Numerical Simulation of Nox Formation in Coal Combustion with Inlet Natural Gas Burning

A full two-fluid model of reacting gas-particle flows and coal combustion is used to simulate coal combustion with and without inlet natural gas added in the inlet. The simulation results for the case without natural gas burning is in fair agreement with the experimental results reported in references. The simulation results of different natural gas adding positions indicate that the natural gas burning can form lean oxygen combustion enviroment at the combustor inlet region and the NOz concentration is reduced. The same result can be obtained from chemical equilibrium analysis.

Studies of the Effect of a Coal Concentrator on NO Formation in Swirling Coal Combustion

To develop low-pollution burners, the effect of a coal concentrator on NO formation in swirling coal combustion is studied using both numerical simulation and experiments. The isothermal gas-particle two-phase velocities and particle concentration in a cold model of swirl burners with and without coal concentrators were measured using the phase Doppler particle anemometer (PDPA). A full two-fluid model of reacting gas-particle flows and coal combustion with an algebraic unified second-order moment (AUSM) turbulence-chemistry model for the turbulent reaction rate of NO formation are used to simulate swirling coal combustion and NO formation with different coal concentrators. The results give the turbulent kinetic energy, particle concentration, temperature and NO concentration in cases of with and without coal concentrators. The predicted results for cold two-phase flows are in good agreement with the PDPA measurement results, showing that the coal concentrator increases the turbulence and particle concentration in the recirculation zone. The combustion modeling results indicate that although the coal concentrator increases the turbulence and combustion temperature, but still can remarkably reduce the NO formation due to creating high coal concentration in the recirculation zone.

Formation of adiabatic shear band in metal matrix composites

A modified single-pulse loading split Hopkinson torsion bar (SSHTB) is introduced to investigate adiabatic shear banding behavior in SiCp particle reinforced 2024 Al composites in this work. The experimental results showed that formation of adiabatic shear band in the composite with smaller particles is more readily observed than that in the composite with larger particles. To characterize this size-dependent deformation localization behavior of particle reinforced metal matrix composites (MMCp), a strain gradient dependent shear instability analysis was performed. The result demonstrated that high strain gradient provides a deriving force for the formation of adiabatic shear banding in MMCp. (C) 2004 Elsevier Ltd. All rights reserved.

Chemical equilibrium analysis and CFD simulation of coal combustion and NOx formation

A full two-fluid model of reacting gas-particle flows with an algebraic unified second-order moment (AUSM) turbulence-chemistry model is used to simulate Beijing coal combustion and NOx formation. The sub-models are the k-epsilon-kp two-phase turbulence model, the EBU-Arrhenius volatile and CO combustion model, the six-flux radiation model, coal devolatilization model and char combustion model. The blocking effect on NOx formation is discussed. In addition, the chemical equilibrium analysis is used to predict NOx concentration at different temperature. Results of CID simulation and chemical equilibrium analysis show that, optimizing air dynamic parameters can delay the NOx formation and decrease NOx emission, but it is effective only in a restricted range. In order to decrease NOx emission near to zero, the re-burning or other chemical methods must be used.

Investigations of secondary organic aerosol formation in laboratory chambers

Secondary organic aerosol (SOA) is produced in the atmosphere by oxidation of volatile organic compounds. Laboratory chambers are used understand the formation mechanisms and evolution of SOA formed under controlled conditions. This thesis presents studies of SOA formed from anthropogenic and biogenic precursors and discusses the effects of chamber walls on suspended vapors and particles.

During a chamber experiment, suspended vapors and particles can interact with the chamber walls. Particle wall loss is relatively well-understood, but vapor wall losses have received little study. Vapor wall loss of 2,3-epoxy-1,4-butanediol (BEPOX) and glyoxal was identified, quantified, and found to depend on chamber age and relative humidity.

Particles reside in the atmosphere for a week or more and can evolve chemically during that time period, a process termed aging. Simulating aging in laboratory chambers has proven to be challenging. A protocol was developed to extend the duration of a chamber experiment to 36 h of oxidation and was used to evaluate aging of SOA produced from m-xylene. Total SOA mass concentration increased and then decreased with increasing photooxidation suggesting a transition from functionalization to fragmentation chemistry driven by photochemical processes. SOA oxidation, measured as the bulk particle elemental oxygen-to-carbon ratio and fraction of organic mass at m/z 44, increased continuously starting after 5 h of photooxidation.

