Search results for: energization of the cold proton
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 1024

Search results for: energization of the cold proton

754 N-Heterocyclic Carbene Based Dearomatized Iridium Complex as an Efficient Catalyst towards Carbon-Carbon Bond Formation via Hydrogen Borrowing Strategy

Authors: Mandeep Kaur, Jitendra K. Bera

Abstract:

The search for atom-economical and green synthetic methods for the synthesis of functionalized molecules has attracted much attention. Metal ligand cooperation (MLC) plays a pivotal role in organometallic catalysis to activate C−H, H−H, O−H, N−H and B−H bonds through reversible bond breaking and bond making process. Towards this goal, a bifunctional N─heterocyclic carbene (NHC) based pyridyl-functionalized amide ligand precursor, and corresponding dearomatized iridium complex was synthesized. The NMR and UV/Vis acid titration study have been done to prove the proton response nature of the iridium complex. Further, the dearomatized iridium complex explored as a catalyst on the platform of MLC via dearomatzation/aromatization mode of action towards atom economical α and β─alkylation of ketones and secondary alcohols by using primary alcohols through hydrogen borrowing methodology. The key features of the catalysis are high turnover frequency (TOF) values, low catalyst loading, low base loading and no waste product. The greener syntheses of quinoline, lactone derivatives and selective alkylation of drug molecules like pregnenolone and testosterone were also achieved successfully. Another structurally similar iridium complex was also synthesized with modified ligand precursor where a pendant amide unit was absent. The inactivity of this analogue iridium complex towards catalysis authenticated the participation of proton responsive imido sidearm of the ligand to accelerate the catalytic reaction. The mechanistic investigation through control experiments, NMR and deuterated labeling study, authenticate the borrowing hydrogen strategy.

Keywords: C-C bond formation, hydrogen borrowing, metal ligand cooperation (MLC), n-heterocyclic carbene

Procedia PDF Downloads 151
753 Effect of Heating Rate on Microstructural Developments in Cold Heading Quality Steel Used for Automotive Applications

Authors: Shahid Hussain Abro, F. Mufadi, A. Boodi

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Microstructural study and phase transformation in steels is a basic and important step during the design of structural steel. There are huge efforts and study has been done so far on phase transformations, due to so many steel grades available commercially the phase development in steel has different consequences. In the present work an effort has been made to study the effect of heating rate on microstructural features of cold heading quality steel. The SEM, optical microscopy, and heat treatment techniques have been applied to observe the microstructural features in the experimental steel. It was observed that heating rate has the strong influence on phase transformation of CHQ steel under investigation. Heating rate increases the austenite formation kinetics with respect to holding time, and this austenite has been transformed to martensite upon cooling. Heating rate also plays a vital role on nucleation sites of austenite formation in the experimental steel.

Keywords: CHQ steel, austenite formation, heating rate, nucleation

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752 Novel Uses of Discarded Work Rolls of Cold Rolling Mills in Hot Strip Mill of Tata Steel India

Authors: Uday Shanker Goel, Vinay Vasant Mahashabde, Biswajit Ghosh, Arvind Jha, Amit Kumar, Sanjay Kumar Patel, Uma Shanker Pattanaik, Vinit Kumar Shah, Chaitanya Bhanu

Abstract:

Pinch rolls of the Hot Mills must possess resistance to wear, thermal stability, high thermal conductivity and through hardness. Conventionally, pinch rolls have been procured either as new ones or refurbished ones. Discarded Work Rolls from the Cold Mill were taken and machined inhouse at Tata Steel to be used subsequently as the bottom pinch rolls of the Hot Mill. The hardness of the scrapped work rolls from CRM is close to 55HRC and the typical composition is ( C - 0.8% , Mn - 0.40 % , Si - 0.40% , Cr - 3.5% , Mo - 0.5% & V - 0.1% ).The Innovation was the use of a roll which would otherwise have been otherwise discarded as scrap. Also, the innovation helped in using the scrapped roll which had better wear and heat resistance. In a conventional Pinch roil (Hardness 50 HRC and typical chemistry - C - 10% , Mo+Co+V+Nb ~ 5 % ) , Pick-up is a condition whereby foreign material becomes adhered to the surface of the pinch roll during service. The foreign material is usually adhered metal from the actual product being rolled. The main attributes of the weld overlay rolls are wear resistance and crack resistance. However, the weld overlay roll has a strong tendency for strip pick-up particularly in the area of bead overlap. However, the greatest disadvantage is the depth of weld deposit, which is less than half of the usable shell thickness in most mills. Because of this, the stainless rolls require re-welding on a routine basis. By providing a significantly cheaper in house and more robust alternative of the existing bottom pinch rolls , this innovation results in significant lower worries for the roll shop. Pinch rolls now don't have to be sent outside Jamshedpur for refurbishment or for procuring new ones. Scrapped rolls from adjacent Cold Mill are procured and sent for machining to our Machine Shop inside Tata Steel works in Jamshedpur. This is far more convenient than the older methodology. The idea is also being deployed to the other hot mills of Tata Steel. Multiple campaigns have been tried out at both down coilers of Hot Strip with significantly lower wear.

Keywords: hot rolling flat, cold mill work roll, hot strip pinch roll, strip surface

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751 Difference in the Expression of CIRBP, RBM3 and HSP70 in the Myocardium and Cerebellum after Death by Hypothermi a and Carbon Monoxide Poisoning

Authors: Satoshi Furukawa, Satomu Morita, Lisa Wingenfeld, Katsuji Nishi, Masahito Hitosugi

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We studied the expression of hypoxia-related antigens (e.g., cold-inducible antigens and apoptotic antigens) in the myocardium and the cerebellumthat were obtained from individuals after death by carbon monoxide or hypothermia. The immunohistochemistry results revealed that expression of cold-inducible RNA binding protein (CIRBP) and RNA-binding protein 3 (RBM3) may be associated with hpyothermic and the hypoxic conditions. The expression of CIRBP and RBM3 in the myocardium was different from their expression in the cerebellum, especially in the Purkinje cells. The results indicate that agonal duration influences antigen expression. In the hypothermic condition, the myocardium uses more ATP since the force of the excitation-contraction coupling of the myocardium increases by more than 400% when the experimental temperature is reduced from 35°C to 25°C. The results obtained in this study indicate that physicians should pay attention to the myocardium when cooling the patient’s body to protect the brain.

