Search results for: Masato Sasaki

Authors: Masato Sasaki, Masayoshi Yamamoto

Abstract:

The majority of wireless power transfer (WPT) systems transfer power in a directional manner. This paper describes a discrete exciting voltage control technique for WPT via magnetic resonant coupling with two orthogonal transmitter coils (2D omni-directional WPT system) which can maximize the power transfer efficiency in response to the change of coupling status. The theory allows the equations of the efficiency of the system to be determined at all the rate of the mutual inductance. The calculated results are included to confirm the advantage to one directional WPT system and the validity of the theory and the equations.

Keywords: wireless power transfer, omni-directional, orthogonal, efficiency

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Authors: Mancho Manev

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The concept of almost paracontact Riemannian manifolds (abbr., apcR manifolds) was introduced by I. Sato in 1976 as an analogue of almost contact Riemannian manifolds. The notion of an apcR manifold of type (p,q) was defined by S. Sasaki in 1980, where p and q are respectively the numbers of the multiplicity of the structure eigenvalues 1 and -1. It also has a simple eigenvalue of 0. In our work, we consider (2n+1)-dimensional apcR manifolds of type (n,n), i.e., the paracontact distribution of the studied manifold can be considered as a 2n-dimensional almost paracomplex Riemannian distribution with almost paracomplex structure and structure group O(n) × O(n). The aim of the present study is to introduce a new class of apcR manifolds. Such a manifold is obtained using the construction of a certain Riemannian cone over it, and the resulting manifold is a paraholomorphic paracomplex Riemannian manifold (abbr., phpcR manifold). We call it a para-Sasaki-like Riemannian manifold (abbr., pSlR manifold) and give some explicit examples. We study the structure of pSlR spaces and find that the paracontact form η is closed and each pSlR manifold locally can be considered as a certain product of the real line with a phpcR manifold, which is locally a Riemannian product of two equidimensional Riemannian spaces. We also obtain that the curvature of the pSlR manifolds is completely determined by the curvature of the underlying local phpcR manifold. Moreover, the ξ-directed Ricci curvature is equal to -2n, while in the Sasaki case, it is 2n. Accordingly, the pSlR manifolds can be interpreted as the counterpart of the Sasaki manifolds; the skew-symmetric part of ∇η vanishes, while in the Sasaki case, the symmetric part vanishes. We define a hyperbolic extension of a (complete) phpcR manifold that resembles a certain warped product, and we indicate that it is a (complete) pSlR manifold. In addition, we consider the hyperbolic extension of a phpcR manifold and prove that if the initial manifold is a complete Einstein manifold with negative scalar curvature, then the resulting manifold is a complete Einstein pSlR manifold with negative scalar curvature. In this way, we produce new examples of a complete Einstein Riemannian manifold with negative scalar curvature. Finally, we define and study para contact conformal/homothetic deformations by deriving a subclass that preserves the para-Sasaki-like condition. We then find that if we apply a paracontact homothetic deformation of a pSlR space, we obtain that the Ricci tensor is invariant.

Keywords: almost paracontact Riemannian manifolds, Einstein manifolds, holomorphic product manifold, warped product manifold

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Authors: Yukiko Sasaki Alam

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This research aims at finding out the causes that led to wrong lexical selections in machine translation (MT) rather than categorizing lexical errors, which has been a main practice in error analysis. By manually examining and analyzing lexical errors outputted by a MT system, it suggests what knowledge would help the system reduce lexical errors.

Keywords: machine translation, error analysis, lexical errors, evaluation

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Authors: Yukiko Sasaki Alam, Shahid Alam

Abstract:

Syntactic parsing is vital for semantic treatment by many applications related to natural language processing (NLP), because form and content coincide in many cases. However, it has not yet reached the levels of reliable performance. By manually examining and analyzing individual machine translation output errors that involve syntax as well as semantics, this study attempts to discover what is required for improving syntactic and semantic parsing.

