Microstructure,texture, and crystallography in Ni–GDC and Co–GDC porous cermets obtained from directionally solidified eutectic ceramics

Lamellar NiO–GDC (Gadolinium-doped Ceria) and CoO–GDC directionally solidified eutectic ceramics (DSECs) were produced by the laser floating-zone technique and subjected to reduction in order to obtain porous cermets of Ni–GDC and Co–GDC, which have potential applications as anodes in solid oxide fuel cells (SOFC). The reduction of these DSECs into porous cermets was studied at 650 °C in NiO–GDC and at 500 and 700 °C in CoO–GDC, all of them processed with similar reduction kinetics. In comparison to similar Ni–YSZ and Co–YSZ lamellar cermets previously studied, no sharp reduction front was observed. The interface between the reduced and nonreduced zones is broader, with pores homogenously distributed in wide areas. Afterwards, the microstructure, texture, and crystallography of the samples were studied by electron microscopy as well as by electron and X-ray diffraction when completely reduced. The single crystal NiO and CoO lamellae transformed into porous polycrystalline metallic lamellae. Moreover, microscopy observations revealed a porous nanostructure of Co particles obtained by reduction at low temperatures (500 °C). Many of the Co and Ni particles seemed to have roughly maintained the previous crystallographic orientation with respect to the GDC phase, although the disorder of the crystallographic orientation increased significantly. In addition, a significant amount of the Ni particles reoriented to form an epitaxial interface with the (100)–GDC surface.     

A redox-stable efficient anode for solid-oxide fuel cells

Solid-oxide fuel cells (SOFCs) promise high efficiencies in a range of fuels. Unlike lower temperature variants, carbon monoxide is a fuel rather than a poison, and so hydrocarbon fuels can be used directly, through internal reforming or even direct oxidation. This provides a key entry strategy for fuel-cell technology into the current energy economy. Present development is mainly based on the yttria-stabilized zirconia (YSZ) electrolyte. The most commonly used anode materials are Ni/YSZ cermets, which display excellent catalytic properties for fuel oxidation and good current collection, but do exhibit disadvantages, such as low tolerance to sulphur and carbon deposition when using hydrocarbon fuels, and poor redox cycling causing volume instability. Here, we report a nickel-free SOFC anode, La0.75Sr0.25Cr0.5Mn0.5O3, with comparable electrochemical performance to Ni/YSZ cermets. The electrode polarization resistance approaches 0.2 Omega cm2 at 900 degrees C in 97% H2/3% H2O. Very good performance is achieved for methane oxidation without using excess steam. The anode is stable in both fuel and air conditions, and shows stable electrode performance in methane. Thus both redox stability and operation in low steam hydrocarbons have been demonstrated, overcoming two of the major limitations of the current generation of nickel zirconia cermet SOFC anodes.     

基于Pr0.6Sr0.4Co0.2Fe0.8O3-δ对称固体氧化物燃料电池的性能优化研究

采用柠檬酸-硝酸盐自蔓延燃烧法分别合成了Pr_0.6Sr_0.4Co_0.2Fe_0.8O_3-δ(PSCF)和Gd_0.2Ce_0.8O_2-δ(GDC)粉体, 高温固相法合成La_0.9Sr_0.1Ga_0.8Mg_0.2O_3-δ(LSGM)电解质粉体。以LSGM为电解质, PSCF同时作为阴极和阳极, GDC作为功能层材料, 构建了对称固体氧化物燃料电池PSCF│GDC│LSGM│GDC│PSCF。利用X射线衍射法研究材料的成相以及相互间的化学稳定性, 交流阻抗法记录界面极化行为, 用扫描电子显微镜观察电池的断面微结构, 用自组装的测试系统评价电池输出性能。结果表明, 合成的PSCF粉体呈立方钙钛矿结构, 具有良好的氧化-还原可逆性。使用GDC功能层明显改善了氢气环境下PSCF与LSGM材料间的化学相容性以及电池的输出性能, 800℃时, 电极│电解质界面极化电阻从6.892 Ω·cm²下降到0.314 Ω·cm²; 以加湿H₂(含体积分数3%的水蒸气)为燃料气, 空气为氧化气时, 单电池输出功率密度由269 mW/cm²增大至463 mW/cm²。研究结果显示, PSCF是对称固体氧化物燃料电池良好的候选电极材料, GDC功能层对改善电池长期稳定性能具有潜在的应用价值。     