Keywords: carbon monoxide death, cerebellum, CIRBP, hypothermic death, myocardium, RBM3

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750 Theoretical Investigations and Simulation of Electromagnetic Ion Cyclotron Waves in the Earth’s Magnetosphere Through Magnetospheric Multiscale Mission

Authors: A. A. Abid

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Wave-particle interactions are considered to be the paramount in the transmission of energy in collisionless space plasmas, where electromagnetic fields confined the charged particles movement. One of the distinct features of energy transfer in collisionless plasma is wave-particle interaction which is ubiquitous in space plasmas. The three essential populations of the inner magnetosphere are cold plasmaspheric plasmas, ring-currents, and radiation belts high energy particles. The transition region amid such populations initiates wave-particle interactions among distinct plasmas and the wave mode perceived in the magnetosphere is the electromagnetic ion cyclotron (EMIC) wave. These waves can interact with numerous particle species resonantly, accompanied by plasma particle heating is still in debate. In this work we paid particular attention to how EMIC waves impact plasma species, specifically how they affect the heating of electrons and ions during storm and substorm in the Magnetosphere. Using Magnetospheric Multiscale (MMS) mission and electromagnetic hybrid simulation, this project will investigate the energy transfer mechanism (e.g., Landau interactions, bounce resonance interaction, cyclotron resonance interaction, etc.) between EMIC waves and cold-warm plasma populations. Other features such as the production of EMIC waves and the importance of cold plasma particles in EMIC wave-particle interactions will also be worth exploring. Wave particle interactions, electromagnetic hybrid simulation, electromagnetic ion cyclotron (EMIC) waves, Magnetospheric Multiscale (MMS) mission, space plasmas, inner magnetosphere

Keywords: MMS, magnetosphere, wave particle interraction, non-maxwellian distribution

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749 Effect of Al Addition on Microstructure and Physical Properties of Fe-36Ni Invar Alloy

Authors: Seok Hong Min, Tae Kwon Ha

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High strength Fe-36Ni-base Invar alloys containing Al contents up to 0.3 weight percent were cast into ingots and thermodynamic equilibrium during solidification has been investigated in this study. From the thermodynamic simulation using Thermo-Calc®, it has been revealed that equilibrium phases which can be formed are two kinds of MC-type precipitates, MoC, and M2C carbides. The mu phase was also expected to form by addition of aluminum. Microstructure observation revealed the coarse precipitates in the as-cast ingots, which was non-equilibrium phase and could be resolved by the successive heat treatment. With increasing Al contents up to 0.3 wt.%, tensile strength of Invar alloy increased as 1400MPa after cold rolling and thermal expansion coefficient increased significantly. Cold rolling appeared to dramatically decrease thermal expansion coefficient.

Keywords: invar alloy, aluminum, phase equilibrium, thermal expansion coefficient, microstructure, tensile properties

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748 In vitro Control of Mycosphaerella arachidis Deighton the Early Leaf Spot Disease Pathogen of Groundnut by the Extracts from Six Medicinal Plants

Authors: Matthew Omoniyi Adebola, Jude E Amadi

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Ground nut (Arachis hypogaea) is one of the most popular commercial crops in Nigeria. Its suc-cessful production has been drastically affected by early leaf spot disease caused by Mycosphae-rella arachidis Deighton. In vitro control of the pathogen by six medicinal plants (Entada afri-cana, Vitex doniana, Lawsonia inermis, Azadirachta indica, Acalypha hispida and Nuaclea lati-folia) was assessed in this study. The extracts of the plants were prepared using cold and hot wa-ter and alcohol. The pathogen was isolated from ground nut infected with early leaf spot disease. The results revealed a great significant difference (P<0.05) in yield of extracts between cold water, hot water, and alcohol extracts. A significant difference (P<0.05) was observed in percentage concentrations of the various phytochemical constituents present in the extracts. Flavonoids per-centage concentration was the highest (0.68 - 1.95%) followed by saponnin(0.09-1.53%) in N. latifolia extracts. Steroiods had the least percentage concentrations (0.00- 0.09%)followed by terpenoids(0.02–0.71%) and proanthocyannin (0.05 – 0.86%). N. latifolia extracts produced the highest percentage concentrations (0.07–1.95%) of all the phytochemicals followed by A. indi-ca(0.05–1.64%)and least concentrations were obtained in A. hispidia(0.09 – 0.87%)and V. do-niana (0.00–0.88%). The extracts inhibited spore germination and growth of M. arachidis. The inhibition by alcohol extracts was high and significantly different (P>0.05) from cold and hot water extracts. Alcohol extract of L. inermis gave 100% spore germination inhibition followed by N. latifolia and A.indica with 97.75% and 85.60% inhibition respectively. Therefore, field trials of these six medicinal plants on the control of early leaf spot disease of ground nut are rec-ommended.

Keywords: groundnut, phytochemicals, medicinal plants, extracts, inhibition

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747 Roll Forming Process and Die Design for a Large Size Square Tube

Authors: Jinn-Jong Sheu, Cang-Fu Liang, Cheng-Hsien Yu

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This paper proposed the cold roll forming process and the die design methods for a 400mm by 400 mm square tube with 16 mm in thickness. The tubular blank made by cold roll forming is 508mm in diameter. The square tube roll forming process was designed considering the layout of rolls and the compression ratio distribution for each stand. The final tube corner radius and the edge straightness in the front end of the tube are to be controlled according to the tube specification. A five-stand forming design using four rolls at each stand was proposed to establish the base reference of square tube roll forming quality. Different numbers of pass and roll designs were proposed and compared to the base design in order to find the feasibility of increase pass number to improve the square tube quality. The proposed roll forming processes were simulated using FEM analysis. The thickness variations of the corner and the edge areas were examined. The maximum loads and the torques of each stand were calculated to study the power consumption of the roll forming machine. The simulation results showed the square tube thickness variations and concavity of the edge are acceptable with the JIS tube specifications for the base design. But the maximum loads and torques are very high. By changing the layout and the number of the rolls were able to obtain better tube geometry and decrease the maximum load and torque of each stand. This paper had shown the feasibility of designing the roll forming process and the layout of dies using FEM simulation. The obtained information is helpful to the roll forming machine design for a large size square tube making.

Keywords: cold roll forming, FEM analysis, roll forming die design, tube roll forming

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746 The Plasma Additional Heating Systems by Electron Cyclotron Waves

Authors: Ghoutia Naima Sabri, Tayeb Benouaz

Abstract:

The interaction between wave and electron cyclotron movement when the electron passes through a layer of resonance at a fixed frequency results an Electron Cyclotron (EC) absorption in Tokamak plasma and dependent magnetic field. This technique is the principle of additional heating (ECRH) and the generation of non-inductive current drive (ECCD) in modern fusion devices. In this paper we are interested by the problem of EC absorption which used a microscopic description of kinetic theory treatment versus the propagation which used the cold plasma description. The power absorbed depends on the optical depth which in turn depends on coefficient of absorption and the order of the excited harmonic for O-mode or X-mode. There is another possibility of heating by dissipation of Alfven waves, based on resonance of cold plasma waves, the shear Alfven wave (SW) and the compressional Alfven wave (FW). Once the (FW) power is coupled to (SW), it stays on the magnetic surface and dissipates there, which cause the heating of bulk plasmas.

Keywords: electron cyclotron, heating, plasma, tokamak

Procedia PDF Downloads 474
745 Waste Heat Recovery Using Spiral Heat Exchanger

Authors: Parthiban S. R.