The physical state and chemical composition of an organic aerosol affect the mixing of aerosol components and its interactions with condensing species. A laboratory chamber protocol was developed to evaluate the mixing of SOA produced sequentially from two different sources by heating the chamber to induce particle evaporation. Using this protocol, SOA produced from toluene was found to be less volatile than that produced from a-pinene. When the two types of SOA were formed sequentially, the evaporation behavior most closely represented that of SOA from the second parent hydrocarbon, suggesting that the structure of the mixed SOA particles resembles a core of SOA from the first precursor coated by a layer of SOA from the second precursor, indicative of limiting mixing.

Solar photospheric and coronal abundances from solar energetic particle measurements

Observations of solar energetic particles (SEPs) from 22 solar flares in the 1977-1982 time period are reported. The observations were made by the Cosmic Ray Subsystem on board the Voyager 1 and 2 spacecraft. SEP abundances have been obtained for all elements with 3 ≤ Z ≤ 30 except Li, Be, B. F, Sc, V, Co and Cu. for which upper limits have been obtained. Statistically meaningful abundances of several rare elements (e.g., P, Cl, K, Ti, Mn) have been determined for the first time, and the average abundances of the more abundant elements have been determined with improved precision, typically a factor of three better than the best previous determinations.

Previously reported results concerning the dependence of the fractionation of SEPs relative to photosphere on first ionization potential (FIP) have been confirmed and amplified upon with the new data. The monotonic Z-dependence of the variation between flares noted by earlier studies was found to be interpretable as a fractionation, produced by acceleration of the particles from the corona and their propagation through interplanetary space, which is ordered by the ionic charge-to-mass ratio Q/ M of the species making up the SEPs. It was found that Q/M is the primary organizing parameter of acceleration and propagation effects in SEPs, as evidenced by the dependence on Q/M of time, spatial and energy dependence within flares and of the abundance variability from flare to flare.

An unfractionated coronal composition was derived by applying a simple Q/M fractionation correction to the observed average SEP composition, to simultaneously correct for all Q/M-correlated acceleration/propagation fractionation of SEPs. The resulting coronal composition agrees well with current XUV/X-ray spectroscopic measurements of coronal composition but is of much higher precision and is available for a much larger set of elements. Compared to spectroscopic photospheric abundances, the SEP-derived corona appears depleted in C and somewhat enriched in Cr (and possibly Ca and Ti).

An unfractionated photospheric composition was derived by applying a simple FIP fractionation correction to the derived coronal composition, to correct for the FIP-associated fractionation of the corona during its formation from photospheric material. The resulting composition agrees well with the photospheric abundance tabulation of Grevesse (1984) except for an at least 50% lower abundance of C and a significantly greater abundance of Cr and possibly Ti. The results support the Grevesse photospheric Fe abundance, about 50% higher than meteoritic and earlier solar values. The SEP-derived photospheric composition is not generally of higher precision than the available spectroscopic data, but it relies on fewer physical parameters and is available for some elements (C, N, Ne, Ar) which cannot be measured spectroscopically in the photosphere.

Investigation of Fundamental Processes Governing Secondary Organic Aerosol Formation in Laboratory Chambers

Our understanding of the processes and mechanisms by which secondary organic aerosol (SOA) is formed is derived from laboratory chamber studies. In the atmosphere, SOA formation is primarily driven by progressive photooxidation of SOA precursors, coupled with their gas-particle partitioning. In the chamber environment, SOA-forming vapors undergo multiple chemical and physical processes that involve production and removal via gas-phase reactions; partitioning onto suspended particles vs. particles deposited on the chamber wall; and direct deposition on the chamber wall. The main focus of this dissertation is to characterize the interactions of organic vapors with suspended particles and the chamber wall and explore how these intertwined processes in laboratory chambers govern SOA formation and evolution.

A Functional Group Oxidation Model (FGOM) that represents SOA formation and evolution in terms of the competition between functionalization and fragmentation, the extent of oxygen atom addition, and the change of volatility, is developed. The FGOM contains a set of parameters that are to be determined by fitting of the model to laboratory chamber data. The sensitivity of the model prediction to variation of the adjustable parameters allows one to assess the relative importance of various pathways involved in SOA formation.

A critical aspect of the environmental chamber is the presence of the wall, which can induce deposition of SOA-forming vapors and promote heterogeneous reactions. An experimental protocol and model framework are first developed to constrain the vapor-wall interactions. By optimal fitting the model predictions to the observed wall-induced decay profiles of 25 oxidized organic compounds, the dominant parameter governing the extent of wall deposition of a compound is identified, i.e., wall accommodation coefficient. By correlating this parameter with the molecular properties of a compound via its volatility, the wall-induced deposition rate of an organic compound can be predicted based on its carbon and oxygen numbers in the molecule.