Keywords: syntactic parsing, error analysis, machine translation, deep parsing

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Authors: Yukinori Fuse, Masato Kawaguchi

Abstract:

A quantitative risk assessment method was developed for fiber emissions from sprayed asbestos-containing materials (ACMs). In Japan, instead of being quantitative, these risk assessments have relied on the subjective judgment of skilled engineers, which may vary from one person to another. Therefore, this closed sampling method aims at avoiding any potential variability between assessments. This method was used to assess emissions from ACM sprayed in eleven buildings and the obtained results were compared with the subjective judgments of a skilled engineer. An approximate correlation tendency was found between both approaches. In spite of existing uncertainties, the closed sampling method is useful for public health protection. We firmly believe that this method may find application in the management and renovation decisions of buildings using friable and sprayed ACM.

Keywords: asbestos, renovation, risk assessment, maintenance

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Authors: Masato Nishi, Tetsushi Kaburagi, Masashi Kurose, Tei Hirashima, Tetsusei Kurasiki

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The process of thermoforming a carbon fiber reinforced thermoplastic (CFRTP) has increased its presence in the automotive industry for its wide applicability to the mass production car. A non-isothermal forming for CFRTP can shorten its cycle time to less than 1 minute. In this paper, the textile reinforcement FE model which the authors proposed in a previous work is extended to the CFRTP model for non-isothermal forming simulation. The effect of thermoplastic is given by adding shell elements which consider thermal effect to the textile reinforcement model. By applying Reuss model to the stress calculation of thermoplastic, the proposed model can accurately predict in-plane shear behavior, which is the key deformation mode during forming, in the range of the process temperature. Using the proposed model, thermoforming simulation was conducted and the results are in good agreement with the experimental results.

Keywords: carbon fiber reinforced thermoplastic, finite element analysis, pre-impregnated textile composite, non-isothermal forming

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Authors: E. Popov, N. Yorino, Y. Zoka, Y. Sasaki, H. Sugihara

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This paper discusses the performance of critical trajectory method (CTrj) for power system transient stability analysis under various loading settings and heavy fault condition. The method obtains Controlling Unstable Equilibrium Point (CUEP) which is essential for estimation of power system stability margins. The CUEP is computed by applying the CTrjto the boundary controlling unstable equilibrium point (BCU) method. The Proposed method computes a trajectory on the stability boundary that starts from the exit point and reaches CUEP under certain assumptions. The robustness and effectiveness of the method are demonstrated via six power system models and five loading conditions. As benchmark is used conventional simulation method whereas the performance is compared with and BCU Shadowing method.

Keywords: power system, transient stability, critical trajectory method, energy function method

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Authors: Ludivine Saint-Mard, Masato Nakajima, Gloria Senfaute

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In areas with low to moderate seismicity, the probabilistic seismic hazard analysis frequently uses a Poisson approach, which assumes independence in time and space of events to determine the annual probability of earthquake occurrence. Nevertheless, in countries with high seismic rate, such as Japan, it is frequently use non-poissonian model which assumes that next earthquake occurrence depends on the date of previous one. The objective of this paper is to apply a non-poissonian models in a region of low to moderate seismicity to get a feedback on the following questions: can we overcome the lack of data to determine some key parameters?, and can we deal with uncertainties to apply largely this methodology on an industrial context?. The Brownian-Passage-Time model was applied to a fault located in France and conclude that even if the lack of data can be overcome with some calculations, the amount of uncertainties and number of scenarios leads to a numerous branches in PSHA, making this method difficult to apply on a large scale of low to moderate seismicity areas and in an industrial context.

Keywords: probabilistic seismic hazard, non-poissonian model, earthquake occurrence, low seismicity

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Authors: Faghihnia Torshizi Mostafa, Saitoh Masato

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An efficient method is developed for the response of a group of vertical, cylindrical fixed-head, finite length piles embedded in a homogeneous elastic stratum, subjected to harmonic force atop the pile group cap. Pile to pile interaction is represented through simplified beam-on-dynamic-Winkler-foundation (BDWF) with realistic frequency-dependent springs and dashpots. Pile group effect is considered through interaction factors. New closed-form expressions for interaction factors and curvature ratios atop the pile are extended by considering different boundary conditions at the tip of the piles (fixed, hinged). In order to investigate the fundamental characteristics of inertial bending strains in pile groups, inertial bending strains at the head of each pile are expressed in terms of slenderness ratio. The results of parametric study give valuable insight in understanding the behavior of fixed head pile groups in fundamental natural frequency of soil stratum.