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Spiral heat exchangers are known as excellent heat exchanger because of far compact and high heat transfer efficiency. An innovative spiral heat exchanger based on polymer materials is designed for waste heat recovery process. Such a design based on polymer film technology provides better corrosion and chemical resistance compared to conventional metal heat exchangers. Due to the smooth surface of polymer film fouling is reduced. A new arrangement for flow of hot flue gas and cold fluid is employed for design, flue gas flows in axial path while the cold fluid flows in a spiral path. Heat load recovery achieved with the presented heat exchanger is in the range of 1.5 kW thermic but potential heat recovery about 3.5 kW might be achievable. To measure the performance of the spiral tube heat exchanger, its model is suitably designed and fabricated so as to perform experimental tests. The paper gives analysis of spiral tube heat exchanger.

Keywords: spiral heat exchanger, polymer based materials, fouling factor, heat load

Procedia PDF Downloads 362
744 Rollet vs Rocket: A New in-Space Propulsion Concept

Authors: Arthur Baraov

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Nearly all rocket and spacecraft propulsion concepts in existence today can be linked one way or the other to one of the two ancient warfare devices: the gun and the sling. Chemical, thermoelectric, ion, nuclear thermal and electromagnetic rocket engines – all fall into the first group which, for obvious reasons, can be categorized as “hot” space propulsion concepts. Space elevator, orbital tower, rolling satellite, orbital skyhook, tether propulsion and gravitational assist – are examples of the second category which lends itself for the title “cold” space propulsion concepts. The “hot” space propulsion concepts skyrocketed – literally and figuratively – from the naïve ideas of Jules Verne to the manned missions to the Moon. On the other hand, with the notable exception of gravitational assist, hardly any of the “cold” space propulsion concepts made any progress in terms of practical application. Why is that? This article aims to show that the right answer to this question has the potential comparable by its implications and practical consequences to that of transition from Jules Verne’s stillborn and impractical conceptions of space flight to cogent and highly fertile ideas of Konstantin Tsiolkovsky and Yuri Kondratyuk.

Keywords: propulsion, rocket, rollet, spacecraft

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743 Suitability of Direct Strength Method-Based Approach for Web Crippling Strength of Flange Fastened Cold-Formed Steel Channel Beams Subjected to Interior Two-Flange Loading: A Comprehensive Investigation

Authors: Hari Krishnan K. P., Anil Kumar M. V.

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The Direct Strength Method (DSM) is used for the computation of the design strength of members whose behavior is governed by any form of buckling. DSM based semiempirical equations have been successfully used for cold-formed steel (CFS) members subjected to compression, bending, and shear. The DSM equations for the strength of a CFS member are based on the parameters accounting for strength [yield load (Py), yield moment (My), and shear yield load (Vy) for compression, bending, and shear respectively] and stability [buckling load (Pcr), buckling moment (Mcr), and shear buckling load (Vcr) for compression, bending and shear respectively]. The buckling of column and beam shall be governed by local, distortional, or global buckling modes and their interaction. Recently DSM-based methods are extended for the web crippling strength of CFS beams also. Numerous DSM-based expressions were reported in the literature, which is the function of loading case, cross-section shape, and boundary condition. Unlike members subjected to axial load, bending, or shear, no unified expression for the design web crippling strength irrespective of the loading case, cross-section shape, and end boundary conditions are available yet. This study, based on nonlinear finite element analysis results, shows that the slenderness of the web, which shall be represented either using web height to thickness ratio (h=t) or Pcr has negligible contribution to web crippling strength. Hence, the results in this paper question the suitability of DSM based approach for the web crippling strength of CFS beams.

Keywords: cold-formed steel, beams, DSM-based procedure, interior two flanged loading, web crippling

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742 Magnetron Sputtered Thin-Film Catalysts with Low Noble Metal Content for Proton Exchange Membrane Water Electrolysis

Authors: Peter Kus, Anna Ostroverkh, Yurii Yakovlev, Yevheniia Lobko, Roman Fiala, Ivan Khalakhan, Vladimir Matolin

Abstract:

Hydrogen economy is a concept of low-emission society which harvests most of its energy from renewable sources (e.g., wind and solar) and in case of overproduction, electrochemically turns the excess amount into hydrogen, which serves as an energy carrier. Proton exchange membrane water electrolyzers (PEMWE) are the backbone of this concept. By fast-response electricity to hydrogen conversion, the PEMWEs will not only stabilize the electrical grid but also provide high-purity hydrogen for variety of fuel cell powered devices, ranging from consumer electronics to vehicles. Wider commercialization of PEMWE technology is however hindered by high prices of noble metals which are necessary for catalyzing the redox reactions within the cell. Namely, platinum for hydrogen evolution reaction (HER), running on cathode, and iridium for oxygen evolution reaction (OER) on anode. Possible way of how to lower the loading of Pt and Ir is by using conductive high-surface nanostructures as catalyst supports in conjunction with thin-film catalyst deposition. The presented study discusses unconventional technique of membrane electron assembly (MEA) preparation. Noble metal catalysts (Pt and Ir) were magnetron sputtered in very low loadings onto the surface of porous sublayers (located on gas diffusion layer or directly on membrane), forming so to say localized three-phase boundary. Ultrasonically sprayed corrosion resistant TiC-based sublayer was used as a support material on anode, whereas magnetron sputtered nanostructured etched nitrogenated carbon (CNx) served the same role on cathode. By using this configuration, we were able to significantly decrease the amount of noble metals (to thickness of just tens of nanometers), while keeping the performance comparable to that of average state-of-the-art catalysts. Complex characterization of prepared supported catalysts includes in-cell performance and durability tests, electrochemical impedance spectroscopy (EIS) as well as scanning electron microscopy (SEM) imaging and X-ray photoelectron spectroscopy (XPS) analysis. Our research proves that magnetron sputtering is a suitable method for thin-film deposition of electrocatalysts. Tested set-up of thin-film supported anode and cathode catalysts with combined loading of just 120 ug.cm⁻² yields remarkable values of specific current. Described approach of thin-film low-loading catalyst deposition might be relevant when noble metal reduction is the topmost priority.

Keywords: hydrogen economy, low-loading catalyst, magnetron sputtering, proton exchange membrane water electrolyzer

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741 Effect of the Alloying Elements on Mechanical Properties of TWIP Steel

Authors: Yuksel Akinay, Fatih Hayat

Abstract:

The influence of the alloying element on mechanical properties and micro structures of the Fe-22Mn-0.6C-0,6Si twinning induced plasticity (TWIP) steel were investigated at different temperatures. This composition was fabricated by a vacuum induction melting method. This steel was homogenized at 1200◦C for 8h. After heat treatment it was hot-rolled at 1100◦C to 6 mm thickness. The hot rolled plates were cold rolled to 3 mm and annealed at 700 800 and 900 °C for 60 and 150 minute and then air-cooled. X-ray diffractometry (XRD), optic microscope and field emission scanning electron microscope (FESEM), hardness and tensile tests were used to analyse the relationship between mechanical properties and micro structure after annealing process. The results show that, the excellent mechanical properties were obtained after heat treatment process. The tensile strength of material was decreased and the ductility of material was improved with increasing annealing temperature. Ni element were increased the mechanical resistance of specimens and because of carbide precipitation the hardness of specimen annealed at 700 C is higher than others.