Heterogeneous transformation of δ-hydroxycarbonyl, a major first-generation product from long-chain alkane photochemistry, is observed on the surface of particles and walls. The uniqueness of this reaction scheme is the production of substituted dihydrofuran, which is highly reactive towards ozone, OH, and NO3, thereby opening a reaction pathway that is not usually accessible to alkanes. A spectrum of highly-oxygenated products with carboxylic acid, ester, and ether functional groups is produced from the substituted dihydrofuran chemistry, thereby affecting the average oxidation state of the alkane-derived SOA.

The vapor wall loss correction is applied to several chamber-derived SOA systems generated from both anthropogenic and biogenic sources. Experimental and modeling approaches are employed to constrain the partitioning behavior of SOA-forming vapors onto suspended particles vs. chamber walls. It is demonstrated that deposition of SOA-forming vapors to the chamber wall during photooxidation experiments can lead to substantial and systematic underestimation of SOA. Therefore, it is likely that a lack of proper accounting for vapor wall losses that suppress chamber-derived SOA yields contribute substantially to the underprediction of ambient SOA concentrations in atmospheric models.

Mechanisms of erosion of unfilled elastomers by solid particle impact

The mechanisms of material removal were studied during the erosion of two unfilled elastomers (natural rubber and epoxidised natural rubber). The effects of impact velocity and of lubrication by silicone oil were investigated. The development of surface features due to single impacts and during the early stages of erosion was followed by scanning electron microscopy. The basic material removal mechanism at impact angles of both 30° and 90° involves the formation and growth of fine fatigue cracks under the tensile surface stresses caused by impact. No damage was observed after single impacts; it was found that many successive impacts are necessary for material removal. It was found that the erosion rate has a very strong dependance on impact velocity above about 50 ms-1.

Techniques to improve the shear strength of impacted bone graft: the effect of particle size and washing of the graft.

BACKGROUND: When fresh morselized graft is compacted, as in impaction bone-grafting for revision hip surgery, fat and marrow fluid is either exuded or trapped in the voids between particles. We hypothesized that the presence of incompressible fluid damps and resists compressive forces during impaction and prevents the graft particles from moving into a closer formation, thus reducing the graft strength. In addition, viscous fluid such as fat may act as an interparticle lubricant, thus reducing the interlocking of the particles. METHODS: We performed mechanical shear testing in the laboratory with use of fresh-frozen human femoral-head allografts that had been passed through different orthopaedic bone mills to produce graft of differing particle-size distributions (grading). RESULTS: After compaction of fresh graft, fat and marrow fluid continued to escape on application of normal loads. Washed graft, however, had little lubricating fluid and better contact between the particles, increasing the shear resistance. On mechanical testing, washed graft was significantly (p < 0.001) more resistant to shearing forces than fresh graft was. This feature was consistent for different bone mills that produced graft of different particle-size distributions and shear strengths. CONCLUSIONS: Removal of fat and marrow fluid from milled human allograft by washing the graft allows the production of stronger compacted graft that is more resistant to shear, which is the usual mode of failure. Further research into the optimum grading of particle sizes from bone mills is required.

Techniques to improve the shear strength of impacted bone graft: The effect of particle size and washing of the graft

Background: When fresh morselized graft is compacted, as in impaction bone-grafting for revision hip surgery, fat and marrow fluid is either exuded or trapped in the voids between particles. We hypothesized that the presence of incompressible fluid damps and resists compressive forces during impaction and prevents the graft particles from moving into a closer formation, thus reducing the graft strength. In addition, viscous fluid such as fat may act as an interparticle lubricant, thus reducing the interlocking of the particles. Methods: We performed mechanical shear testing in the laboratory with use of fresh-frozen human femoral-head allografts that had been passed through different orthopaedic bone mills to produce graft of differing particle-size distributions (grading). Results: After compaction of fresh graft, fat and marrow fluid continued to escape on application of normal loads. Washed graft, however, had little lubricating fluid and better contact between the particles, increasing the shear resistance. On mechanical testing, washed graft was significantly (p < 0.001) more resistant to shearing forces than fresh graft was. This feature was consistent for different bone mills that produced graft of different particle-size distributions and shear strengths. Conclusions: Removal of fat and marrow fluid from milled human allograft by washing the graft allows the production of stronger compacted graft that is more resistant to shear, which is the usual mode of failure. Further research into the optimum grading of particle sizes from bone mills is required. Clinical Relevance: Understanding the mechanical properties of milled human allograft is important when impaction grafting is used for mechanical support. A simple means of improving the mechanical strength of graft produced by currently available bone mills, including an intraoperative washing technique, is described.