Keywords: Winkler-foundation, fundamental frequency of soil stratum, normalized inertial bending strain, harmonic excitation

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Authors: Chanmoly Or, Kyuro Sasaki, Yuichi Sugai, Masanori Nakano, Motonao Imai

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Cold drainage mechanism of oil production is a complicated process which involves with solubility and foaming processes. Laboratory experiments were carried out to investigate the CO2 gas solubility in hexadecane (as light oil) and the effect of depressurization processes on microbubble generation. The experimental study of sensitivity parameters of temperature and pressure on CO2 gas solubility in hexadecane was conducted at temperature of 20 °C and 50 °C and pressure ranged 2.0–7.0 MPa by using PVT (RUSKA Model 2370) apparatus. The experiments of foamy hexadecane were also prepared by depressurizing from saturated pressure of 6.4 MPa and temperature of 50 °C. The experimental results show the CO2 gas solubility in hexadecane linearly increases with increasing pressure. At pressure 4.5 MPa, CO2 gas dissolved in hexadecane 2.5 mmol.g-1 for temperature of 50 °C and 3.5 mmol.g-1 for temperature of 20 °C. The bubbles of foamy hexadecane were observed that most of large bubbles were coalesced shortly whereas the small one keeps presence. The experimental result of foamy hexadecane indicated large depressurization step (∆P) produces high quality of foam with high microbubble distribution.

Keywords: CO2 gas solubility, depressurization process, foamy hexadecane, microbubble distribution

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Authors: Takashi Ehara, Takayoshi Nakanishi, Kohei Sasaki, Marina Abe, Hiroshi Abe, Kiyoaki Abe, Ryo Iizaka, Takuya Sato

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CuAlO₂ thin films are prepared on Si or sapphire substrate by sol-gel method using two kinds of sols. One is combination of Cu acetate and Al acetate basic, and the other is Cu nitrate and Al nitrate. In the case of acetate sol, XRD peaks of CuAlO₂ observed at annealing temperature of 800-950 ºC on both Si and sapphire substrates. In contrast, in the case of the films prepared using nitrate on Si substrate, XRD peaks of CuAlO₂ have been observed only at the annealing temperature of 800-850 ºC. At annealing temperature of 850ºC, peaks of other species have been observed beside the CuAlO₂ peaks, then, the CuAlO₂ peaks disappeared at annealing temperature of 900 °C with increasing in intensity of the other peaks. Intensity of the other peaks decreased at annealing temperature of 950 ºC with appearance of broad SiO₂ peak. In the present, we ascribe these peaks as metal silicide.

Keywords: CuAlO2, silicide, thin Films, transparent conducting oxide

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Authors: Ryoko Yoshida, Jyunpei Yoshida, Hua Fang Yu, Yasushi Sasaki, Tetsuya Nagasaka

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Phosphorous is an important element for agriculture and industry and is a non-renewable resource. Especially, yellow phosphorus is an essential material in advanced industrial technology, but phosphorus resources were not produced in Japan at all, and all depend on imports. It has been suggested, however, that the remaining accessible reserves of phosphate ore will be depleted within 50 years. Therefore, alternative resources for phosphate ore must be found. In this research, we have developed a process that enables the production of high-purity yellow phosphorus from domestic unused phosphorus resources such as steelmaking slags. The process consists of two parts: (1) the production of crude phosphoric acid from wastes such as steelmaking slag; (2) producing high-purity yellow phosphorus by low-temperature carbothermic reduction of phosphoric acid (H₃PO₄). The details of the carbothermic reduction of phosphoric acid are presented in this paper. Yellow phosphorus is commercially produced by carbothermic reduction of phosphate ore in an electric arc furnace at more than 1673K. In the newly developed system, gaseous P₄O₁₀ evaporated from H₃PO₄ is successfully reduced to yellow phosphorus by using carbon packed bed at less than 1273K. To meet the depletion of phosphate ore, the proposed process in this study to produce yellow phosphorus by carbothermic reduction of H₃PO₄ that are extracted from dephosphorization slags will be one of the effective and economical solutions.

