shown after ion irradiation up to 10 dpa. This observation constitutes the first result after irradiation on these new coated claddings materials.

Keywords: accident tolerant fuel, HRTEM, interface, ion-irradiation

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Authors: Mohamed Habireche, Nacer E. Bacha, Mohamed Djeghdjough

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In the brick industry, smooth double roll crusher is used for medium and fine crushing of soft to medium hard material. Due to opposite inward rotation of the rolls, the feed material is nipped between the rolls and crushed by compression. They are subject to intense wear, known as three-body abrasion, due to the action of abrasive products. The production downtime affecting productivity stems from two sources: the bi-monthly rectification of the roll crushers and their replacement when they are completely worn out. Choosing the right material for the roll crushers should result in longer machine cycles, and reduced repair and maintenance costs. All roll crushers are imported from outside Algeria. This results in sometimes very long delivery times which handicap the brickyards, in particular in respecting delivery times and honored the orders made by customers. The aim of this work is to investigate the effect of alloying additions on microstructure and wear behavior of grey lamellar cast iron for smooth roll crushers in brick industry. The base gray iron was melted in an induction furnace with low frequency at a temperature of 1500 °C, in which return cast iron scrap, new cast iron ingot, and steel scrap were added to the melt to generate the desired composition. The chemical analysis of the bar samples was carried out using Emission Spectrometer Systems PV 8050 Series (Philips) except for the carbon, for which a carbon/sulphur analyser Elementrac CS-i was used. Unetched microstructure was used to evaluate the graphite flake morphology using the image comparison measurement method. At least five different fields were selected for quantitative estimation of phase constituents. The samples were observed under X100 magnification with a Zeiss Axiover T40 MAT optical microscope equipped with a digital camera. SEM microscope equipped with EDS was used to characterize the phases present in the microstructure. The hardness (750 kg load, 5mm diameter ball) was measured with a Brinell testing machine for both treated and as-solidified condition test pieces. The test bars were used for tensile strength and metallographic evaluations. Mechanical properties were evaluated using tensile specimens made as per ASTM E8 standards. Two specimens were tested for each alloy. From each rod, a test piece was made for the tensile test. The results showed that the quenched and tempered alloys had best wear resistance at 400 °C for alloyed grey cast iron (containing 0.62%Mn, 0.68%Cr, and 1.09% Cu) due to fine carbides in the tempered matrix. In quenched and tempered condition, increasing Cu content in cast irons improved its wear resistance moderately. Combined addition of Cu and Cr increases hardness and wear resistance for a quenched and tempered hypoeutectic grey cast iron.

Keywords: casting, cast iron, microstructure, heat treating

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Authors: Igor B. Sivaev

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Design of molecular machines is an extraordinary growing and very important area of research that it was recognized by awarding Sauvage, Stoddart and Feringa the Nobel Prize in Chemistry in 2016 'for the design and synthesis of molecular machines'. Based on the type of motion being performed, molecular machines can be divided into two main types: molecular motors and molecular switches. Molecular switches are molecules or supramolecular complexes having bistability, i.e., the ability to exist in two or more stable forms, among which may be reversible transitions under external influence (heating, lighting, changing the medium acidity, the action of chemicals, exposure to magnetic or electric field). Molecular switches are the main structural element of any molecular electronics devices. Therefore, the design and the study of molecules and supramolecular systems capable of performing mechanical movement is an important and urgent problem of modern chemistry. There is growing interest in molecular switches and other devices of molecular electronics based on transition metal complexes; therefore choice of suitable stable organometallic unit is of great importance. An example of such unit is bis(dicarbollide) complexes of transition metals [3,3’-M(1,2-C₂B₉H₁₁)₂]ⁿ⁻. The control on the ligand rotation in such complexes can be reached by introducing substituents which could provide stabilization of certain rotamers due to specific interactions between the ligands, on the one hand, and which can participate as Lewis bases in complex formation with external metals resulting in a change in the rotation angle of the ligands, on the other hand. A series of isomeric methyl sulfide derivatives of cobalt bis(dicarbollide) complexes containing methyl sulfide substituents at boron atoms in different positions of the pentagonal face of the dicarbollide ligands [8,8’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻, rac-[4,4’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ and meso-[4,7’-(MeS)₂-3,3’-Co(1,2-C₂B₉H₁₀)₂]⁻ were synthesized by the reaction of CoCl₂ with the corresponding methyl sulfide carborane derivatives [10-MeS-7,8-C₂B₉H₁₁)₂]⁻ and [10-MeS-7,8-C₂B₉H₁₁)₂]⁻. In the case of asymmetrically substituted cobalt bis(dicarbollide) complexes the corresponding rac- and meso-isomers were successfully separated by column chromatography as the tetrabutylammonium salts. The compounds obtained were studied by the methods of ¹H, ¹³C, and ¹¹B NMR spectroscopy, single crystal X-ray diffraction, cyclic voltammetry, controlled potential coulometry and quantum chemical calculations. It was found that in the solid state, the transoid- and gauche-conformations of the 8,8’- and 4,4’-isomers are stabilized by four intramolecular CH···S(Me)B hydrogen bonds each one (2.683-2.712 Å and 2.709-2.752 Å, respectively), whereas gauche-conformation of the 4,7’-isomer is stabilized by two intramolecular CH···S hydrogen bonds (2.699-2.711 Å). The existence of the intramolecular CH·S(Me)B hydrogen bonding in solutions was supported by the 1H NMR spectroscopy. These data are in a good agreement with results of the quantum chemical calculations. The corresponding iron and nickel complexes were synthesized as well. The reaction of the methyl sulfide derivatives of cobalt bis(dicarbollide) with various labile transition metal complexes results in rupture of intramolecular hydrogen bonds and complexation of the methyl sulfide groups with external metal. This results in stabilization of other rotational conformation of cobalt bis(dicarbollide) and can be used in design of molecular switches. This work was supported by the Russian Science Foundation (16-13-10331).

