Search results for: Yasushi Sasaki
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 20

Search results for: Yasushi Sasaki

20 Introduction of Para-Sasaki-Like Riemannian Manifolds and Construction of New Einstein Metrics

Authors: Mancho Manev

Abstract:

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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19 Carbothermic Reduction of Phosphoric Acid Extracted from Dephosphorization Slags to Produce Yellow Phosphorus

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

Abstract:

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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18 Knowledge Required for Avoiding Lexical Errors at Machine Translation

Authors: Yukiko Sasaki Alam

Abstract:

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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17 A Study on Inference from Distance Variables in Hedonic Regression

Authors: Yan Wang, Yasushi Asami, Yukio Sadahiro

Abstract:

In urban area, several landmarks may affect housing price and rents, hedonic analysis should employ distance variables corresponding to each landmarks. Unfortunately, the effects of distances to landmarks on housing prices are generally not consistent with the true price. These distance variables may cause magnitude error in regression, pointing a problem of spatial multicollinearity. In this paper, we provided some approaches for getting the samples with less bias and method on locating the specific sampling area to avoid the multicollinerity problem in two specific landmarks case.

Keywords: landmarks, hedonic regression, distance variables, collinearity, multicollinerity

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16 Study of Syntactic Errors for Deep Parsing at Machine Translation

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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15 Effects of Macrophyte Vallisneria asiatica Biomasses on the Algae Community

Authors: Caixia Kang, Takahiro Kuba, Aimin Hao, Yasushi Iseri, Chunjie Li, Zhenjia Zhang

Abstract:

To improve the water quality of lakes and control algae blooms, The effects of Vallisneria asiatica which is one of aquatic plants spread over Lake Taihu. With different biomasses on the water quality and algae communities were researched. The results indicated that V. asiatica could control an excess of Microcystis spp. When the V. asiatica biomass was larger than 50g in the tank with 30L solution in the laboratory, Planktonic and epiphytic algae responded differently to V. asiatica. The presence of macrophyte V. asiatica in eutrophic waters has a positive effect on algae compositions because of different sensitivities of algae species to allelopathic substances released by macrophyte V. asiatica. That is, V. asiatica could inhibit the growth of Microcystis spp. effectively and was benefited to the diatom on the condition in the laboratory.

Keywords: algae bloom, algae community, Microcystis spp., Vallisneria asiatica

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14 A Research on Inference from Multiple Distance Variables in Hedonic Regression Focus on Three Variables

Authors: Yan Wang, Yasushi Asami, Yukio Sadahiro

Abstract:

In urban context, urban nodes such as amenity or hazard will certainly affect house price, while classic hedonic analysis will employ distance variables measured from each urban nodes. However, effects from distances to facilities on house prices generally do not represent the true price of the property. Distance variables measured on the same surface are suffering a problem called multicollinearity, which is usually presented as magnitude variance and mean value in regression, errors caused by instability. In this paper, we provided a theoretical framework to identify and gather the data with less bias, and also provided specific sampling method on locating the sample region to avoid the spatial multicollinerity problem in three distance variable’s case.

Keywords: hedonic regression, urban node, distance variables, multicollinerity, collinearity

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13 Exciting Voltage Control for Efficiency Maximization for 2-D Omni-Directional Wireless Power Transfer Systems

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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12 Direct Transient Stability Assessment of Stressed Power Systems

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

Abstract:

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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11 Design of an Acoustic System for Small-Scale Power Plants

Authors: Mohammadreza Judaki, Hosein Mohammadnezhad Shourkaei

Abstract:

Usually, noise generated by industrial units, is a pollution and disturbs people and causes problems for human health and sometimes these units will be closed because they cannot eliminate this pollution. Small-scale power plants usually are built close to residential areas, and noise generated by these power plants is an important factor in choosing their location and their design. Materials used to reduce noise are studied by measuring their absorption and reflection index numerically and experimentally. We can use MIKI model (Yasushi Miki, 1990) to simulate absorption index by using software like Ansys or Soundflow and compare calculation results with experimental simulation data. We consider high frequency sounds of power plant engines octave band diagram because dB value of high frequency noise is more noticeable for human ears. To prove this, in this study we first will study calculating octave band of engines exhausts and then we will study acoustic behavior of materials that we will use in high frequencies and this will give us our optimum noise reduction plan.

Keywords: acoustic materials, eliminating engine noise, octave level diagram, power plant noise

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10 CO2 Gas Solubility and Foam Generation

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

Abstract:

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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9 Preparation of CuAlO2 Thin Films on Si or Sapphire Substrate by Sol-Gel Method Using Metal Acetate or Nitrate

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

Abstract:

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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8 Proposal of Analytical Model for the Seismic Performance Evaluation of Reinforced Concrete Frames with Coupled Cross-laminated Timber Infill Panels

Authors: Velázquez Alejandro, Pradhan Sujan, Yoon Rokhyun, Sanada Yasushi

Abstract:

The utilization of new materials as an alternative solution to decrease the environmental impact of the construction industry has been gaining more relevance in the architectural design and construction industry. One such material is cross-laminated timber (CLT), an engineered timber solution that excels for its faster construction times, workability, lightweight, and capacity for carbon storage. This material is usually used alone for the entire structure or combined with steel frames, but a hybrid with reinforced concrete (RC) is rarer. Since RC is one of the most used materials worldwide, a hybrid with CLT would allow further utilization of the latter, and in the process, it would help reduce the environmental impact of RC construction to achieve a sustainable society, but first, the structural performance of such hybrids must be understood. This paper focuses on proposing a model to predict the seismic performance of RC frames with CLT panels as infills. A series of static horizontal cyclic loading experiments were conducted on two 40% scale specimens of reinforced concrete frames with and without CLT panels at Osaka University, Japan. An analytical model was created to simulate the seismic performance of the RC frame with CLT infill based on the experimental results. The proposed model was verified by comparing the experimental and analytical results, showing that the load-deformation relationship and the failure mechanism agreed well with limited error. Hence, the proposed analytical model can be implemented for the seismic performance evaluation of the RC frames with CLT infill.