Keywords: carbothermic reduction, phosphoric acid, dephosphorization slags, yellow phosphorus

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Authors: Mohammad Najmol Haque, Takeshi Maki, Jun Sasaki

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Headed stud shear connections are widely used in the junction or embedded zone of hybrid girder to achieve whole composite action with continuity that can sustain steel-concrete interfacial tensile and shear forces. In Japan, Japan Road Association (JRA) specifications are used for hybrid girder design that utilizes very low level of stud capacity than those of American Institute of Steel Construction (AISC) specifications, Japan Society of Civil Engineers (JSCE) specifications and EURO code. As low design shear strength is considered in design of connections, the time dependent shear behavior due to sustained external loading is not considered, even not fully studied. In this study, a finite element approach was used to evaluate the time dependent shear behavior for headed studs used as connections at the junction. This study clarified, how the sustained loading distinctively impacted on changing the interfacial shear of connections with time which was sensitive to lodging history, positions of flanges, neighboring studs, position of prestress bar and reinforcing bar, concrete strength, etc. and also identified a shear influence area. Stud strength was also confirmed through pushout tests. The outcome obtained from the study may provide an important basis and reference data in designing connections of hybrid girders with enhanced stud capacity with due consideration of their long-term shear behavior.

Keywords: finite element, hybrid girder, shear connections, sustained loading, time dependent behavior

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Authors: Masato Saeki

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Presented herein is a novel algorithms for calculating the damping performance of particle dampers. The particle damper is a passive vibration control technique and has many practical applications due to simple design. It consists of granular materials constrained to move between two ends in the cavity of a primary vibrating system. The damping effect results from the exchange of momentum during the impact of granular materials against the wall of the cavity. This damping has the advantage of being independent of the environment. Therefore, particle damping can be applied in extreme temperature environments, where most conventional dampers would fail. It was shown experimentally in many papers that the efficiency of the particle dampers is high in the case of resonant vibration. In order to use the particle dampers effectively, it is necessary to solve the equations of motion for each particle, considering the granularity. The discrete element method (DEM) has been found to be effective for revealing the dynamics of particle damping. In this method, individual particles are assumed as rigid body and interparticle collisions are modeled by mechanical elements as springs and dashpots. However, the computational cost is significant since the equation of motion for each particle must be solved at each time step. In order to improve the computational efficiency of the DEM, the new algorithms are needed. In this study, new algorithms are proposed for implementing the high performance DEM. On the assumption that behaviors of the granular particles in the each divided area of the damper container are the same, the contact force of the primary system with all particles can be considered to be equal to the product of the divided number of the damper area and the contact force of the primary system with granular materials per divided area. This convenience makes it possible to considerably reduce the calculation time. The validity of this calculation method was investigated and the calculated results were compared with the experimental ones. This paper also presents the results of experimental studies of the performance of particle dampers. It is shown that the particle radius affect the noise level. It is also shown that the particle size and the particle material influence the damper performance.

Keywords: particle damping, discrete element method (DEM), granular materials, numerical analysis, equivalent noise level

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Authors: Shinsuke Udagawa, Masato Yamagishi, Masanori Ota

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The Schlieren method, which has been conventionally used to visualize high-speed flows, has disadvantages such as the complexity of the experimental setup and the inability to quantitatively analyze the amount of refraction of light. The Background Oriented Schlieren (BOS) method proposed by Meier is one of the measurement methods that solves the problems, as mentioned above. The refraction of light is used for BOS method same as the Schlieren method. The BOS method is characterized using a digital camera to capture the images of the background behind the observation area. The images are later analyzed by a computer to quantitatively detect the amount of shift of the background image. The experimental setup for BOS does not require concave mirrors, pinholes, or color filters, which are necessary in the conventional Schlieren method, thus simplifying the experimental setup. However, the defocusing of the observation results is caused in case of using BOS method. Since the focus of camera on the background image leads to defocusing of the observed object. The defocusing of object becomes greater with increasing the distance between the background and the object. On the other hand, the higher sensitivity can be obtained. Therefore, it is necessary to adjust the distance between the background and the object to be appropriate for the experiment, considering the relation between the defocus and the sensitivity. The purpose of this study is to experimentally clarify the effect of defocus on density field reconstruction. In this study, the visualization experiment of underexpanded jet using BOS measurement system with ronchi ruling as the background that we constructed, have been performed. The reservoir pressure of the jet and the distance between camera and axis of jet is fixed, and the distance between background and axis of jet has been changed as the parameter. The images have been later analyzed by using personal computer to quantitatively detect the amount of shift of the background image from the comparison between the background pattern and the captured image of underexpanded jet. The quantitatively measured amount of shift have been reconstructed into a density flow field using the Abel transformation and the Gradstone-Dale equation. From the experimental results, it is found that the reconstructed density image becomes blurring, and noise becomes decreasing with increasing the distance between background and axis of underexpanded jet. Consequently, it is cralified that the sensitivity constant should be greater than 20, and the circle of confusion diameter should be less than 2.7mm at least in this experimental setup.

