Interaction between Fe-based oxygen carriers and n-heptane during chemical looping combustion

Chemical looping combustion (CLC) uses a metal oxide (the oxygen carrier) to provide oxygen for the combustion of a fuel and gives an inherent separation of pure CO2 with minimal energy penalty. In solid-fuel CLC, volatile matter will interact with oxygen carriers. Here, the interaction between iron-based oxygen carriers and a volatile hydrocarbon (n-heptane) was investigated in both a laboratory-scale fluidised bed and a thermogravimetric analyser (TGA). Experiments were undertaken to characterise the thermal decomposition of the n-heptane occurring in the presence and in the absence of the oxygen carrier. In a bed of inert particles, carbon deposition increased with temperature and acetylene appeared as a possible precursor. For a bed of carrier consisting of pure Fe2O3, carbon deposition occurred once the Fe2O3 was fully reduced to Fe. When the Fe2O3 was doped with 10 mol % Al2O3 (Fe90Al), deposition started when the carrier was reduced to a mixture of Fe and FeAl2O4, the latter being very unreactive. Furthermore, when pure Fe2O3 was fully reduced to Fe, agglomeration of the fluidised bed occurred. However, Fe90Al did not give agglomeration even after extended reduction. The results suggest that Fe90Al is promising for the CLC of solid fuels. © 2012 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Analysis of oxide and vanadate supports for catalytic hydrogen combustion: Kinetic and mechanistic investigations

Combustion synthesized oxide and vanadate compounds (CeO2, Fe2O3, CeVO4, and FeVO4) were tested for catalytic hydrogen combustion. The compounds were characterized by X-ray diffraction and X-ray photoelectron spectroscopy. All the four compounds showed good activity and stability for catalytic hydrogen combustion and more than 95% conversion was observed over all the compounds within 500 degrees C. The mechanisms for the reaction over the different classes of compounds (cerium-based and iron-based compounds) were proposed on the basis of spectroscopic observations. The main difference in the mechanisms was in the nature of adsorption of H2 over the sites. The elementary processes for the reaction were proposed, corresponding rate expressions were derived, and the rate parameters for the reaction were estimated using nonlinear regression. Langmuir-Hinshelwood and Eley-Rideal mechanisms were also tested for the reaction and the proposed mechanism was compared with these mechanisms. (c) 2011 American Institute of Chemical Engineers AIChE J, 2012

Antiferromagnetism in Fe1+y Te and Superconductivity in K (x) Fe2Se2

Iron-based layered chalcogenides are interesting because of their structural magnetic and superconducting properties. Single crystals of the parent binary chalcogenides, Fe1+y Te, and intercalated ternary chalcogenides, K0.8Fe2Se2, are grown and investigated in detail. Single crystals are grown by modified horizontal Bridgman method. Fe1+y Te demonstrates an antiferromagnetic (AFM) transition at T (N) =67 K which is identified as a magnetostructural transition. By varying the concentration of excess Fe, we have tuned T (N) over a range of temperature from 67 to 57 K. The superconducting properties of K0.8Fe2Se2 crystals are explored by magnetization measurements. A superconducting transition is observed at T (C) =31 K. The lower critical field of K0.8Fe2Se2 is estimated from field variation of magnetization measurements.

Interaction-induced singular Fermi surface in a high-temperature oxypnictide superconductor

In the family of iron-based superconductors, LaFeAsO-type materials possess the simplest electronic structure due to their pronounced two-dimensionality. And yet they host superconductivity with the highest transition temperature T-c approximate to 55K. Early theoretical predictions of their electronic structure revealed multiple large circular portions of the Fermi surface with a very good geometrical overlap (nesting), believed to enhance the pairing interaction and thus superconductivity. The prevalence of such large circular features in the Fermi surface has since been associated with many other iron-based compounds and has grown to be generally accepted in the field. In this work we show that a prototypical compound of the 1111-type, SmFe0.92Co0.08AsO, is at odds with this description and possesses a distinctly different Fermi surface, which consists of two singular constructs formed by the edges of several bands, pulled to the Fermi level from the depths of the theoretically predicted band structure by strong electronic interactions. Such singularities dramatically affect the low-energy electronic properties of the material, including superconductivity. We further argue that occurrence of these singularities correlates with the maximum superconducting transition temperature attainable in each material class over the entire family of iron-based superconductors.