煤气组分对固体氧化物燃料电池碳沉积的影响

以煤气化合成气作为固体氧化物燃料电池的燃料是煤炭清洁利用的重要方式之一, 但是存在碳沉积会对SOFC的运行造成一定影响. 本文构建了基于实验的全三维SOFC数学模型, 考虑了化学/电化学反应、气体的流动和扩散、气固耦合换热、过电势等多种运行参数, 计算了煤气化合成气中不同组分对以Ni-YSZ为阳极的SOFC碳沉积的影响. 可以看出, 增加水蒸气以及二氧化碳有助于碳沉积的降低, 但是过多的水蒸气和二氧化碳也会导致SOFC输出电压的降低. 较高的氢气含量对碳沉积也有一定的抑制作用. 一氧化碳含量的增加有助于减少碳沉积的范围, 但在SOFC入口处却增加了碳沉积活性. 同时, 甲烷能导致剧烈的碳沉积, 因此, 在煤气化合成气中应尽量去除甲烷.     

La2BO4(B:B位元素)系列混合导体掺杂成份优化规律研究

基于材料基因组计划(MGI)研究方式, 利用密度泛函理论(DFT)的第一性原理的总能量计算方法, 以K₂NiF₄型La₂BO₄(B:B位元素)相关的几种相结构为计算模型, 针对4~6周期48种B位金属元素替换, 进行几何优化的总能量计算, 得到这些相关虚拟相结构的结合能随元素的变化规律。通过层状相La₂BO₄与立方相LaBO₃的比较, 着重讨论了一些重要B位元素(Fe、Co、Ni、Cu、Zn、Se)对稳定La₂BO₄复合氧化物相稳定性的影响作用和趋势。结合相关的实验数据, 进一步讨论了掺杂B位元素的优化稳定区域。本定量分析方法为此类材料的合成和成份优化设计提供了一种行之有效的分析方法。     

溶胶-燃烧法制备Ce0.8 Gd0.2 O1.9及其性能

采用溶胶-燃烧法合成了Gd掺杂CeO2的Ce0.8Gd0.2O1.9(GDC)电解质粉末.研究了热处理温度对其相组成、颗粒大小、晶胞参数的影响.并对GDC烧结体的性能进行了研究.结果表明,溶胶一燃烧法可以成功制备出具有良好的烧结性的GDC电解质粉末,1500℃下得到的GDC烧结体的相对密度可以达到95%.电性能测试表明烧结体在中温范围内具有较高的氧离子电导率.     

电动汽车和相关电源材料的现状与前景

论述了电动汽车（EV）、电动汽车用镍氢电池、锂离子电池、质子交换膜燃料电池（PEMFC）、固体氧化物燃料电池（SOFC）及相关材料的研发现状、产业化前景，指出以电动汽车代替燃油内燃机汽车，以氢能代替碳基燃料，是当前运输业的主要发展方向。     

Characterisation of paraffin-based hybrid rocket fuels loaded with nano-additives

ABSTRACT

In this work, a new composition based on Paraffin wax and HTPB fuel, loaded with nanoparticles has been proposed for hybrid propulsion system. Lithium aluminium hydride (LiAlH₄) and Magnesium hydride (MgH₂) nanoparticles have been used as additives. A detailed rheological, thermal and ballistic characterisation has been carried out. The Magnesium hydride doped hybrid fuel exhibits lower viscosity as compared to the Lithium aluminium hydride doped one, leading to comparatively enhanced entrainment-aided combustion. LiAlH₄ doped hybrid fuels also exhibit solid-like behaviour and thus greater stability in the solid phase in contrast to the MgH₂ doped fuel. LiAlH₄ doped fuel is thermally more stable and produces relatively greater residual-mass. The loading of nanoparticles significantly improves the fuel regression performance during ballistic firing. This can be attributed to the release of nascent hydrogen and metal nanoparticles during dehydrogenation of metal hydrides. Regression rate enhancement in the range of 350%–475% is observed in comparison to the conventional HTPB hybrid fuels. A power law governing regression rate has been proposed for the tested hybrid fuels.     