Keywords: BOS method, underexpanded jet, abel transformation, density field visualization

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Authors: T. Sikram, M. Ichinose, R. Sasaki

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In the tropics, indoor thermal environment is usually provided by a cooling mode to maintain comfort all year. Indoor thermal environment performance is sometimes different from the standard or from the first design process because of operation, maintenance, and utilization. The field study of thermal environment in the green building is still limited in this region, while the green building continues to increase. This study aims to clarify thermal performance and subjective perception in the green building by testing the temperature set-points. A Thai green office was investigated twice in October 2018 and in May 2019. Indoor environment variables (temperature, relative humidity, and wind velocity) were collected continuously. The temperature set-point was normally set as 23 °C, and it was changed into 24 °C and 25 °C. The study found that this gap of temperature set-point produced average room temperature from 22.7 to 24.6 °C and average relative humidity from 55% to 62%. Thermal environments slight shifted out of the ASHRAE comfort zone when the set-point was increased. Based on the thermal sensation vote, the feeling-colder vote decreased by 30% and 18% when changing +1 °C and +2 °C, respectively. Predicted mean vote (PMV) shows that most of the calculated median values were negative. The values went close to the optimal neutral value (0) when the set-point was set at 25 °C. The neutral temperature was slightly decreased when changing warmer temperature set-points. Building-related symptom reports were found in this study that the number of votes reduced continuously when the temperature was warmer. The symptoms that occurred by a cooler condition had the number of votes more than ones that occurred by a warmer condition. In sum, for this green office, there is a possibility to adjust a higher temperature set-point to +1 °C (24 °C) in terms of reducing cold sensitivity, discomfort, and symptoms. All results could support the policy of changing a warmer temperature of this office to become “a better green building”.

Keywords: thermal environment, green office, temperature set-point, comfort

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Authors: Yuko Hiramatsu, Fumihiro Sato, Atsushi Ito, Hiroyuki Hatano, Mie Sato, Yu Watanabe, Akira Sasaki

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This paper presents a mobile phone application developed for sightseeing in Nikko, one of the cultural world heritages in Japan, using the BLE (Bluetooth Low Energy) beacon. Based on our pre-research, we decided to design our application for young people who walk around the area actively, but know little about the tradition and culture of Nikko. One solution is to construct many information boards to explain; however, it is difficult to construct new guide plates in cultural world heritage sites. The smartphone is a good solution to send such information to such visitors. This application was designed using a combination of the smartphone and beacons, set in the area, so that when a tourist passes near a beacon, the application displays information about the area including a map, historical or cultural information about the temples and shrines, and local shops nearby as well as a bus timetable. It is useful for foreigners, too. In addition, we developed quizzes relating to the culture and tradition of Nikko to provide information based on the Zeigarnik effect, a psychological effect. According to the results of our trials, tourists positively evaluated the basic information and young people who used the quiz function were able to learn the historical and cultural points. This application helped young visitors at Nikko to understand the cultural elements of the site. In addition, this application has a function to send notifications. This function is designed to provide information about the local community such as shops, local transportation companies and information office. The application hopes to also encourage people living in the area, and such cooperation from the local people will make this application vivid and inspire young visitors to feel that the cultural heritage site is still alive today. This is a gateway for young people to learn about a traditional place and understand the gravity of preserving such areas.