Keywords: analytical model, multi spring, performance evaluation, reinforced concrete, rocking mechanism, wooden wall

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7 Finite Element Approach to Evaluate Time Dependent Shear Behavior of Connections in Hybrid Steel-PC Girder under Sustained Loading

Authors: Mohammad Najmol Haque, Takeshi Maki, Jun Sasaki

Abstract:

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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6 Field Study on Thermal Performance of a Green Office in Bangkok, Thailand: A Possibility of Increasing Temperature Set-Points

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

Abstract:

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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5 Comparing the Gap Formation around Composite Restorations in Three Regions of Tooth Using Optical Coherence Tomography (OCT)

Authors: Rima Zakzouk, Yasushi Shimada, Yuan Zhou, Yasunori Sumi, Junji Tagami

Abstract:

Background and Purpose: Swept source optical coherence tomography (OCT) is an interferometric imaging technique that has been recently used in cariology. In spite of progress made in adhesive dentistry, the composite restoration has been failing due to secondary caries which occur due to environmental factors in oral cavities. Therefore, a precise assessment to effective marginal sealing of restoration is highly required. The aim of this study was evaluating gap formation at composite/cavity walls interface with or without phosphoric acid etching using SS-OCT. Materials and Methods: Round tapered cavities (2×2 mm) were prepared in three locations, mid-coronal, cervical, and root of bovine incisors teeth in two groups (SE and PA Groups). While self-etching adhesive (Clearfil SE Bond) was applied for the both groups, Group PA had been already pretreated with phosphoric acid etching (K-Etchant gel). Subsequently, both groups were restored by Estelite Flow Quick Flowable Composite Resin. Following 5000 thermal cycles, three cross-sectionals were obtained from each cavity using OCT at 1310-nm wavelength at 0°, 60°, 120° degrees. Scanning was repeated after two months to monitor the gap progress. Then the average percentage of gap length was calculated using image analysis software, and the difference of mean between both groups was statistically analyzed by t-test. Subsequently, the results were confirmed by sectioning and observing representative specimens under Confocal Laser Scanning Microscope (CLSM). Results: The results showed that pretreatment with phosphoric acid etching, Group PA, led to significantly bigger gaps in mid-coronal and cervical compared to SE group, while in the root cavity no significant difference was observed between both groups. On the other hand, the gaps formed in root’s cavities were significantly bigger than those in mid-coronal and cervical within the same group. This study investigated the effect of phosphoric acid on gap length progress on the composite restorations. In conclusions, phosphoric acid etching treatment did not reduce the gap formation even in different regions of the tooth. Significance: The cervical region of tooth was more exposing to gap formation than mid-coronal region, especially when we added pre-etching treatment.

Keywords: image analysis, optical coherence tomography, phosphoric acid etching, self-etch adhesives

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4 Designing Mobile Application to Motivate Young People to Visit Cultural Heritage Sites

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

Abstract:

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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3 Optical Assessment of Marginal Sealing Performance around Restorations Using Swept-Source Optical Coherence Tomography

Authors: Rima Zakzouk, Yasushi Shimada, Yasunori Sumi, Junji Tagami

Abstract:

Background and purpose: The resin composite has become the main material for the restorations of caries in recent years due to aesthetic characteristics, especially with the development of the adhesive techniques. The quality of adhesion to tooth structures is depending on an exchange process between inorganic tooth material and synthetic resin and a micromechanical retention promoted by resin infiltration in partially demineralized dentin. Optical coherence tomography (OCT) is a noninvasive diagnostic method for obtaining cross-sectional images that produce high-resolution of the biological tissue at the micron scale. The aim of this study was to evaluate the gap formation at adhesive/tooth interface of two-step self-etch adhesives that are preceded with or without phosphoric acid pre-etching in different regions of teeth using SS-OCT. Materials and methods: Round tapered cavities (2×2 mm) were prepared in cervical part of bovine incisors teeth and divided into 2 groups (n=10): first group self-etch adhesive (Clearfil SE Bond) was applied for SE group and second group treated with acid etching before applying the self-etch adhesive for PA group. Subsequently, both groups were restored with Estelite Flow Quick Flowable Composite Resin and observed under OCT. Following 5000 thermal cycles, the same section was obtained again for each cavity using OCT at 1310-nm wavelength. Scanning was repeated after two months to monitor the gap progress. Then the gap length was measured using image analysis software, and the statistics analysis were done between both groups using SPSS software. After that, the cavities were sectioned and observed under Confocal Laser Scanning Microscope (CLSM) to confirm the result of OCT. Results: Gaps formed at the bottom of the cavity was longer than the gap formed at the margin and dento-enamel junction in both groups. On the other hand, pre-etching treatment led to damage the DEJ regions creating longer gap. After 2 months the results showed almost progress in the gap length significantly at the bottom regions in both groups. In conclusions, phosphoric acid etching treatment did not reduce the gap lrngth in most regions of the cavity. Significance: The bottom region of tooth was more exposed to gap formation than margin and DEJ regions, The DEJ damaged with phosphoric acid treatment.

Keywords: optical coherence tomography, self-etch adhesives, bottom, dento enamel junction

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2 Extraction and Electrochemical Behaviors of Au(III) using Phosphonium-Based Ionic Liquids

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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1 Carbon-Foam Supported Electrocatalysts for Polymer Electrolyte Membrane Fuel Cells

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

Abstract:

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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