Synthesis and characterization of electrolyte-grade 10%Gd-doped ceria thin film/ceramic substrate structures for solid oxide fuel cells

In the present research, spray pyrolysis technique is employed to synthesize 10%Gd-doped ceria (GDC) thin films on ceramic substrates with an intention to use the "film/substrate" structure in solid oxide fuel cells. GDC films deposited on GDC substrate showed enhanced crystallite formation. In case of NiO-GDC composite substrate, the thickness of film was higher (~ 13 μm) as compared to the film thickness on GDC substrate (~ 2 μm). The relative density of the films deposited on both the substrates was of the order of 95%. The impedance measurements revealed that ionic conductivity of GDC/NiO-GDC structure was of the order of 0.10 S/cm at 500 °C, which is a desirable property for its prospective application.     

Microscopy and neutron diffraction study of a zirconium-8 wt% stainless steel alloy

The electrometallurgical treatment of zirconium-based and Zircaloy-clad spent nuclear fuels will yield a metal waste form. The baseline composition for the waste form is zirconium-8 wt% stainless steel (Zr-8SS). The microstructure of the Zr-8SS alloy has been studied by scanning electron microscopy, energy dispersive spectroscopy, and neutron diffraction. The phases present in the as-cast alloy include Zr(), Zr₃(Fe,Ni), Zr₂(Fe,Ni), Zr₂(Fe,Cr), and Zr(Fe,Cr)₂; a solidification sequence has been proposed to explain the formation and morphology of these phases. Alloy phase stability has been studied by thermal aging at 780°C for periods up to 30 days. The phase changes that occur during thermal aging include an increase in Zr₃(Fe,Ni) and a decrease in Zr₂(Fe,Ni) content; reaction mechanisms have been proposed to explain these changes. The lattice parameters of alloy phases have been determined by neutron diffraction and found to be in agreement with those previously reported for similar phases. This study of alloy microstructures is the first step towards understanding the actinide and fission product distribution and predicting the corrosion behavior of the Zr-8SS metal waste form.     

Degradation of heat exchanger materials under biomass co-firing conditions

Abstract

Co-firing biomass in conventional pulverised coal fired power stations offers a means to rapidly introduce renewable and CO₂ neutral biomass fuels into the power generation market. Existing coalfired power stations are both much larger and more efficient than current designs of new biomass combustion systems, so feeding a few percent of biomass feed into an existing large coal fired station will give more biomass derived power than a new dedicated biomass station. Co-firing levels started at ～2% biomass, but this has increased to ～5–10% biomass, with higher levels of biomass co-firing being investigated, although supply of biomass becomes an issue with increasing co-firing levels. The lower levels of biomass co-firing (up to ～5%) can be achieved with relatively minor modifications to existing plants, so avoiding the large capital costs and risks of building new biomass-only fired power systems. However higher levels of co-firing are more difficult to achieve, requiring dedicated biomass supply systems and burners. For existing coal-fired power stations, the co-firing of biomass causes some practical problems, e.g.: the control of co-firing two fuels; changes to bottom/fly ash chemistry; changes to deposition (fouling and slagging) within the boiler; reduced reliability of key high temperature components (e.g. heat exchangers) due to increased corrosion problems relative to those experienced with coal alone.

This paper reports the results of assessments carried out to evaluate the potential operating conditions of heat exchangers in combustion systems with biomass (wood or straw) and coal cofiring, as well as laboratory corrosion tests that have been carried out to give an initial assessment of potential effects of biomass-co-firing.