Keywords: molecular switches, NMR spectroscopy, single crystal X-ray diffraction, transition metal bis(dicarbollide) complexes, quantum chemical calculations

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Authors: J. Martin, A. Nominé, T. Czerwiec, G. Henrion, T. Belmonte

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The plasma electrolytic oxidation (PEO) is a particular electrochemical process to produce protective oxide ceramic coatings on light-weight metals (Al, Mg, Ti). When applied to aluminum alloys, the resulting PEO coating exhibit improved wear and corrosion resistance because thick, hard, compact and adherent crystalline alumina layers can be achieved. Several investigations have been carried out to improve the efficiency of the PEO process and one particular way consists in tuning the suitable electrical regime. Despite the considerable interest in this process, there is still no clear understanding of the underlying discharge mechanisms that make possible metal oxidation up to hundreds of µm through the ceramic layer. A key parameter that governs the PEO process is the numerous short-lived micro-discharges (micro-plasma in liquid) that occur continuously over the processed surface when the high applied voltage exceeds the critical dielectric breakdown value of the growing ceramic layer. By using a bipolar pulsed current to supply the electrodes, we previously observed that micro-discharges are delayed with respect to the rising edge of the anodic current. Nevertheless, explanation of the origin of such phenomena is still not clear and needs more systematic investigations. The aim of the present communication is to identify the relationship that exists between this delay and the mechanisms responsible of the oxide growth. For this purpose, the delay of micro-discharges ignition is investigated as the function of various electrical parameters such as the current density (J), the current pulse frequency (F) and the anodic to cathodic charge quantity ratio (R = Qp/Qn) delivered to the electrodes. The PEO process was conducted on Al2214 aluminum alloy substrates in a solution containing potassium hydroxide [KOH] and sodium silicate diluted in deionized water. The light emitted from micro-discharges was detected by a photomultiplier and the micro-discharge parameters (number, size, life-time) were measured during the process by means of ultra-fast video imaging (125 kfr./s). SEM observations and roughness measurements were performed to characterize the morphology of the elaborated oxide coatings while XRD was carried out to evaluate the amount of corundum -Al203 phase. Results show that whatever the applied current waveform, the delay of micro-discharge appearance increases as the process goes on. Moreover, the delay is shorter when the current density J (A/dm2), the current pulse frequency F (Hz) and the ratio of charge quantity R are high. It also appears that shorter delays are associated to stronger micro-discharges (localized, long and large micro-discharges) which have a detrimental effect on the elaborated oxide layers (thin and porous). On the basis of the results, a model for the growth of the PEO oxide layers will be presented and discussed. Experimental results support that a mechanism of electrical charge accumulation at the oxide surface / electrolyte interface takes place until the dielectric breakdown occurs and thus until micro-discharges appear.

Keywords: aluminium, micro-discharges, oxidation mechanisms, plasma electrolytic oxidation

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Authors: Till Fehlauer, Blanche Collin, Bernard Angeletti, Andrea Somogyi, Claire Lallemand, Perrine Chaurand, Cédric Dentant, Clement Levard, Jerome Rose