Keywords: high manganese, heat treatment, SEM, XRD, cold-rolling

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740 Leuco Dye-Based Thermochromic Systems for Application in Temperature Sensing

Authors: Magdalena Wilk-Kozubek, Magdalena Rowińska, Krzysztof Rola, Joanna Cybińska

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Leuco dye-based thermochromic systems are classified as intelligent materials because they exhibit thermally induced color changes. Thanks to this feature, they are mainly used as temperature sensors in many industrial sectors. For example, placing a thermochromic material on a chemical reactor may warn about exceeding the maximum permitted temperature for a chemical process. Usually two components, a color former and a developer are needed to produce a system with irreversible color change. The color former is an electron donating (proton accepting) compound such as fluoran leuco dye. The developer is an electron accepting (proton donating) compound such as organic carboxylic acid. When the developer melts, the color former - developer complex is created and the termochromic system becomes colored. Typically, the melting point of the applied developer determines the temperature at which the color change occurs. When the lactone ring of the color former is closed, then the dye is in its colorless state. The ring opening, induced by the addition of a proton, causes the dye to turn into its colored state. Since the color former and the developer are often solid, they can be incorporated into polymer films to facilitate their practical use in industry. The objective of this research was to fabricate a leuco dye-based termochromic system that will irreversibly change color after reaching the temperature of 100°C. For this purpose, benzofluoran leuco dye (as color former) and phenoxyacetic acid (as developer with a melting point of 100°C) were introduced into the polymer films during the drop casting process. The film preparation process was optimized in order to obtain thin films with appropriate properties such as transparency, flexibility and homogeneity. Among the optimized factors were the concentration of benzofluoran leuco dye and phenoxyacetic acid, the type, average molecular weight and concentration of the polymer, and the type and concentration of the surfactant. The selected films, containing benzofluoran leuco dye and phenoxyacetic acid, were combined by mild heat treatment. Structural characterization of single and combined films was carried out by FTIR spectroscopy, morphological analysis was performed by optical microscopy and SEM, phase transitions were examined by DSC, color changes were investigated by digital photography and UV-Vis spectroscopy, while emission changes were studied by photoluminescence spectroscopy. The resulting thermochromic system is colorless at room temperature, but after reaching 100°C the developer melts and it turns irreversibly pink. Therefore, it could be used as an additional sensor to warn against boiling of water in power plants using water cooling. Currently used electronic temperature indicators are prone to faults and unwanted third-party actions. The sensor constructed in this work is transparent, thanks to which it can be unnoticed by an outsider and constitute a reliable reference for the person responsible for the apparatus.

Keywords: color developer, leuco dye, thin film, thermochromism

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739 Molecular Dynamic Simulation of Cold Spray Process

Authors: Aneesh Joshi, Sagil James

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Cold Spray (CS) process is deposition of solid particles over a substrate above a certain critical impact velocity. Unlike thermal spray processes, CS process does not melt the particles thus retaining their original physical and chemical properties. These characteristics make CS process ideal for various engineering applications involving metals, polymers, ceramics and composites. The bonding mechanism involved in CS process is extremely complex considering the dynamic nature of the process. Though CS process offers great promise for several engineering applications, the realization of its full potential is limited by the lack of understanding of the complex mechanisms involved in this process and the effect of critical process parameters on the deposition efficiency. The goal of this research is to understand the complex nanoscale mechanisms involved in CS process. The study uses Molecular Dynamics (MD) simulation technique to understand the material deposition phenomenon during the CS process. Impact of a single crystalline copper nanoparticle on copper substrate is modelled under varying process conditions. The quantitative results of the impacts at different velocities, impact angle and size of the particles are evaluated using flattening ratio, von Mises stress distribution and local shear strain. The study finds that the flattening ratio and hence the quality of deposition was highest for an impact velocity of 700 m/s, particle size of 20 Å and an impact angle of 90°. The stress and strain analysis revealed regions of shear instabilities in the periphery of impact and also revealed plastic deformation of the particles after the impact. The results of this study can be used to augment our existing knowledge in the field of CS processes.

Keywords: cold spray process, molecular dynamics simulation, nanoparticles, particle impact

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738 2,7-Diazaindole as a Photophysical Probe for Excited State Hydrogen/Proton Transfer

Authors: Simran Baweja, Bhavika Kalal, Surajit Maity

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Photoinduced tautomerization reactions have been the centre of attention among the scientific community over the past several decades because of their significance in various biological systems. 7-azaindole (7AI) is considered a model system for DNA base pairing and to understand the role of such tautomerization reactions in mutations. To the best of our knowledge, extensive studies have been carried out on 7-azaindole and its solvent clusters exhibiting proton/ hydrogen transfer in both solution as well as gas phases. Derivatives of the above molecule, like 2,7- and 2,6-diazaindoles are proposed to have even better photophysical properties due to the presence of -aza group on the 2nd position. However, there are studies in the solution phase that suggest the relevance of these molecules, but there are no experimental studies reported in the gas phase yet. In our current investigation, we present the first gas phase spectroscopic data of 2,7-diazaindole (2,7-DAI) and its solvent cluster (2,7-DAI-H2O). In this, we have employed state-of-the-art laser spectroscopic methods such as fluorescence excitation (LIF), dispersed fluorescence (DF), resonant two-photon ionization-time of flight mass spectrometry (2C-R2PI), photoionization efficiency spectroscopy (PIE), IR-UV double resonance spectroscopy, i.e., fluorescence-dip infrared spectroscopy (FDIR) and resonant ion-dip infrared spectroscopy (IDIR) to understand the electronic structure of the molecule. The origin band corresponding to the S1 ← S0 transition of the bare 2,7-DAI is found to be positioned at 33910 cm-1, whereas the origin band corresponding to S1 ← S0 transition of the 2,7-DAI-H2O is positioned at 33074 cm-1. The red-shifted transition in the case of solvent cluster suggests the enhanced feasibility of excited state hydrogen/ proton transfer. The ionization potential for the 2,7-DAI molecule is found to be 8.92 eV which is significantly higher than the previously reported 7AI (8.11 eV) molecule, making it a comparatively complex molecule to study. The ionization potential is reduced by 0.14 eV in the case of 2,7-DAI-H2O (8.78 eV) cluster compared to that of 2,7-DAI. Moreover, on comparison with the available literature values of 7AI, we found the origin band of 2,7-DAI and 2,7-DAI-H2O to be red-shifted by -729 and -280 cm-1 respectively. The ground and excited state N-H stretching frequencies of the 27DAI molecule were determined using fluorescence-dip infrared spectra (FDIR) and resonant ion dip infrared spectroscopy (IDIR), obtained at 3523 and 3467 cm-1, respectively. The lower value of vNH in the electronically excited state of 27DAI implies the higher acidity of the group compared to the ground state. Moreover, we have done extensive computational analysis, which suggests that the energy barrier in the excited state reduces significantly as we increase the number of catalytic solvent molecules (S= H2O, NH3) as well as the polarity of solvent molecules. We found that the ammonia molecule is a better candidate for hydrogen transfer compared to water because of its higher gas-phase basicity. Further studies are underway to understand the excited state dynamics and photochemistry of such N-rich chromophores.