Thermal transport in high porosity cellular metal foams

The heat dissipation capability of highly porous cellular metal foams with open cells subject to forced air convection is studied using a combined experimental and analytical approach. The cellular morphologies of six FeCrAlY (an iron-based alloy) foams and six copper alloy foams with a range of pore sizes and porosities are quantified with the scanning electronic microscope and image analysis. Experimental measurements on pressure drop and heat transfer for copper foams are carried out. A numerical model for forced convection across open-celled metal foams is subsequently developed, and the predictions are compared with those measured. Reasonably good agreement with test data is obtained, given the complexity of the cellular foam morphology and the associated momentum/energy transport. The results show that cell size has a more significant effect on the overall heat transfer than porosity. An optimal porosity is obtained based on the balance between pressure drop and overall heat transfer, which decreases as the Reynolds number is increased.

铁基激光熔覆合金设计及微观组织与性能研究

本文设计并制备了具有优良的强韧性能和高温性能的激光熔覆涂层。利用 SEM、TEMEY X－射线衍射仪等研究了涂层的化学成分、宏微观结构及其转变机制，同时研究了涂层强韧性及耐高温磨损性能及其影响机制。对激光溶覆涂层进行了合金化、微观组织、强韧化机制、加工工艺性能设计。合金系为 Fe-Cr-C-W-Ni，成分配比（质量分数），Fe:52-60%, Cr:24-30%, C:5-6%, W:4.5-7.5%, Ni:5-6%。强化机制为两相强化、亚结构强化及固溶强化，其中强化相为合金碳化物，基体相为合金元素过饱和度极高的韧性奥氏体。亚共晶及过共晶组织的领先凝固相分别为奥氏体及 M_7C_3 合金碳化物，两相共晶组织均为韧性相奥氏体和强化相 M_7C_3 合金碳化物。加工工艺控制领先凝固相的结构、组织演化及力学性能。熔覆组织在高温时效过程中形成大量新的碳化物。在过饱和奥氏体内部，可弥散析出细小的 Mc、M_2C 及 M_(23)C_6碳化物；在奥氏体与 M_7C_3 相界面，亚稳相M_7C_3发生原位转变，形成 M_(23)C_6 及 M_6C碳化物。激光熔覆合金具有较高的综合力学性能，熔覆涂层有高的显微硬度、优良的抗回火稳定性、显著的二次硬化特征、优异的抗磨粒磨损和冲击磨损性能。Fe-Cr-C-W-Ni 激光熔覆合金具有较低的裂纹形成倾向和良好的表面成形性能，这与奥氏体较高的高温韧塑性及合金的低熔点共晶特征密切相关；实验及理论分析表明，通过调整合金成分、激光工艺参数和后续热处理工艺，可获得具有不同强韧性能的熔覆涂层。

Scanning tunneling spectroscopic studies on high-temperature superconductors and Dirac materials

This thesis details the investigations of the unconventional low-energy quasiparticle excitations in electron-type cuprate superconductors and electron-type ferrous superconductors as well as the electronic properties of Dirac fermions in graphene and three-dimensional strong topological insulators through experimental studies using spatially resolved scanning tunneling spectroscopy (STS) experiments.