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Over the last decades, yttrium (Y) has gained importance in high-tech applications. It is an essential part of alloys and compounds used for lasers, displays, or cell phones, for example. Due to its chemical similarities with the lanthanides, Y is often considered a rare earth element (REE). Despite their increased usage, the environmental behavior of REEs remains poorly understood. Especially regarding their interactions with plants, many uncertainties exist. On the one hand, Y is known to have a negative effect on root development and germination, but on the other hand, it appears to promote plant growth at low concentrations. In order to understand these phenomena, a precise knowledge is necessary about how Y is absorbed by the plant and how it is handled once inside the organism. Contradictory studies exist, stating that due to a similar ionic radius, Y and the other REEs might be absorbed through Ca²⁺-channels, while others suspect that Y has a shared pathway with Al³⁺. In this study, laser ablation coupled ICP-MS, and synchrotron-based micro-X-ray fluorescence (µXRF, beamline Nanoscopium, SOLEIL, France) have been used in order to localize Y within the plant tissue and identify associated elements. The plant used in this study is Saxifraga paniculata, a rugged alpine plant that has shown an affinity for Y in previous studies (in prep.). Furthermore, Saxifraga paniculata performs guttation, which means that it possesses phloem sap secreting openings on the leaf surface that serve to regulate root pressure. These so-called hydathodes could provide special insights in elemental transport in plants. The plants have been grown on Y doped soil (500mg/kg DW) for four months. The results showed that Y was mainly concentrated in the roots of Saxifraga paniculata (260 ± 85mg/kg), and only a small amount was translocated to the leaves (10 ± 7.8mg/kg). µXRF analysis indicated that within the root transects, the majority of Y remained in the epidermis and hardly penetrated the stele. Laser ablation coupled ICP-MS confirmed this finding and showed a positive correlation in the roots between Y, Fe, Al, and to a lesser extent Ca. In the stem transect, Y was mainly detected in a hotspot of approximately 40µm in diameter situated in the endodermis area. Within the stem and especially in the hotspot, Y was highly colocalized with Al and Fe. Similar-sized Y hotspots have been detected in/on the leaves. All of them were strongly colocalized with Al and Fe, except for those situated within the hydathodes, which showed no colocalization with any of the measured elements. Accordingly, a relation between Y and Ca during root uptake remains possible, whereas a correlation to Fe and Al appears to be dominant in the aerial parts, suggesting common storage compartments, the formation of complexes, or a shared pathway during translocation.

Keywords: laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), Phytoaccumulation, Rare earth elements, Saxifraga paniculata, Synchrotron-based micro-X-ray fluorescence, Yttrium

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Authors: Hamda M. Al-Ali

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The ultimate aim of space exploration has been centralized around the possibility of life on other planets in the solar system. This aim is driven by the detrimental effects that climate change could potentially have on human survival on Earth in the future. This drives humans to search for feasible solutions to increase environmental and economical sustainability on Earth and to evaluate and explore the ability of human survival on other planets such as Mars. To do that, frequent space missions are required to meet the ambitious human goals. This means that reliable and affordable access to space is required, which could be largely achieved through the use of reusable spacecrafts. Therefore, materials and resources must be used wisely to meet the increasing demand. Space missions are currently extremely expensive to operate. However, reusing materials hence spacecrafts, can potentially reduce overall mission costs as well as the negative impact on both space and Earth environments. This is because reusing materials leads to less waste generated per mission, and therefore fewer landfill sites are required. Reusing materials reduces resource consumption, material production, and the need for processing new and replacement spacecraft and launch vehicle parts. Consequently, this will ease and facilitate human access to outer space as it will reduce the demand for scarce resources, which will boost material efficiency in the space industry. Material efficiency expresses the extent to which resources are consumed in the production cycle and how the waste produced by the industrial process is minimized. The strategies proposed in this paper to boost material efficiency in the space sector are the introduction of key performance indicators that are able to measure material efficiency as well as the introduction of clearly defined policies and legislation that can be easily implemented within the general practices in the space industry. Another strategy to improve material efficiency is by amplifying energy and resource efficiency through reusing materials. The circularity of various spacecraft materials such as Kevlar, steel, and aluminum alloys could be maximized through reusing them directly or after galvanizing them with another layer of material to act as a protective coat. This research paper has an aim to investigate and discuss how to improve material efficiency in space missions considering circular economy concepts so that space and Earth become more economically and environmentally sustainable. The circular economy is a transition from a make-use-waste linear model to a closed-loop socio-economic model, which is regenerative and restorative in nature. The implementation of a circular economy will reduce waste and pollution through maximizing material efficiency, ensuring that businesses can thrive and sustain. Further research into the extent to which reusable launch vehicles reduce space mission costs have been discussed, along with the environmental and economic implications it could have on the space sector and the environment. This has been examined through research and in-depth literature review of published reports, books, scientific articles, and journals. Keywords such as material efficiency, circular economy, reusable launch vehicles and spacecraft materials were used to search for relevant literature.