Keywords: excited state hydrogen transfer, supersonic expansion, gas phase spectroscopy, IR-UV double resonance spectroscopy, laser induced fluorescence, photoionization efficiency spectroscopy

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737 Disinfestation of Harvest Celery Apium graveolens var. dulce Using Low Temperature as Quarantine Treatment for Springtails Hypogastrura vernalis (Carl) (Collembola: Hypogastruridae)

Authors: Q. Ahmed, Y. Ren, R. Emery, J. Newman, M. Agarwal

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Celery (Apium graveolens var. dulce) is grown in Australia for domestic consumption and export markets. Quarantine treatment enables export of celery to the world that enforces quarantine against springtails. In the field, celery bunches become host to the Australian native springtail (Hypogastrura vernalis) (Collembola: Hypogastruridae). Springtails live inside the celery bunch and do not cause damage to the product. Springtails are, however, considered a quarantine pest and have had a significant impact on celery exports. In this experiment, cold treatments were conducted on fresh celery to investigate their effect on springtail mortality. Four low-temperature treatments were used (3, 5, 10, and 15 ºC) over four treatment periods (3, 5, 7, and 14 days). Springtail mortality was not affected by the 3, 5, 10 and 15 ºC treatments for the treatment periods of 3, 5, 7, and 14 days. Low-temperature damage was observed most noticeably on celery in the 3 and 5 ºC treatments.

Keywords: springtails, fresh celery, cold treatment, quarantine treatment

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736 Shear Strength of Reinforced Web Openings in Steel Beams

Authors: K. S. Sivakumaran, Bo Chen

Abstract:

The floor beams of steel buildings, cold-formed steel floor joists, in particular, often require large web openings, which may affect their shear capacities. A cost effective way to mitigate the detrimental effects of such openings is to weld/fasten reinforcements. A difficulty associated with an experimental investigation to establish suitable reinforcement schemes for openings in shear zone is that moment always coexists with the shear, and thus, it is impossible to create pure shear state in experiments, resulting in moment influenced results. However, finite element analysis can be conveniently used to investigate the pure shear behaviour of webs including webs with reinforced opening. This paper presents that the details associated with the finite element analysis of thick/thin-plates (representing the web of hot-rolled steel beam, and the web of a cold-formed steel member) having a large reinforced openings. The study considered thin simply supported rectangular plates subjected to inplane shear loadings until failure (including post-buckling behaviour). The plate was modelled using geometrically non-linear quadrilateral shell elements, and non-linear stress-strain relationship based on experiments. Total Lagrangian (TL) with large displacement/small strain formulation was used for such analysis. The model also considered the initial geometric imperfections. This study considered three reinforcement schemes, namely, flat, lip, and angle reinforcements. This paper discusses the modelling considerations and presents the results associated with the various reinforcement schemes under consideration. The paper briefly compares the analysis results with the experimental results.

Keywords: cold-formed steel, finite element analysis, opening, reinforcement, shear resistance

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735 Effects of the Gap on the Cooling Performance of Microchannels Heat Sink

Authors: Mohammed W. Sulaiman, Chi-Chuan Wang

Abstract:

Due to the improved performance of electronic systems, the demand for electronic cooling devices with high heat dissipation has increased. This research evaluates plain microchannel cold plates with a gap above the microchannels. The present study examines the effect of the gap above straight fin microchannels in the cold plate using the dielectric Novec 7000 as a working fluid. The experiments compared two transparency cover with the same geometry and dimension for the test section. One has a gap above the microchannels (GAM) 1/3 of fin height, and another one with no gap above the microchannels (NGAM); the mass flux ranges from 25 to 260 kg/m2s, while the heat flux spans from 50 to 150 W/cm2. The results show quite an improvement in performance with this space gap above the microchannels. The test results showed that the design of the GAM shows a superior heat transfer coefficient (HTC), up 90% than that of NCBM. The GAM design has a much lower pressure drop by about 7~24% compared to the NGAM design at different mass flux and heat flux at the fully liquid inlet. The proposed space gap of 0.33% of fin height above the microchannels enables the surface temperature to decrease by around 3~7 °C compared to no gap above the microchannels, especially at high heat fluxes.

Keywords: microchannels, pressure drop, enhanced performance, electronic cooling, gap

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734 Polymer Spiral Film Gas-Liquid Heat Exchanger for Waste Heat Recovery in Exhaust Gases

Authors: S. R. Parthiban, C. Elajchet Senni

Abstract:

Spiral heat exchangers are known as excellent heat exchanger because of far compact and high heat transfer efficiency. An innovative spiral heat exchanger based on polymer materials is designed for waste heat recovery process. Such a design based on polymer film technology provides better corrosion and chemical resistance compared to conventional metal heat exchangers. Due to the smooth surface of polymer film fouling is reduced. A new arrangement for flow of hot flue gas and cold fluid is employed for design, flue gas flows in axial path while the cold fluid flows in a spiral path. Heat load recovery achieved with the presented heat exchanger is in the range of 1.5 kW thermic but potential heat recovery about 3.5kW might be achievable. To measure the performance of the spiral tube heat exchanger, its model is suitably designed and fabricated so as to perform experimental tests. The paper gives analysis of spiral tube heat exchanger.

Keywords: spiral heat exchanger, polymer based materials, fouling factor, heat load

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733 Manganese Imidazole Complexes: Electrocatalytic Hydrogen Production

Authors: Vishakha Kaim, Mookan Natarajan, Sandeep Kaur-Ghumaan

Abstract:

Hydrogen is one of the most abundant elements present on earth’s crust and considered to be the simplest element in existence. It is not found naturally as a gas on earth and thus has to be manufactured. Hydrogen can be produced from a variety of sources, i.e., water, fossil fuels, or biomass and it is a byproduct of many chemical processes. It is also considered as a secondary source of energy commonly referred to as an energy carrier. Though hydrogen is not widely used as a fuel, it still has the potential for greater use in the future as a clean and renewable source of energy. Electrocatalysis is one of the important source for the production of hydrogen which could contribute to this prominent challenge. Metals such as platinum and palladium are considered efficient for hydrogen production but with limited applications. As a result, a wide variety of metal complexes with earth abundant elements and varied ligand environments have been explored for the electrochemical production of hydrogen. In nature, [FeFe] hydrogenase enzyme present in DesulfoVibrio desulfuricans and Clostridium pasteurianum catalyses the reversible interconversion of protons and electrons into dihydrogen. Since the first structure for the enzyme was reported in 1990s, a range of iron complexes has been synthesized as structural and functional mimics of the enzyme active site. Mn is one of the most desirable element for sustainable catalytic transformations, immediately behind Fe and Ti. Only limited number manganese complexes have been reported in the last two decades as catalysts for proton reduction. Furthermore, redox reactions could be carried out in a facile manner, due to the capability of manganese complexes to be stable at different oxidation states. Herein are reported, four µ2-thiolate bridged manganese complexes [Mn₂(CO)₆(μ-S₂N₄C₁₄H₁₀)] 1, [Mn₂(CO)7(μ- S₂N₄C₁₄H₁₀)] 2, Mn₂(CO)₆(μ-S₄N₂C₁₄H₁₀)] 3 and [Mn₂(CO)(μ- S₄N₂C₁₄H₁₀)] 4 have been synthesized and characterized. The cyclic voltammograms of the complexes displayed irreversible reduction peaks in the range - 0.9 to -1.3 V (vs. Fc⁺/Fc in acetonitrile at 0.1 Vs⁻¹). The complexes were catalytically active towards proton reduction in the presence of trifluoroacetic acid as seen from electrochemical investigations.

Keywords: earth abundant, electrocatalytic, hydrogen, manganese

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732 Evaluation of Hepatic Metabolite Changes for Differentiation Between Non-Alcoholic Steatohepatitis and Simple Hepatic Steatosis Using Long Echo-Time Proton Magnetic Resonance Spectroscopy

Authors: Tae-Hoon Kim, Kwon-Ha Yoon, Hong Young Jun, Ki-Jong Kim, Young Hwan Lee, Myeung Su Lee, Keum Ha Choi, Ki Jung Yun, Eun Young Cho, Yong-Yeon Jeong, Chung-Hwan Jun

Abstract:

Purpose: To assess the changes of hepatic metabolite for differentiation between non-alcoholic steatohepatitis (NASH) and simple steatosis on proton magnetic resonance spectroscopy (1H-MRS) in both humans and animal model. Methods: The local institutional review board approved this study and subjects gave written informed consent. 1H-MRS measurements were performed on a localized voxel of the liver using a point-resolved spectroscopy (PRESS) sequence and hepatic metabolites of alanine (Ala), lactate/triglyceride (Lac/TG), and TG were analyzed in NASH, simple steatosis and control groups. The group difference was tested with the ANOVA and Tukey’s post-hoc tests, and diagnostic accuracy was tested by calculating the area under the receiver operating characteristics (ROC) curve. The associations between metabolic concentration and pathologic grades or non-alcoholic fatty liver disease(NAFLD) activity scores were assessed by the Pearson’s correlation. Results: Patient with NASH showed the elevated Ala(p<0.001), Lac/TG(p < 0.001), TG(p < 0.05) concentration when compared with patients who had simple steatosis and healthy controls. The NASH patients were higher levels in Ala(mean±SEM, 52.5±8.3 vs 2.0±0.9; p < 0.001), Lac/TG(824.0±168.2 vs 394.1±89.8; p < 0.05) than simple steatosis. The area under the ROC curve to distinguish NASH from simple steatosis was 1.00 (95% confidence interval; 1.00, 1.00) with Ala and 0.782 (95% confidence interval; 0.61, 0.96) with Lac/TG. The Ala and Lac/TG levels were well correlated with steatosis grade, lobular inflammation, and NAFLD activity scores. The metabolic changes in human were reproducible to a mice model induced by streptozotocin injection and a high-fat diet. Conclusion: 1H-MRS would be useful for differentiation of patients with NASH and simple hepatic steatosis.

Keywords: non-alcoholic fatty liver disease, non-alcoholic steatohepatitis, 1H MR spectroscopy, hepatic metabolites

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731 Estimation of Grinding Force and Material Characterization of Ceramic Matrix Composite

Authors: Lakshminarayanan, Vijayaraghavan, Krishnamurthy

Abstract:

The ever-increasing demand for high efficiency in automotive and aerospace applications requires new materials to suit to high temperature applications. The Ceramic Matrix Composites nowadays find its applications for high strength and high temperature environments. In this paper, Al2O3 and Sic ceramic materials are taken in particulate form as matrix and reinforcement respectively. They are blended together in Ball Milling and compacted in Cold Compaction Machine by powder metallurgy technique. Scanning Electron Microscope images are taken for the samples in order to find out proper blending of powders. Micro harness testing is also carried out for the samples in Vickers Micro Hardness Testing Equipment. Surface grinding of the samples is also carried out in Surface Grinding Machine in order to find out grinding force estimates. The surface roughness of the grounded samples is also taken in Surface Profilometer. These are yielding promising results.

Keywords: ceramic matrix composite, cold compaction, material characterization, particulate and surface grinding

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730 Effect of Al Contents on Magnetic Domains of {100} Grains in Electrical Steels

Authors: Hyunseo Choi, Jaewan Hong, Seil Lee, Yang Mo Koo

Abstract:

Non-oriented (NO) electrical steel is one of the most important soft magnetic materials for rotating machines. Si has usually been added to electrical steels to reduce eddy current loss by increasing the electrical resistivity. Si content more than 3.5 wt% causes cracks during cold rolling due to increase of brittleness. Al also increases the electrical resistivity of the materials as much as Si. In addition, cold workability of Fe-Al is better than Fe-Si, so that Al can be added up to 6.0 wt%. However, the effect of Al contents on magnetic properties of electrical steels has not been studied in detail. Magnetic domains of {100} grains in electrical steels, ranging from 1.85 to 6.54 wt% Al, were observed by magneto-optic Kerr microscopy. Furthermore, the correlation of magnetic domains with magnetic properties was investigated. As Al contents increased, the magnetic domain size of {100} grains decreased due to lowered domain wall energy. Reorganization of magnetic domain structure became more complex as domain size decreased. Therefore, the addition of Al to electrical steel caused hysteresis loss to increase. Anomalous loss decreased and saturated after 4.68% Al.