The corrosion tests have been carried out using the deposit recoat method in controlled atmosphere furnaces. A series of 1000 hour tests have been carried out at typical superheater and evaporator metal temperatures using simulated deposit compositions and gaseous environments (selected on the basis of plant experience and potential fuel compositions). Five materials were exposed in these tests: 1Cr steel, T22 steel, X20CrMoV121, TP347HFG and alloy 625. In order to produce statistically valid data on the actual metal loss from the materials, the performance of the materials in these tests was determined from dimensional metrology before and after exposure. For each material, these data have been used to determine the sensitivity of the corrosion damage to changes in the exposure conditions (e.g. deposit composition, gas composition) thereby producing initial models of the corrosion performance of the materials. The corrosion data and model outputs have been compared with data available from power plants operating on coal, straw or wood fuels.     

Preparation of polymer composites using nanostructured carbon produced at large scale by catalytic decomposition of methane

Polymer-based composites were prepared using different concentrations of nanostructured carbons (NCs), produced by catalytic decomposition of methane (CDM). Four carbonaceous nanostructures were produced using different catalysts (with Ni and Fe as active phases) in a rotary bed reactor capable of producing up to 20 g of carbon per hour. The effect of nanostructured carbon on the thermal and electrical behaviour of epoxy-based composites is studied. An increase in the thermal stability and the decrease of electrical resistivity were observed for the composites at carbon contents as low as 1 wt%. The highest reduction of the electrical resistivity was obtained using multi-walled carbon nanotubes obtained with the Fe based catalysts. This effect could be related to the high degree of structural order of these materials. The results were compared with those obtained using a commercial carbon nanofibre, showing that the use of carbon nanostructures from CDM can be a valid alternative to the commercial nanofibres.     

Development of oxides at TBC – bond coat interfaces in burner rig exposures

Abstract

There is a desire to use gases derived from increasingly ‘dirty’ fuels (e.g. coal and biomass) in industrial gas turbines. The contaminants in these fuels have the potential to cause significant damage to the gas turbine hot gas path materials, many of which were developed and selected for natural gas fired conditions. This paper reports results of a study investigating the performance of thermal barrier coatings (TBCs) and bond coatings, applied to current industrial gas turbine materials, within clean and ‘dirty’ gas environments generated within a burner rig.

The materials covered by this study included: ? TBCs based on 8%Y₂O₃–ZrO₂ applied by both air plasma sprayed (APS) and electron beam – physical vapour deposition (EB–PVD) routes.

? Bond coats of the overlay and diffusion classes, applied by vacuum plasma spraying (VPS), electroplating (EP), chemical vapour deposition (CVD) and high velocity oxy-fuel (HVOF) spraying

? Base alloys of IN6203, CMSX-4 and Haynes 230

The required TBC/bond coat combinations were applied by commercial coating processes to cylindrical samples of base alloys manufactured for use in a burner rig.

The burner rig used in this study is designed to enable air-cooled probes of cylindrical samples to be exposed to a natural gas combustion environment. In this study, this enabled specific metal temperatures (~800 and ~900°C) to be targeted within a much higher temperature combustion gas stream (~1150°C). ‘Dirty’ fuel gas environments were simulated by introducing gaseous (SO₂ and HCl) and vapour phase (Na, K, Pb, Zn) contaminants into the burner rig just upstream of the edge of the gas flame. These conditions enabled continuous tests to be performed for 1,000 hours in both natural gas and ‘dirty’ fuel environments.

The relative performance of the materials was determined from cross-sections prepared after the 1000 hour exposures. These cross-sections were examined by optical and SEM/EDX to determine the thicknesses of the oxides at the TBC – bond coat interfaces, the morphologies of these interfaces and to characterise the elemental distributions in these regions.     

Reactions between La1−x CaxMnO3 and CaO-stabilized ZrO2 part I Powder mixtures

The chemistry and microstructure of the interface between calcium substituted lanthanum manganite and cubic calcia stabilized zirconia have been studied. The aim was to investigate the chemical stability of these materials as a model system for, respectively, the cathode and the electrolyte in solid oxide fuel cells. The relative amounts and time dependence of the formation of secondary phases (La₂Zr₂O₇ and CaZrO₃) and inter-diffusion between the primary phases were observed to depend on temperature, partial pressure of oxygen, and composition of the manganite. 30 mole % Ca on La-site and A-site deficiency of the manganite were shown to stabilize the heterophase interface in air. Reducing conditions were shown to destabilize the primary phases and increase the rate of formation of secondary phases. Pore-coarsening with increasing amount of Ca in the manganite was the most striking feature in the time dependence of the microstructure. The present findings are discussed in relation to the thermodynamic and kinetic stability of the cathode/electrolyte interface of conventional solid oxide fuel cells consisting of yttria stabilized zirconia and strontium substituted lanthanum manganite.     