Keywords: circular economy, key performance indicator, material efficiency, reusable launch vehicles, spacecraft materials

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Authors: Reyna Singh, David Lokhat, Milan Carsky

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The world crude oil demand is projected to rise to 108.5 million bbl/d by the year 2035. With reserves estimated at 869 billion tonnes worldwide, coal is an abundant resource. This work was aimed at producing a high value hydrocarbon liquid product from the Direct Coal Liquefaction (DCL) process at, comparatively, mild operating conditions. Via hydrogenation, the temperature-staged approach was investigated. In a two reactor lab-scale pilot plant facility, the objectives included maximising thermal dissolution of the coal in the presence of a hydrogen donor solvent in the first stage, subsequently promoting hydrogen saturation and hydrodesulphurization (HDS) performance in the second. The feed slurry consisted of high grade, pulverized bituminous coal on a moisture-free basis with a size fraction of < 100μm; and Tetralin mixed in 2:1 and 3:1 solvent/coal ratios. Magnetite (Fe3O4) at 0.25wt% of the dry coal feed was added for the catalysed runs. For both stages, hydrogen gas was used to maintain a system pressure of 100barg. In the first stage, temperatures of 250℃ and 300℃, reaction times of 30 and 60 minutes were investigated in an agitated batch reactor. The first stage liquid product was pumped into the second stage vertical reactor, which was designed to counter-currently contact the hydrogen rich gas stream and incoming liquid flow in the fixed catalyst bed. Two commercial hydrotreating catalysts; Cobalt-Molybdenum (CoMo) and Nickel-Molybdenum (NiMo); were compared in terms of their conversion, selectivity and HDS performance at temperatures 50℃ higher than the respective first stage tests. The catalysts were activated at 300°C with a hydrogen flowrate of approximately 10 ml/min prior to the testing. A gas-liquid separator at the outlet of the reactor ensured that the gas was exhausted to the online VARIOplus gas analyser. The liquid was collected and sampled for analysis using Gas Chromatography-Mass Spectrometry (GC-MS). Internal standard quantification methods for the sulphur content, the BTX (benzene, toluene, and xylene) and alkene quality; alkanes and polycyclic aromatic hydrocarbon (PAH) compounds in the liquid products were guided by ASTM standards of practice for hydrocarbon analysis. In the first stage, using a 2:1 solvent/coal ratio, an increased coal to liquid conversion was favoured by a lower operating temperature of 250℃, 60 minutes and a system catalysed by magnetite. Tetralin functioned effectively as the hydrogen donor solvent. A 3:1 ratio favoured increased concentrations of the long chain alkanes undecane and dodecane, unsaturated alkenes octene and nonene and PAH compounds such as indene. The second stage product distribution showed an increase in the BTX quality of the liquid product, branched chain alkanes and a reduction in the sulphur concentration. As an HDS performer and selectivity to the production of long and branched chain alkanes, NiMo performed better than CoMo. CoMo is selective to a higher concentration of cyclohexane. For 16 days on stream each, NiMo had a higher activity than CoMo. The potential to cover the demand for low–sulphur, crude diesel and solvents from the production of high value hydrocarbon liquid in the said process, is thus demonstrated.

Keywords: catalyst, coal, liquefaction, temperature-staged

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Authors: Oscar Bareiro, Johannes Sackmann, Thomas Gries

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Carbon fiber reinforced polymer composites (CFRP) are used in a wide variety of applications due to its advantageous properties and design versatility. The braiding process enables the manufacture of components with good toughness and fatigue strength. However, failure mechanisms of CFRPs are complex and still present challenges associated with their maintenance and repair. Within the broad scope of structural health monitoring (SHM), strain monitoring can be applied to composite materials to improve reliability, reduce maintenance costs and safely exhaust service life. Traditional SHM systems employ e.g. fiber optics, piezoelectrics as sensors, which are often expensive, time consuming and complicated to implement. A cost-efficient alternative can be the exploitation of the conductive properties of fiber-based sensors such as carbon, copper, or constantan - a copper-nickel alloy – that can be utilized as sensors within composite structures to achieve strain monitoring. This allows the structure to provide feedback via electrical signals to a user which are essential for evaluating the structural condition of the structure. This work presents a strategy for the in-process integration of resistance-based sensors (Elektrisola Feindraht AG, CuNi23Mn, Ø = 0.05 mm) into textile preforms during its manufacture via the braiding process (Herzog RF-64/120) to achieve strain monitoring of braided composites. For this, flat samples of instrumented composite laminates of carbon fibers (Toho Tenax HTS40 F13 24K, 1600 tex) and epoxy resin (Epikote RIMR 426) were manufactured via vacuum-assisted resin infusion. These flat samples were later cut out into test specimens and the integrated sensors were wired to the measurement equipment (National Instruments, VB-8012) for data acquisition during the execution of mechanical tests. Quasi-static tests were performed (tensile, 3-point bending tests) following standard protocols (DIN EN ISO 527-1 & 4, DIN EN ISO 14132); additionally, dynamic tensile tests were executed. These tests were executed to assess the sensor response under different loading conditions and to evaluate the influence of the sensor presence on the mechanical properties of the material. Several orientations of the sensor with regards to the applied loading and sensor placements inside the laminate were tested. Strain measurements from the integrated sensors were made by programming a data acquisition code (LabView) written for the measurement equipment. Strain measurements from the integrated sensors were then correlated to the strain/stress state for the tested samples. From the assessment of the sensor integration approach it can be concluded that it allows for a seamless sensor integration into the textile preform. No damage to the sensor or negative effect on its electrical properties was detected during inspection after integration. From the assessment of the mechanical tests of instrumented samples it can be concluded that the presence of the sensors does not alter significantly the mechanical properties of the material. It was found that there is a good correlation between resistance measurements from the integrated sensors and the applied strain. It can be concluded that the correlation is of sufficient accuracy to determinate the strain state of a composite laminate based solely on the resistance measurements from the integrated sensors.