Keywords: electrical steel, magnetic domain structure, Al addition, core loss, rearrangement of domains

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729 CFD Modeling of Stripper Ash Cooler of Circulating Fluidized Bed

Authors: Ravi Inder Singh

Abstract:

Due to high heat transfer rate, high carbon utilizing efficiency, fuel flexibilities and other advantages numerous circulating fluidized bed boilers have grown up in India in last decade. Many companies like BHEL, ISGEC, Thermax, Cethar Limited, Enmas GB Power Systems Projects Limited are making CFBC and installing the units throughout the India. Due to complexity many problems exists in CFBC units and only few have been reported. Agglomeration i.e clinker formation in riser, loop seal leg and stripper ash coolers is one of problem industry is facing. Proper documentation is rarely found in the literature. Circulating fluidized bed (CFB) boiler bottom ash contains large amounts of physical heat. While the boiler combusts the low-calorie fuel, the ash content is normally more than 40% and the physical heat loss is approximately 3% if the bottom ash is discharged without cooling. In addition, the red-hot bottom ash is bad for mechanized handling and transportation, as the upper limit temperature of the ash handling machinery is 200 °C. Therefore, a bottom ash cooler (BAC) is often used to treat the high temperature bottom ash to reclaim heat, and to have the ash easily handled and transported. As a key auxiliary device of CFB boilers, the BAC has a direct influence on the secure and economic operation of the boiler. There are many kinds of BACs equipped for large-scale CFB boilers with the continuous development and improvement of the CFB boiler. These ash coolers are water cooled ash cooling screw, rolling-cylinder ash cooler (RAC), fluidized bed ash cooler (FBAC).In this study prototype of a novel stripper ash cooler is studied. The Circulating Fluidized bed Ash Coolers (CFBAC) combined the major technical features of spouted bed and bubbling bed, and could achieve the selective discharge on the bottom ash. The novel stripper ash cooler is bubbling bed and it is visible cold test rig. The reason for choosing cold test is that high temperature is difficult to maintain and create in laboratory level. The aim of study to know the flow pattern inside the stripper ash cooler. The cold rig prototype is similar to stripper ash cooler used industry and it was made after scaling down to some parameter. The performance of a fluidized bed ash cooler is studied using a cold experiment bench. The air flow rate, particle size of the solids and air distributor type are considered to be the key parameters of the operation of a fluidized bed ash cooler (FBAC) are studied in this.

Keywords: CFD, Eulerian-Eulerian, Eulerian-Lagraingian model, parallel simulations

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728 Performance Optimization of Polymer Materials Thanks to Sol-Gel Chemistry for Fuel Cells

Authors: Gondrexon, Gonon, Mendil-Jakani, Mareau

Abstract:

Proton Exchange Membrane Fuel Cells (PEMFCs) seems to be a promising device used for converting hydrogen into electricity. PEMFC is made of a Membrane Electrode Assembly (MEA) composed of a Proton Exchange Membrane (PEM) sandwiched by two catalytic layers. Nowadays, specific performances are targeted in order to ensure the long-term expansion of this technology. Current polymers used (perfluorinated as Nafion®) are unsuitable (loss of mechanical properties) for the high-temperature range. To overcome this issue, sulfonated polyaromatic polymers appear to be a good alternative since it has very good thermomechanical properties. However, their proton conductivity and chemical stability (oxidative resistance to H2O2 formed during fuel cell (FC) operating) are very low. In our team, we patented an original concept of hybrid membranes able to fulfill the specific requirements for PEMFC. This idea is based on the improvement of commercialized polymer membrane via an easy and processable stabilization thanks to sol-gel (SG) chemistry with judicious embeded chemical functions. This strategy is thus breaking up with traditional approaches (design of new copolymers, use of inorganic charges/additives). In 2020, we presented the elaboration and functional properties of a 1st generation of hybrid membranes with promising performances and durability. The latter was made by self-condensing a SG phase with 3(mercaptopropyl)trimethoxysilane (MPTMS) inside a commercial sPEEK host membrane. The successful in-situ condensation reactions of the MPTMS was demonstrated by measures of mass uptakes, FTIR spectroscopy (presence of C-Haliphatics) and solid state NMR 29Si (T2 & T3 signals of self-condensation products). The ability of the SG phase to prevent the oxidative degradation of the sPEEK phase (thanks to thiol chemical functions) was then proved with H2O2 accelerating tests and FC operating tests. A 2nd generation made of thiourea functionalized SG precursors (named HTU & TTU) was made after. By analysing in depth the morphologies of these different hybrids by direct space analysis (AFM/SEM/TEM) and reciprocal space analysis (SANS/SAXS/WAXS), we highlighted that both SG phase morphology and its localisation into the host has a huge impact on the PEM functional properties observed. This relationship is also dependent on the chemical function embedded. The hybrids obtained have shown very good chemical resistance during aging test (exposed to H2O2) compared to the commercial sPEEK. But the chemical function used is considered as “sacrificial” and cannot react indefinitely with H2O2. Thus, we are now working on a 3rd generation made of both sacrificial/regenerative chemical functions which are expected to inhibit the chemical aging of sPEEK more efficiently. With this work, we are confident to reach a predictive approach of the key parameters governing the final properties.

Keywords: fuel cells, ionomers, membranes, sPEEK, chemical stability

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727 Intriguing Modulations in the Excited State Intramolecular Proton Transfer Process of Chrysazine Governed by Host-Guest Interactions with Macrocyclic Molecules

Authors: Poojan Gharat, Haridas Pal, Sharmistha Dutta Choudhury

Abstract:

Tuning photophysical properties of guest dyes through host-guest interactions involving macrocyclic hosts are the attractive research areas since past few decades, as these changes can directly be implemented in chemical sensing, molecular recognition, fluorescence imaging and dye laser applications. Excited state intramolecular proton transfer (ESIPT) is an intramolecular prototautomerization process display by some specific dyes. The process is quite amenable to tunability by the presence of different macrocyclic hosts. The present study explores the interesting effect of p-sulfonatocalix[n]arene (SCXn) and cyclodextrin (CD) hosts on the excited-state prototautomeric equilibrium of Chrysazine (CZ), a model antitumour drug. CZ exists exclusively in its normal form (N) in the ground state. However, in the excited state, the excited N* form undergoes ESIPT along with its pre-existing intramolecular hydrogen bonds, giving the excited state prototautomer (T*). Accordingly, CZ shows a single absorption band due to N form, but two emission bands due to N* and T* forms. Facile prototautomerization of CZ is considerably inhibited when the dye gets bound to SCXn hosts. However, in spite of lower binding affinity, the inhibition is more profound with SCX6 host as compared to SCX4 host. For CD-CZ system, while prototautomerization process is hindered by the presence of β-CD, it remains unaffected in the presence of γCD. Reduction in the prototautomerization process of CZ by SCXn and βCD hosts is unusual, because T* form is less dipolar in nature than the N*, hence binding of CZ within relatively hydrophobic hosts cavities should have enhanced the prototautomerization process. At the same time, considering the similar chemical nature of two CD hosts, their effect on prototautomerization process of CZ would have also been similar. The atypical effects on the prototautomerization process of CZ by the studied hosts are suggested to arise due to the partial inclusion or external binding of CZ with the hosts. As a result, there is a strong possibility of intermolecular H-bonding interaction between CZ dye and the functional groups present at the portals of SCXn and βCD hosts. Formation of these intermolecular H-bonds effectively causes the pre-existing intramolecular H-bonding network within CZ molecule to become weak, and this consequently reduces the prototautomerization process for the dye. Our results suggest that rather than the binding affinity between the dye and host, it is the orientation of CZ in the case of SCXn-CZ complexes and the binding stoichiometry in the case of CD-CZ complexes that play the predominant role in influencing the prototautomeric equilibrium of the dye CZ. In the case of SCXn-CZ complexes, the results obtained through experimental findings are well supported by quantum chemical calculations. Similarly for CD-CZ systems, binding stoichiometries obtained through geometry optimization studies on the complexes between CZ and CD hosts correlate nicely with the experimental results. Formation of βCD-CZ complexes with 1:1 stoichiometry while formation of γCD-CZ complexes with 1:1, 1:2 and 2:2 stoichiometries are revealed from geometry optimization studies and these results are in good accordance with the observed effects by the βCD and γCD hosts on the ESIPT process of CZ dye.