Keywords: BLE beacon, smartphone application, Zeigarnik effect, world heritage site, school trip

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Authors: Masato Koizumi, Yuya Oshio, Ikkoh Funaki

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Magnetoplasma Sail (MPS) is a future spacecraft propulsion that generates high levels of thrust by inducing an artificial magnetosphere to capture and deflect solar wind charged particles in order to transfer momentum to the spacecraft. By injecting plasma in the spacecraft’s magnetic field region, the ring current azimuthally drifts on the equatorial plane about the dipole magnetic field generated by the current flowing through the solenoid attached on board the spacecraft. This ring current results in magnetosphere inflation which improves the thrust performance of MPS spacecraft. In this present study, the ring current was experimentally measured using three Rogowski Current Probes positioned in a circular array about the laboratory model of MPS spacecraft. This investigation aims to determine the detailed structure of ring current through physical experimentation performed under two different magnetic field strengths engendered by varying the applied voltage on the solenoid with 300 V and 600 V. The expected outcome was that the three current probes would detect the same current since all three probes were positioned at equal radial distance of 63 mm from the center of the solenoid. Although experimental results were numerically implausible due to probable procedural error, the trends of the results revealed three pieces of perceptive evidence of the ring current behavior. The first aspect is that the drift direction of the ring current depended on the strength of the applied magnetic field. The second aspect is that the diamagnetic current developed at a radial distance not occupied by the three current probes under the presence of solar wind. The third aspect is that the ring current distribution varied along the circumferential path about the spacecraft’s magnetic field. Although this study yielded experimental evidence that differed from the original hypothesis, the three key findings of this study have informed two critical MPS design solutions that will potentially improve thrust performance. The first design solution is the positioning of the plasma injection point. Based on the implication of the first of the three aspects of ring current behavior, the plasma injection point must be located at a distance instead of at close proximity from the MPS Solenoid for the ring current to drift in the direction that will result in magnetosphere inflation. The second design solution, predicated by the third aspect of ring current behavior, is the symmetrical configuration of plasma injection points. In this study, an asymmetrical configuration of plasma injection points using one plasma source resulted in a non-uniform distribution of ring current along the azimuthal path. This distorts the geometry of the inflated magnetosphere which minimizes the deflection area for the solar wind. Therefore, to realize a ring current that best provides the maximum possible inflated magnetosphere, multiple plasma sources must be spaced evenly apart for the plasma to be injected evenly along its azimuthal path.

Keywords: Magnetoplasma Sail, magnetosphere inflation, ring current, spacecraft propulsion

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Authors: Kyohei Yoshino, Masahiko Matsumiya, Yuji Sasaki

Abstract:

Recently, studies have been conducted on Au(III) extraction using ionic liquids (ILs) as extractants or diluents. ILs such as piperidinium, pyrrolidinium, and pyridinium have been studied as extractants for noble metal extractions. Furthermore, the polarity, hydrophobicity, and solvent miscibility of these ILs can be adjusted depending on their intended use. Therefore, the unique properties of ILs make them functional extraction media. The extraction mechanism of Au(III) using phosphonium-based ILs and relevant thermodynamic studies are yet to be reported. In the present work, we focused on the mechanism of Au(III) extraction and related thermodynamic analyses using phosphonium-based ILs. Triethyl-n-pentyl, triethyl-n-octyl, and triethyl-n-dodecyl phosphonium bis(trifluoromethyl-sulfonyl)amide, [P₂₂₂ₓ][NTf₂], (X = 5, 8, and 12) were investigated for Au(III) extraction. The IL–Au complex was identified as [P₂₂₂₅][AuCl₄] using UV–Vis–NIR and Raman spectroscopic analyses. The extraction behavior of Au(III) was investigated with a change in the [P₂₂₂ₓ][NTf₂]IL concentration from 1.0 × 10–4 to 1.0 × 10–1 mol dm−3. The results indicate that Au(III) can be easily extracted by the anion-exchange reaction in the [P₂₂₂ₓ][NTf₂]IL. The slope range 0.96–1.01 on the plot of log D vs log[P₂₂₂ₓ][NTf2]IL indicates the association of one mole of IL with one mole of [AuCl4−] during extraction. Consequently, [P₂₂₂ₓ][NTf₂] is an anion-exchange extractant for the extraction of Au(III) in the form of anions from chloride media. Thus, this type of phosphonium-based IL proceeds via an anion exchange reaction with Au(III). In order to evaluate the thermodynamic parameters on the Au(III) extraction, the equilibrium constant (logKₑₓ’) was determined from the temperature dependence. The plot of the natural logarithm of Kₑₓ’ vs the inverse of the absolute temperature (T–1) yields a slope proportional to the enthalpy (ΔH). By plotting T–1 vs lnKₑₓ’, a line with a slope range 1.129–1.421 was obtained. Thus, the result indicated that the extraction reaction of Au(III) using the [P₂₂₂ₓ][NTf₂]IL (X=5, 8, and 12) was exothermic (ΔH=-9.39〜-11.81 kJ mol-1). The negative value of TΔS (-4.20〜-5.27 kJ mol-1) indicates that microscopic randomness is preferred in the [P₂₂₂₅][NTf₂]IL extraction system over [P₂₂₂₁₂][NTf₂]IL. The total negative alternation in Gibbs energy (-5.19〜-6.55 kJ mol-1) for the extraction reaction would thus be relatively influenced by the TΔS value on the number of carbon atoms in the alkyl side length, even if the efficiency of ΔH is significantly influenced by the total negative alternations in Gibbs energy. Electrochemical analysis revealed that extracted Au(III) can be reduced in two steps: (i) Au(III)/Au(I) and (ii) Au(I)/Au(0). The diffusion coefficients of the extracted Au(III) species in [P₂₂₂ₓ][NTf₂] (X = 5, 8, and 12) were evaluated from 323 to 373 K using semi-integral and semi-differential analyses. Because of the viscosity of the IL medium, the diffusion coefficient of the extracted Au(III) increases with increasing alkyl chain length. The 4f7/2 spectrum based on X-ray photoelectron spectroscopy revealed that the Au electrodeposits obtained after 10 cycles of continuous extraction and electrodeposition were in the metallic state.