Keywords: braiding process, in-process sensor integration, instrumented composite material, resistance-based sensor, strain monitoring

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Authors: Binbin Chen, Dennis Y. C. Leung

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Aluminium (Al) -air cell holds a high volumetric capacity density of 8.05 Ah cm-3, benefit from the trivalence of Al ions. Additional benefits of Al-air cell are low price and environmental friendliness. Furthermore, the Al energy conversion process is characterized of 100% recyclability in theory. Along with a large base of raw material reserve, Al attracts considerable attentions as a promising material to be integrated within the global energy system. However, despite the early successful applications in military services, several problems exist that prevent the Al-air cells from widely civilian use. The most serious issue is the parasitic corrosion of Al when contacts with electrolyte. To overcome this problem, super-pure Al alloyed with various traces of metal elements are used to increase the corrosion resistance. Nevertheless, high-purity Al alloys are costly and require high energy consumption during production process. An alternative approach is to add inexpensive inhibitors directly into the electrolyte. However, such additives would increase the internal ohmic resistance and hamper the cell performance. So far these methods have not provided satisfactory solutions for the problem within Al-air cells. For the operation of alkaline Al-air cell, there are still other minor problems. One of them is the formation of aluminium hydroxide in the electrolyte. This process decreases ionic conductivity of electrolyte. Another one is the carbonation process within the gas diffusion layer of cathode, blocking the porosity of gas diffusion. Both these would hinder the performance of cells. The present work optimizes the above problems by building an Al-air cell operation system, consisting of four components. A top electrolyte tank containing fresh electrolyte is located at a high level, so that it can drive the electrolyte flow by gravity force. A mechanical rechargeable Al-air cell is fabricated with low-cost materials including low grade Al, carbon paper, and PMMA plates. An electrolyte waste tank with elaborate channel is designed to separate the hydrogen generated from the corrosion, which would be collected by gas collection device. In the first section of the research work, we investigated the performance of the mechanical rechargeable Al-air cell with a constant flow rate of electrolyte, to ensure the repeatability experiments. Then the whole system was assembled together and the feasibility of operating was demonstrated. During experiment, pure hydrogen is collected by collection device, which holds potential for various applications. By collecting this by-product, high utilization efficiency of aluminum is achieved. Considering both electricity and hydrogen generated, an overall utilization efficiency of around 90 % or even higher under different working voltages are achieved. Fluidic electrolyte could remove aluminum hydroxide precipitate and solve the electrolyte deterioration problem. This operation system provides a low-cost strategy for harvesting energy from the abundant secondary Al. The system could also be applied into other metal-air cells and is suitable for emergency power supply, power plant and other applications. The low cost feature implies great potential for commercialization. Further optimization, such as scaling up and optimization of fabrication, will help to refine the technology into practical market offerings.

Keywords: aluminium-air cell, high efficiency, hydrogen, mechanical recharge

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Authors: Hongyan Chen, Megan Jobson, Andrew J. Masters, Maria Gonzalez-Miquel, Simon Halstead, Mayri Diaz de Rienzo