Probes to monitor in-plant material degradation

Abstract

Fireside corrosion in coal fired boilers has been well-investigated. The main causes of water wall fireside corrosion are: (1) impurities in the fuel, such as sulphur alkali metals and chlorine; (2) the lack of control of the combustion process resulting in a reducing gaseous environment at the tube surface; (3) flame impingement; and (4) overtemperature of tube metal.

Co-firing secondary fuels in coal fired boilers is becoming common practice in many power stations in Europe. Secondary fuels like wood, refuse derived fuels, meat and bone meal, straw, poultry litter or mixtures of several secondary fuels are co-fired up to 20-wt%.

Most of these biomass fuels contain high concentrations of alkali chlorides. Considering the composition of these fuels, limitations on the maximum amount of secondary fuels to be co-fired in coal fired boilers are expected.

In addition to the environmental benefits from biomass fired power plants, co-firing can result in “green” power labelling and governmental subsidy. Also savings on fuel costs may be a driving force for an increase of the amount of biomass or secondary fuels to be co-fired.

However, without corrosion monitoring, short-term policies concerning co-firing secondary fuels in large volumes can lead to high costs in the medium or long term. These costs can be due to corrosion damage both in the furnace and superheater sections and penalties due to unplanned outages in a highly competitive electricity market.

This paper summarizes practical experiences from corrosion monitoring programs with KEMA corrosion probes. The first prototype was successfully tested in 1997 at the Hemweg Unit 8 coal fired power plant of Reliant Energy in Amsterdam, the Netherlands. Other corrosion monitoring programs were carried out at coal fired power plants and at a waste incineration plant.

At present a large-scale corrosion monitoring and material testing program is in progress at the Maasvlakte power station Unit 1 near Rotterdam, the Netherlands. In this 520 MWe power plant of E.on Benelux more than 10-wt% of mixtures of secondary fuels are directly co-fired.

In addition to aspects such as emissions, fuel handling and fuel cost savings, co-firing secondary fuels requires corrosion monitoring to check the tolerance to different fuel types of coal fired boilers.     

Effect of Fuel on the Synthesis and Properties of Poly(methyl methacrylate) Modified SrFe12O19 Nanoparticles

Nanosized strontium hexaferrite (SrFe₁₂O₁₉) has been synthesized by citrate, urea, oxalic, and glycine precursor via a sol-gel route with poly(methyl methacrylate) (PMMA) as a templating agent. Crystal structure, morphology, and magnetic properties of as-synthesized nanoparticles were characterized by XRD, SEM, FT-IR, and VSM techniques. The formation of strontium hexaferrite and its crystallite size in presence of different fuels were compared. The influence of different fuels was reflected on the phase purity, morphology of the final powders as well as the magnetic properties. Magnetic measurements revealed that samples prepared by citric acid and glycine as fuel have high specific saturation magnetization and moderate coercivity, while urea and oxalic acid fuels resulted in low phase purity, and thus inferior magnetic properties.     

A review of anode materials development in solid oxide fuel cells

High temperature solid oxide fuel cell (SOFC) has prospect and potential to generate electricity from fossil fuels with high efficiency and very low greenhouse gas emissions as compared to traditional thermal power plants. In the last 10 years, there has been significant progress in the materials development and stack technologies in SOFC. The objective of this paper is to review the development of anode materials in SOFC from the viewpoint of materials microstructure and performance associated with the fabrication and optimization processes. Latest development and achievement in the Ni/Y₂O₃-ZrO₂ (Ni/YSZ) cermet anodes, alternative and conducting oxide anodes and anode-supported substrate materials are presented. Challenges and research trends based on the fundamental understanding of the materials science and engineering for the anode development for the commercially viable SOFC technologies are discussed.     