Occurrence of particle debris field during focused Ga ion beam milling of glassy carbon

To explore the machining characteristics of glassy carbon by focused ion beam (FIB), particles induced by FIB milling on glassy carbon have been studied in the current work. Nano-sized particles in the range of tens of nanometers up to 400 nm can often be found around the area subject to FIB milling. Two ion beam scanning modes - slow single scan and fast repetitive scan - have been tested. Fewer particles are found in single patterns milled in fast repetitive scan mode. For a group of test patterns milled in a sequence, it was found that a greater number of particles were deposited around sites machined early in the sequence. In situ EDX analysis of the particles showed that they were composed of C and Ga. The formation of particles is related to the debris generated at the surrounding areas, the low melting point of gallium used as FIB ion source and the high contact angle of gallium on glassy carbon induces de-wetting of Ga and the subsequent formation of Ga particles. Ultrasonic cleaning can remove over 98% of visible particles. The surface roughness (Ra) of FIB milled areas after cleaning is less than 2 nm. © 2010.

Failure and formation of axial nanowire heterostructures in vapor-liquid-solid growth

To observe the axial growth behavior of InAs on GaAs nanowires, InAs was grown for different growth durations on GaAs nanowires using Au nanoparticles. Through transmission electron microscopy, we have observed the following evolution steps for the InAs growth. (1) In the initial stages of the InAs growth, InAs clusters into a wedge shape preferentially at an edge of the Au/GaAs interface by minimizing Au/InAs interfacial area; (2) with further growth of InAs, the Au particle moves sidewards and then downwards by preserving an interface with GaAs nanowire sidewalls. The lower interfacial energy of Au/GaAs than that of Au/In As is attributed to be the reason for such Au movement. This downward movement of the Au nanoparticle later terminates when the nanoparticle encounters InAs growing radially on the GaAs nanowire sidewalls, and with further supply of In and As vapor reactants, the Au nanoparticle assists the formation of InAs branches. These observations give some insights into vapor-liquid-solid growth and the formation of kinks in nanowire heterostructures. © 2008 Materials Research Society.

Influence of 5A-Type Zeolite Powder on Tetrahydrofuran Hydrate Formation and Dissociation Process

Visual observations of tetrahydrofuran (THF) hydrate formation and dissociation processes with 5A-type zeolite powder were made at normal atmospheric conditions and below zero temperature by microscope. Results indicate that 5A-type zeolite powder can promote THF hydrate growth. At the same time, in the presence of 5A-type zeolite, agglomerated crystals and vein-like crystals of THF hydrate were also formed. SA-type zeolite powder increases the crystallization temperature and decreases the dissociation temperature. The particle size distribution of 5A-type zeolite powder influences THF hydrate formation and its dissociation characteristics significantly.

Formation of an fcc phase through a bcc metastable state in crystallization of charged colloidal particles

By in situ monitoring structural changes with the reflection spectrometer during the colloidal crystallization, we present direct experimental evidence of liquid-bcc-fcc phase transition in crystallization of charged colloidal particles, as a manifestation of the Ostwald's step rule. In addition, the lifetime of the bcc metastable structure in this system decreases significantly with increasing particle volume fraction, offering a possible explanation for "exceptions" to the step rule.

Preparation and application of a novel core-shell-particle-supported zirconocene catalyst

The use of functional groups bearing silica/poly(styrene-co-4-vinylpyridine) core-shell particles as a support for a zirconocene catalyst in ethylene polymerization was studied. Several factors affecting the behavior of the supported catalyst and the properties of the resulting polymer, such as time, temperature, Al/N (molar ratio), and Al/Zr (molar ratio), were examined. The conditions of the supported catalyst preparation were more important than those of the ethylene polymerization. The state of the supported catalyst itself played a decisive role in both the catalytic behavior of the supported catalyst and the properties of polyethylene (PE). IR and X-ray photoelectron spectroscopy were used to follow the formation of the supports. The formation of cationic active species is hypothesized, and the performance of the core-shell-particle-supported zirconocene catalyst is discussed as well. The bulk density of the PE formed was higher than that of the polymer obtained from homogeneous and polymer-supported Cp2ZrCl2/methylaluminoxane catalyst systems. (C) 2001 John Wiley & Sons, Inc.