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Ionic liquids offer excellent advantages over conventional solvents for industrial extraction of metals from aqueous solutions, where such extraction processes bring opportunities for recovery, reuse, and recycling of valuable resources and more sustainable production pathways. Recent research on the use of ionic liquids for extraction confirms their high selectivity and low volatility, but there is relatively little focus on how their properties can be best exploited in practice. This work addresses gaps in research on process modelling and simulation, to support development, design, and optimisation of these processes, focusing on the separation of the highly similar transition metals, cobalt, and nickel. The study exploits published experimental results, as well as new experimental results, relating to the separation of Co and Ni using trihexyl (tetradecyl) phosphonium chloride. This extraction agent is attractive because it is cheaper, more stable and less toxic than fluorinated hydrophobic ionic liquids. This process modelling work concerns selection and/or development of suitable models for the physical properties, distribution coefficients, for mass transfer phenomena, of the extractor unit and of the multi-stage extraction flowsheet. The distribution coefficient model for cobalt and HCl represents an anion exchange mechanism, supported by the literature and COSMO-RS calculations. Parameters of the distribution coefficient models are estimated by fitting the model to published experimental extraction equilibrium results. The mass transfer model applies Newman’s hard sphere model. Diffusion coefficients in the aqueous phase are obtained from the literature, while diffusion coefficients in the ionic liquid phase are fitted to dynamic experimental results. The mass transfer area is calculated from the surface to mean diameter of liquid droplets of the dispersed phase, estimated from the Weber number inside the extractor. New experiments measure the interfacial tension between the aqueous and ionic phases. The empirical models for predicting the density and viscosity of solutions under different metal loadings are also fitted to new experimental data. The extractor is modelled as a continuous stirred tank reactor with mass transfer between the two phases and perfect phase separation of the outlet flows. A multistage separation flowsheet simulation is set up to replicate a published experiment and compare model predictions with the experimental results. This simulation model is implemented in gPROMS software for dynamic process simulation. The results of single stage and multi-stage flowsheet simulations are shown to be in good agreement with the published experimental results. The estimated diffusion coefficient of cobalt in the ionic liquid phase is in reasonable agreement with published data for the diffusion coefficients of various metals in this ionic liquid. A sensitivity study with this simulation model demonstrates the usefulness of the models for process design. The simulation approach has potential to be extended to account for other metals, acids, and solvents for process development, design, and optimisation of extraction processes applying ionic liquids for metals separations, although a lack of experimental data is currently limiting the accuracy of models within the whole framework. Future work will focus on process development more generally and on extractive separation of rare earths using ionic liquids.

Keywords: distribution coefficient, mass transfer, COSMO-RS, flowsheet simulation, phosphonium

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Authors: Iryna P. Dzieciuch, Michael D. Putman

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Humidity is known to degrade Navy ship electronic equipment, especially in hot moist environments. If left untreated, it can cause significant and permanent damage. Even rigorous inspection and frequent clean-up would not prevent further equipment contamination and degradation because of the constant presence of favorable growth conditions for many microorganisms. Generally, relative humidity levels of less than 60% will inhibit corrosion in electronic equipment, but because NAVY electronics often operate in hot and humid environments, prevention via dehumidification is not always possible. Currently, there is no defined research that fully describes key mechanisms which cause electronics and its coating degradation. The corrosive action of most bacteria is mainly developed through (i) mycelium adherence to the metal plates, (ii) facilitation the formation of pitting areas, (iii) production of organic acids such as citric, iso-citric, cis-aconitic, alpha-ketoglutaric, which are corrosive to electronic equipment and its components. Our approach studies corrosive action in electronic equipment: circuit-board, wires and connections that are exposed in the humid environment that gets worse during condensation. In our new approach the technical task is built on work with the bacterial communities in public areas, bacterial genetics, bioinformatics, biostatistics and Scanning Electron Microscopy (SEM) of corroded circuit boards. Based on these methods, we collect and examine environmental samples from biofilms of the corroded and non-corroded sites, where bacterial contamination of electronic equipment, such as machine racks and shore boats, is an ongoing concern. Sample collection and sample analysis is focused on addressing the key questions identified above through the following tasks: laboratory sample processing and evaluation under scanning electron microscopy, initial sequencing and data evaluation; bioinformatics and data analysis. Preliminary results from scanning electron microscopy (SEM) have revealed that metal particulates and alloys in corroded samples consists mostly of Tin ( < 40%), Silicon ( < 4%), Sulfur ( < 1%), Aluminum ( < 2%), Magnesium ( < 2%), Copper ( < 1%), Bromine ( < 2%), Barium ( <1%) and Iron ( < 2%) elements. We have also performed X 12000 magnification of the same sites and that proved existence of undisrupted biofilm organelles and crystal structures. Non-corrosion sites have revealed high presence of copper ( < 47%); other metals remain at the comparable level as on the samples with corrosion. We have performed X 1000 magnification on the non-corroded at the sites and have documented formation of copper crystals. The next step of this study, is to perform metagenomics sequencing at all sites and to compare bacterial composition present in the environment. While copper is nontoxic to the living organisms, the process of bacterial adhesion creates acidic environment by releasing citric, iso-citric, cis-aconitic, alpha-ketoglutaric acidics, which in turn release copper ions Cu++, which that are highly toxic to the bacteria and higher order living organisms. This phenomenon, might explain natural “antibiotic” properties that are lacking in elements such as tin. To prove or deny this hypothesis we will use next - generation sequencing (NGS) methods to investigate types and growth cycles of bacteria that from bacterial biofilm the on corrosive and non-corrosive samples.