Magnetic-field- and temperature-dependent evolution of the spatially resolved quasiparticle spectra in the electron-type cuprate La_0.1Sr_0.9CuO₂ (La-112) T_C = 43 K, are investigated experimentally. For temperature (T) less than the superconducting transition temperature (TC), and in zero field, the quasiparticle spectra of La-112 exhibits gapped behavior with two coherence peaks and no satellite features. For magnetic field measurements at T < TC, first ever observation of vortices in La-112 are reported. Moreover, pseudogap-like spectra are revealed inside the core of vortices, where superconductivity is suppressed. The intra-vortex pseudogap-like spectra are characterized by an energy gap of V_PG = 8.5 ± 0.6 meV, while the inter-vortex quasiparticle spectra shows larger peak-to-peak gap values characterized by Δ_pk-pk(H) >V_PG, and Δ_pk-pk (0)=12.2 ± 0.8 meV > Δ_pk-pk (H > 0). The quasiparticle spectra are found to be gapped at all locations up to the highest magnetic field examined (H = 6T) and reveal an apparent low-energy cutoff at the V_PG energy scale.

Magnetic-field- and temperature-dependent evolution of the spatially resolved quasiparticle spectra in the electron-type "122" iron-based Ba(Fe_1-xCo_x)₂A_s2 are investigated for multiple doping levels (x = 0.06, 0.08, 0.12 with T_C= 14 K, 24 K, and 20 K). For all doping levels and the T < T_C, two-gap superconductivity is observed. Both superconducting gaps decrease monotonically in size with increasing temperature and disappear for temperatures above the superconducting transition temperature, T_C. Magnetic resonant modes that follow the temperature dependence of the superconducting gaps have been identified in the tunneling quasiparticle spectra. Together with quasiparticle interference (QPI) analysis and magnetic field studies, this provides strong evidence for two-gap sign-changing s-wave superconductivity.

Additionally spatial scanning tunneling spectroscopic studies are performed on mechanically exfoliated graphene and chemical vapor deposition grown graphene. In all cases lattice strain exerts a strong influence on the electronic properties of the sample. In particular topological defects give rise to pseudomagnetic fields (B ~ 50 Tesla) and charging effects resulting in quantized conductance peaks associated with the integer and fractional Quantum Hall States.

Finally, spectroscopic studies on the 3D-STI, Bi₂Se₃ found evidence of impurity resonance in the surface state. The impurities are in the unitary limit and the spectral resonances are localized spatially to within ~ 0.2 nm of the impurity. The spectral weight of the impurity resonance diverges as the Fermi energy approaches the Dirac point and the rapid recovery of the surface state suggests robust topological protection against perturbations that preserve time reversal symmetry.

铁系催化剂聚合1，3-双烯烃的研究

1，2-聚丁二烯和3，4-聚异戊二烯是制造高性能轮胎的原料。本论文研究了以含磷化合物为第三组份的铁催化剂合成1，2-聚丁二烯和3，4-聚异戊二烯的反应规律：1．以二乙基亚磷酸酷为第三组份的铁催化剂可在己烷中，较高温度（50℃）下聚合1，3-丁二烯。通过控制催化剂组份的配比，可制备间同和无规1，2-聚丁二烯。所得间同1，2-聚丁二烯的1，2-结构含量为91％，间规度为90％；所得无规1，2-聚丁二烯的硫化胶具有优异的抗干、湿滑性能。2．以三苯基磷酸酷为第三组份的铁催化剂是合成高间同1，2一聚丁二烯的高效催化剂。所得聚合物具有高的1，2-结构含量（ca.95％），高的间规度（ca.95％）。聚合物的微观结构与催化剂组成等反应因素无关。3．以二烷基亚磷酸醋为第三组份的铁催化剂可在己烷中，较高温度（50℃）下聚合异戊二烯。二烷基亚磷酸醋中烷基影响聚合活性的顺序为乙基一甲基＞正丁基＞异辛基。所得聚异戊二烯的3，4（含1，2）结构含量保持在60％左右，不受反应条件的影响。4．改性甲基铝氧烷（MMAO）活化的铁催化剂聚合异戊二烯，在相当低的MMAO用量下（Al／Fe=20，摩尔比）即有高的催化活性。溶剂影响聚合活性的顺序为甲苯＞环己烷＞己烷＞二氯甲烷。所得聚异戊二烯的3，4（含1，2）结构含量稳定在60％。