Crystallite size reduction of Cr doped Al2O3 materials via optimized high-energy ball milling method

α-Al₂O₃ based compounds have large crystals and it is very difficult to reduce the crystallite size because they are very stable and hard. One way of reducing the crystallite size of the materials is by using high-energy ball milling method. Pure and single-phase micron-sized α-Al_2−xCr_xO₃ (x = 0.1, 0.2, 0.3) materials were successfully obtained via self-propagating combustion method. These materials were then subjected to a simple milling process from their microcrystalline powders. Comparisons between the micron-sized and milled samples in terms of their phase, structure, morphology and crystallite size were discussed. The XRD results reveal that all the milled samples were pure with no impurity or other phases present. Structural parameters are extracted via the Rietveld method, revealing that the cell constant, a, of the milled samples is higher than that of the micron-sized materials by 0.09 % to 0.11 %, resulting in a 0.28 % to 0.39 % increase in cell volume. FESEM results show a gradual decrease in crystallite size with increased milling time. Notably, the method successfully reduces the crystallite size without changing the phase of the materials and preserving the stoichiometry of the Al_2−xCr_xO₃ materials which may offer improved properties in various applications.     

Materials,technological status,and fundamentals of PEM fuel cells – A review

PEM (Polymer Electrolyte Membrane) fuel cells have the potential to reduce our energy use, pollutant emissions, and dependence on fossil fuels. In the past decade, significant advances have been achieved for commercializing the technology. For example, several PEM fuel cell buses are currently rated at the technical readiness stage of full-scale validation in realistic driving environments and have met or closely met the ultimate 25,000-h target set by the U.S. Department of Energy. So far, Toyota has sold more than 4000 Mirai PEM fuel cell vehicles (FCVs). Over 30 hydrogen gas stations are being operated throughout the U.S. and over 60 in Germany. In this review, we cover the material, design, fundamental, and manufacturing aspects of PEM fuel cells with a focus on the portable, automobile, airplane, and space applications that require careful consideration in system design and materials. The technological status and challenges faced by PEM fuel cells toward their commercialization in these applications are described and explained. Fundamental issues that are key to fuel cell design, operational control, and material development, such as water and thermal management, dynamic operation, cold start, channel two-phase flow, and low-humidity operation, are discussed. Fuels and fuel tanks pertinent to PEM fuel cells are briefly evaluated.The objective of this review is three fold: (1) to present the latest status of PEM fuel cell technology development and applications in the portable and transportation power through an overview of the state of the art and most recent technological advances; (2) to describe materials and water/thermal transport management for fuel cell design and operational control; and (3) to outline major challenges in the technology development and the needs for fundamental research for the near future and prior to fuel cell world-wide deployment.     

Cell-protecting regeneration from anode carbon deposition using in situ produced oxygen and steam: A combined experimental and theoretical study

Carbon deposition is a primary concern during the operation of solid oxide fuel cells (SOFCs) fueled with hydrocarbon fuels, leading to cell degradation and even cell damage. Carbon elimination is expected to be a promising approach to prolong cell life. This work reports on a combined experimental and theoretical investigation of cell regeneration from anode carbon deposition of tubular SOFCs fabricated by phase-inversion and co-sintering techniques. The as-prepared cell exhibits a maximum power density of 0.20?W?cm^?2 at 800?°C fueling with wet CH₄, but fails to stable operation due to severe carbon deposition. Based on thermodynamic predictions, a successive cell-protecting regeneration process is proposed to eliminate deposited carbon without oxidizing Ni catalysts, during which CH₄ and H₂ fuels are provided in circulation. Through a total of 35 cycling tests, cell performance can always successfully restore to the initial level. The possible carbon elimination mechanism is investigated in detail based on thermodynamic and first-principle calculations. The feasibility of carbon elimination using in situ produced oxygen or steam through electrochemical reaction has been revealed, providing a novel continuous operation mode for hydrocarbon-based SOFCs.