Keywords: au(III), electrodeposition, phosphonium-based ionic liquids, solvent extraction

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Authors: Albert Mufundirwa, Satoru Yoshioka, K. Ogi, Takeharu Sugiyama, George F. Harrington, Bretislav Smid, Benjamin Cunning, Kazunari Sasaki, Akari Hayashi, Stephen M. Lyth

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Polymer electrolyte membrane fuel cells (PEMFCs) are electrochemical energy conversion devices used for portable, residential and vehicular applications due to their low emissions, high efficiency, and quick start-up characteristics. However, PEMFCs generally use expensive, Pt-based electrocatalysts as electrode catalysts. Due to the high cost and limited availability of platinum, research and development to either drastically reduce platinum loading, or replace platinum with alternative catalysts is of paramount importance. A combination of high surface area supports and nano-structured active sites is essential for effective operation of catalysts. We synthesize carbon foam supports by thermal decomposition of sodium ethoxide, using a template-free, gram scale, cheap, and scalable pyrolysis method. This carbon foam has a high surface area, highly porous, three-dimensional framework which is ideal for electrochemical applications. These carbon foams can have surface area larger than 2500 m²/g, and electron microscopy reveals that they have micron-scale cells, separated by few-layer graphene-like carbon walls. We applied this carbon foam as a platinum catalyst support, resulting in the improved electrochemical surface area and mass activity for the oxygen reduction reaction (ORR), compared to carbon black. Similarly, silver-decorated carbon foams showed higher activity and efficiency for electrochemical carbon dioxide conversion than silver-decorated carbon black. A promising alternative to Pt-catalysts for the ORR is iron-impregnated nitrogen-doped carbon catalysts (Fe-N-C). Doping carbon with nitrogen alters the chemical structure and modulates the electronic properties, allowing a degree of control over the catalytic properties. We have adapted our synthesis method to produce nitrogen-doped carbon foams with large surface area, using triethanolamine as a nitrogen feedstock, in a novel bottom-up protocol. These foams are then infiltrated with iron acetate (FeAc) and pyrolysed to form Fe-N-C foams. The resulting Fe-N-C foam catalysts have high initial activity (half-wave potential of 0.68 VRHE), comparable to that of commercially available Pt-free catalysts (e.g., NPC-2000, Pajarito Powder) in acid solution. In alkaline solution, the Fe-N-C carbon foam catalysts have a half-wave potential of 0.89 VRHE, which is higher than that of NPC-2000 by almost 10 mVRHE, and far out-performing platinum. However, the durability is still a problem at present. The lessons learned from X-ray absorption spectroscopy (XAS), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements will be used to carefully design Fe-N-C catalysts for higher performance PEMFCs.

Keywords: carbon-foam, polymer electrolyte membrane fuel cells, platinum, Pt-free, Fe-N-C, ORR

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