Keywords: bacteria, biofilm, circuit board, copper, corrosion, electronic equipment, organic acids, tin

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Authors: Keivan Davami, Michael Munther, Lloyd Hackel

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The control of properties and material behavior by implementing thermal-mechanical processes is based on mechanical deformation and annealing according to a precise schedule that will produce a unique and stable combination of grain structure, dislocation substructure, texture, and dispersion of precipitated phases. The authors recently developed a thermal-mechanical technique to stabilize the microstructure of additively manufactured nickel-based superalloys even after exposure to high temperatures. However, the mechanism(s) that controls this stability is still under investigation. Laser peening (LP), also called laser shock peening (LSP), is a shock based (50 ns duration) post-processing technique used for extending performance levels and improving service life of critical components by developing deep levels of plastic deformation, thereby generating high density of dislocations and inducing compressive residual stresses in the surface and deep subsurface of components. These compressive residual stresses are usually accompanied with an increase in hardness and enhance the material’s resistance to surface-related failures such as creep, fatigue, contact damage, and stress corrosion cracking. While the LP process enhances the life span and durability of the material, the induced compressive residual stresses relax at high temperatures (>0.5Tm, where Tm is the absolute melting temperature), limiting the applicability of the technology. At temperatures above 0.5Tm, the compressive residual stresses relax, and yield strength begins to drop dramatically. The principal reason is the increasing rate of solid-state diffusion, which affects both the dislocations and the microstructural barriers. Dislocation configurations commonly recover by mechanisms such as climbing and recombining rapidly at high temperatures. Furthermore, precipitates coarsen, and grains grow; virtually all of the available microstructural barriers become ineffective.Our results indicate that by using “cyclic” treatments with sequential LP and annealing steps, the compressive stresses survive, and the microstructure is stable after exposure to temperatures exceeding 0.5Tm for a long period of time. When the laser peening process is combined with annealing, dislocations formed as a result of LPand precipitates formed during annealing have a complex interaction that provides further stability at high temperatures. From a scientific point of view, this research lays the groundwork for studying a variety of physical, materials science, and mechanical engineering concepts. This research could lead to metals operating at higher sustained temperatures enabling improved system efficiencies. The strengthening of metals by a variety of means (alloying, work hardening, and other processes) has been of interest for a wide range of applications. However, the mechanistic understanding of the often complex processes of interactionsbetween dislocations with solute atoms and with precipitates during plastic deformation have largely remained scattered in the literature. In this research, the elucidation of the actual mechanisms involved in the novel cyclic LP/annealing processes as a scientific pursuit is investigated through parallel studies of dislocation theory and the implementation of advanced experimental tools. The results of this research help with the validation of a novel laser processing technique for high temperature applications. This will greatly expand the applications of the laser peening technology originally devised only for temperatures lower than half of the melting temperature.

Keywords: laser shock peening, mechanical properties, indentation, high temperature stability

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Authors: Zbigniew Czyz, Ksenia Siadkowska, Krzysztof Skiba, Karol Scislowski

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Today’s progress in the rotorcraft is mostly associated with an optimization of aircraft performance achieved by active and passive modifications of main rotor assemblies and a tail propeller. The key task is to improve their performance, improve the hover quality factor for rotors but not change in specific fuel consumption. One of the tasks to improve the helicopter is an active optimization of the main rotor providing for flight stages, i.e., an ascend, flight, a descend. An active interference with the airflow around the rotor blade section can significantly change characteristics of the aerodynamic airfoil. The efficiency of actuator systems modifying aerodynamic coefficients in the current solutions is relatively high and significantly affects the increase in strength. The solution to actively change aerodynamic characteristics assumes a periodic change of geometric features of blades depending on flight stages. Changing geometric parameters of blade warping enables an optimization of main rotor performance depending on helicopter flight stages. Structurally, an adaptation of shape memory alloys does not significantly affect rotor blade fatigue strength, which contributes to reduce costs associated with an adaptation of the system to the existing blades, and gains from a better performance can easily amortize such a modification and improve profitability of such a structure. In order to obtain quantitative and qualitative data to solve this research problem, a number of numerical analyses have been necessary. The main problem is a selection of design parameters of the main rotor and a preliminary optimization of its performance to improve the hover quality factor for rotors. This design concept assumes a three-bladed main rotor with a chord of 0.07 m and radius R = 1 m. The value of rotor speed is a calculated parameter of an optimization function. To specify the initial distribution of geometric warping, a special software has been created that uses a numerical method of a blade element which respects dynamic design features such as fluctuations of a blade in its joints. A number of performance analyses as a function of rotor speed, forward speed, and altitude have been performed. The calculations were carried out for the full model assembly. This approach makes it possible to observe the behavior of components and their mutual interaction resulting from the forces. The key element of each rotor is the shaft, hub and pins holding the joints and blade yokes. These components are exposed to the highest loads. As a result of the analysis, the safety factor was determined at the level of k > 1.5, which gives grounds to obtain certification for the strength of the structure. The construction of the joint rotor has numerous moving elements in its structure. Despite the high safety factor, the places with the highest stresses, where the signs of wear and tear may appear, have been indicated. The numerical analysis carried out showed that the most loaded element is the pin connecting the modular bearing of the blade yoke with the element of the horizontal oscillation joint. The stresses in this element result in a safety factor of k=1.7. The other analysed rotor components have a safety factor of more than 2 and in the case of the shaft, this factor is more than 3. However, it must be remembered that the structure is as strong as the weakest cell is. Designed rotor for unmanned aerial vehicles adapted to work with blades with intelligent materials in its structure meets the requirements for certification testing. Acknowledgement: This work has been financed by the Polish National Centre for Research and Development under the LIDER program, Grant Agreement No. LIDER/45/0177/L-9/17/NCBR/2018.