Keywords: intermolecular proton transfer, macrocyclic hosts, quantum chemical studies, photophysical studies

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726 Effects of Bipolar Plate Coating Layer on Performance Degradation of High-Temperature Proton Exchange Membrane Fuel Cell

Authors: Chen-Yu Chen, Ping-Hsueh We, Wei-Mon Yan

Abstract:

Over the past few centuries, human requirements for energy have been met by burning fossil fuels. However, exploiting this resource has led to global warming and innumerable environmental issues. Thus, finding alternative solutions to the growing demands for energy has recently been driving the development of low-carbon and even zero-carbon energy sources. Wind power and solar energy are good options but they have the problem of unstable power output due to unpredictable weather conditions. To overcome this problem, a reliable and efficient energy storage sub-system is required in future distributed-power systems. Among all kinds of energy storage technologies, the fuel cell system with hydrogen storage is a promising option because it is suitable for large-scale and long-term energy storage. The high-temperature proton exchange membrane fuel cell (HT-PEMFC) with metallic bipolar plates is a promising fuel cell system because an HT-PEMFC can tolerate a higher CO concentration and the utilization of metallic bipolar plates can reduce the cost of the fuel cell stack. However, the operating life of metallic bipolar plates is a critical issue because of the corrosion phenomenon. As a result, in this work, we try to apply different coating layer on the metal surface and to investigate the protection performance of the coating layers. The tested bipolar plates include uncoated SS304 bipolar plates, titanium nitride (TiN) coated SS304 bipolar plates and chromium nitride (CrN) coated SS304 bipolar plates. The results show that the TiN coated SS304 bipolar plate has the lowest contact resistance and through-plane resistance and has the best cell performance and operating life among all tested bipolar plates. The long-term in-situ fuel cell tests show that the HT-PEMFC with TiN coated SS304 bipolar plates has the lowest performance decay rate. The second lowest is CrN coated SS304 bipolar plate. The uncoated SS304 bipolar plate has the worst performance decay rate. The performance decay rates with TiN coated SS304, CrN coated SS304 and uncoated SS304 bipolar plates are 5.324×10⁻³ % h⁻¹, 4.513×10⁻² % h⁻¹ and 7.870×10⁻² % h⁻¹, respectively. In addition, the EIS results indicate that the uncoated SS304 bipolar plate has the highest growth rate of ohmic resistance. However, the ohmic resistance with the TiN coated SS304 bipolar plates only increases slightly with time. The growth rate of ohmic resistances with TiN coated SS304, CrN coated SS304 and SS304 bipolar plates are 2.85×10⁻³ h⁻¹, 3.56×10⁻³ h⁻¹, and 4.33×10⁻³ h⁻¹, respectively. On the other hand, the charge transfer resistances with these three bipolar plates all increase with time, but the growth rates are all similar. In addition, the effective catalyst surface areas with all bipolar plates do not change significantly with time. Thus, it is inferred that the major reason for the performance degradation is the elevated ohmic resistance with time, which is associated with the corrosion and oxidation phenomena on the surface of the stainless steel bipolar plates.

Keywords: coating layer, high-temperature proton exchange membrane fuel cell, metallic bipolar plate, performance degradation

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725 Protonic Conductivity Highlighted by Impedance Measurement of Y-Doped BaZrO3 Synthesized by Supercritical Hydrothermal Process

Authors: Melanie Francois, Gilles Caboche, Frederic Demoisson, Francois Maeght, Maria Paola Carpanese, Lionel Combemale, Pascal Briois

Abstract:

Finding new clean, and efficient way for energy production is one of the actual global challenges. Advances in fuel cell technology have shown that, for few years, Protonic Ceramic Fuel Cell (PCFC) has attracted much attention in the field of new hydrogen energy thanks to their lower working temperature, possible higher efficiency, and better durability than classical SOFC. On the contrary of SOFC, where O²⁻ oxygen ion is the charge carrier, PCFC works with H⁺ proton as a charge carrier. Consequently, the lower activation energy of proton diffusion compared to the one of oxygen ion explains those benefits and allows PCFC to work in the 400-600°C temperature range. Doped-BaCeO₃ is currently the most chosen material for this application because of its high protonic conductivity; for example, BaCe₀.₉Y₀.₁O₃ δ exhibits a total conductivity of 1.5×10⁻² S.cm⁻¹ at 600°C in wet H₂. However, BaCeO₃ based perovskite has low stability in H₂O and/or CO₂ containing atmosphere, which limits their practical application. On the contrary, BaZrO₃ based perovskite exhibits good chemical stability but lower total conductivity than BaCeO₃ due to its larger grain boundary resistance. By substituting zirconium with 20% of yttrium, it is possible to achieve a total conductivity of 2.5×10⁻² S.cm⁻¹ at 600°C in wet H₂. However, the high refractory property of BaZr₀.₈Y₀.₂O₃-δ (noted BZY20) causes problems to obtain a dense membrane with large grains. Thereby, using a synthesis process that gives fine particles could allow better sinterability and thus decrease the number of grain boundaries leading to a higher total conductivity. In this work, BaZr₀.₈Y₀.₂O₃-δ have been synthesized by classical batch hydrothermal device and by a continuous hydrothermal device developed at ICB laboratory. The two variants of this process are able to work in supercritical conditions, leading to the formation of nanoparticles, which could be sintered at a lower temperature. The as-synthesized powder exhibits the right composition for the perovskite phase, impurities such as BaCO₃ and YO-OH were detected at very low concentration. Microstructural investigation and densification rate measurement showed that the addition of 1 wt% of ZnO as sintering aid and a sintering at 1550°C for 5 hours give high densified electrolyte material. Furthermore, it is necessary to heat the synthesized powder prior to the sintering to prevent the formation of secondary phases. It is assumed that this thermal treatment homogenizes the crystal structure of the powder and reduces the number of defects into the bulk grains. Electrochemical impedance spectroscopy investigations in various atmospheres and a large range of temperature (200-700°C) were then performed on sintered samples, and the protonic conductivity of BZY20 has been highlighted. Further experiments on half-cell, NiO-BZY20 as anode and BZY20 as electrolyte, are in progress.

Keywords: hydrothermal synthesis, impedance measurement, Y-doped BaZrO₃, proton conductor

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