Keywords: main rotor, rotorcraft aerodynamics, shape memory alloy, materials, unmanned helicopter

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Authors: Mina Naeini, Thomas A. Adams II

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Solid Oxide Fuel Cells (SOFCs) feature high electrical efficiency and generate substantial amounts of waste heat that make them suitable for integrated community energy systems (ICEs). By harvesting and distributing the waste heat through hot water pipelines, SOFCs can meet thermal demand of the communities. Therefore, they can replace traditional gas boilers and reduce greenhouse gas (GHG) emissions. Despite these advantages of SOFCs over competing power generation units, this technology has not been successfully commercialized in large-scale to replace traditional generators in ICEs. One reason is that SOFC performance deteriorates over long-term operation, which makes it difficult to find the proper sizing of the cells for a particular ICE system. In order to find the optimal sizing and operating conditions of SOFCs in a community, a proper knowledge of degradation mechanisms and effects of operating conditions on SOFCs long-time performance is required. The simplified SOFC models that exist in the current literature usually do not provide realistic results since they usually underestimate rate of performance drop by making too many assumptions or generalizations. In addition, some of these models have been obtained from experimental data by curve-fitting methods. Although these models are valid for the range of operating conditions in which experiments were conducted, they cannot be generalized to other conditions and so have limited use for most ICEs. In the present study, a general, detailed degradation-based model is proposed that predicts the performance of conventional SOFCs over a long period of time at different operating conditions. Conventional SOFCs are composed of Yttria Stabilized Zirconia (YSZ) as electrolyte, Ni-cermet anodes, and LaSr₁₋ₓMnₓO₃ (LSM) cathodes. The following degradation processes are considered in this model: oxidation and coarsening of nickel particles in the Ni-cermet anodes, changes in the pore radius in anode, electrolyte, and anode electrical conductivity degradation, and sulfur poisoning of the anode compartment. This model helps decision makers discover the optimal sizing and operation of the cells for a stable, efficient performance with the fewest assumptions. It is suitable for a wide variety of applications. Sulfur contamination of the anode compartment is an important cause of performance drop in cells supplied with hydrocarbon-based fuel sources. H₂S, which is often added to hydrocarbon fuels as an odorant, can diminish catalytic behavior of Ni-based anodes by lowering their electrochemical activity and hydrocarbon conversion properties. Therefore, the existing models in the literature for H₂-supplied SOFCs cannot be applied to hydrocarbon-fueled SOFCs as they only account for the electrochemical activity reduction. A regression model is developed in the current work for sulfur contamination of the SOFCs fed with hydrocarbon fuel sources. The model is developed as a function of current density and H₂S concentration in the fuel. To the best of authors' knowledge, it is the first model that accounts for impact of current density on sulfur poisoning of cells supplied with hydrocarbon-based fuels. Proposed model has wide validity over a range of parameters and is consistent across multiple studies by different independent groups. Simulations using the degradation-based model illustrated that SOFCs voltage drops significantly in the first 1500 hours of operation. After that, cells exhibit a slower degradation rate. The present analysis allowed us to discover the reason for various degradation rate values reported in literature for conventional SOFCs. In fact, the reason why literature reports very different degradation rates, is that literature is inconsistent in definition of how degradation rate is calculated. In the literature, the degradation rate has been calculated as the slope of voltage versus time plot with the unit of voltage drop percentage per 1000 hours operation. Due to the nonlinear profile of voltage over time, degradation rate magnitude depends on the magnitude of time steps selected to calculate the curve's slope. To avoid this issue, instantaneous rate of performance drop is used in the present work. According to a sensitivity analysis, the current density has the highest impact on degradation rate compared to other operating factors, while temperature and hydrogen partial pressure affect SOFCs performance less. The findings demonstrated that a cell running at lower current density performs better in long-term in terms of total average energy delivered per year, even though initially it generates less power than if it had a higher current density. This is because of the dominant and devastating impact of large current densities on the long-term performance of SOFCs, as explained by the model.

Keywords: degradation rate, long-term performance, optimal operation, solid oxide fuel cells, SOFCs

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