Graphitizable Pitch from Microwave Plasma Pyrolysis of Natural Gas.

An innovative approach of microwave plasma was utilized to convert natural gas into tar, from which a highly graphitizable pitch was derived using fractional distillation. The natural gas-derived pitch (NGDP) was thoroughly characterized, and the graphitizability of the carbonized NGDP was assessed using polarized light microscopy. The NGDP and, for comparison, needle coke, petroleum coke, and shot coke were subjected to graphitization heat treatment (GR) at 2500 °C. Results indicate that the graphitizability of the NGDP exceeds those of all industrial standard cokes. The GR-NGDP showed the highest degree of graphitization and crystallite size among all samples.

Structural Characteristics and Graphitizability of Tars from Thermal versus Microwave Plasma Pyrolysis of Coals.

This work investigates the structural characteristics and graphitizability of tars obtained from thermal pyrolysis versus the reactive microwave (MW) plasma pyrolysis of coals. Powder River Basin (PRB) coal tars obtained by thermal pyrolysis have been compared with tars obtained from MW plasma pyrolysis containing H2. To study the effect of coal rank and MW plasma environment, the PRB tars have been compared with Middle Kittanning (MK) coal tars obtained from an argon-hydrogen MW plasma (hp) and an argon-CO2 MW plasma (cdp) environment. Fourier transform infrared spectroscopy has been used for investigating the structural differences among the tar samples. The tars have been graphitized (GR-) at 2500 °C and the graphitic quality assessment has been performed using X-ray diffraction and transmission electron microscopy. MW plasma-derived tars have higher aromaticity, lower condensation, and lower oxygenated molecules compared to thermally derived tars. These advantageous features of MW plasma-derived tars lead to the formation of crystallites several times larger than thermally derived tars after graphitization. When considering coal of the same rank (bituminous), the choice of the MW plasma environment has a substantial impact on the graphitic quality of the tars. The utilization of MW plasma containing H2 leads to a significant increase in both the crystallite diameter (by 60%) and stacking height (by 40%) compared to MW plasma containing CO2. Furthermore, within the same MW plasma environment, the coal rank plays a significant role in determining the crystallite diameter and stacking height of the GR-tars. In particular, GR-MK tar obtained from hp exhibits a 135% larger crystallite diameter and 85% larger stacking height compared with GR-PRB tar obtained from hp. These findings demonstrate the potential to tailor the composition of coal-derived tars and consequently influence their graphitizability by adjusting the reactive environment during MW plasma treatment.

Enhancing Graphitic Carbon Precursors from Coal Pyrolysis: A Comparative Analysis of Microwave Plasma and Conventional Thermal Upgradation Methods.

This study investigates and compares the efficacy of conventional thermal pyrolysis and microwave (MW) plasma pyrolysis in upgrading coal-derived precursors. Coal samples presenting a range of ranks were pyrolyzed under various reactive and nonreactive atmospheres using a pyroprobe, with the pyrolyzates analyzed by gas chromatography-mass spectrometry (GC-MS). Comparative MW plasma tests were conducted using a modified countertop MW unit, with condensed products similarly analyzed by GC-MS. A predominant coal devolatilization product-benzene was selected for analyzing the reactive MW plasma upgradation. Results demonstrate that conventional thermal pyrolysis lacks effectiveness in upgrading the precursors. To gain insight into the underlying reasons, chemical kinetic simulations were conducted. Oppositely, reactive MW plasma pyrolysis demonstrated remarkable precursor upgradation. These condensed MW plasma pyrolysis products were then subjected to a carbonization and graphitization heat-treatment with a comprehensive graphitic quality assessment conducted using X-ray diffraction and transmission electron microscopy. After graphitization, the MW plasma-upgraded precursor produced a carbon with a crystallite size several times greater than that of the initial benzene. By MW plasma processing, the poorly graphitizable benzene precursor was transformed into a highly graphitizable precursor comparable to coal tar pitch. The underlying reasons for this significant improvement were investigated by analyzing the compositional changes in the precursor under various reactive environments.

Characterization and Hazard Identification of Respirable Cement and Concrete Dust from Construction Activities.

Construction is an important segment of the economy that employs millions of people. Construction dust is an occupational health hazard to millions of construction workers worldwide. The hazards associated with respirable dust depend upon its particulate size distribution and chemical composition, as these determine the deposition pattern in the respiratory tract and reactivity, respectively. This study presents characterization of the size and composition of the dust from two key construction materials-cast cement and poured concrete. The dust was generated by cutting the cured cement and concrete blocks using an 18" hand-held circular saw as used in highway and building construction. Transmission electron microscopy, scanning electron microscopy, dynamic light scattering, and laser diffraction were performed for the size analysis of the particles. Energy dispersive spectroscopy and X-ray photoelectron spectroscopy were used for chemical analysis. X-ray diffraction was used for phase identification. Electron diffraction patterns were obtained to assess the crystallinity of individual particles. They confirm the crystallinity of particles of different size and shapes. With a particle size range between 0.5 µm and 10 µm, greater than 90% of particles fell below 2.5 µm, presenting a respirable health concern. Crystalline compounds including the metals Al, Ca, Fe, Mg, Na, and K were detected. The concrete particles were most enriched in crystalline silica with a concentration of more than 30% by weight. The presence of metals and high crystalline silica content pose a serious health concern to construction workers.

A Laboratory Comparison of Emission Factors, Number Size Distributions, and Morphology of Ultrafine Particles from 11 Different Household Cookstove-Fuel Systems.

Ultrafine particle (UFP) emissions and particle number size distributions (PNSD) are critical in the evaluation of air pollution impacts; however, data on UFP number emissions from cookstoves, which are a major source of many pollutants, are limited. In this study, 11 fuel-stove combinations covering a variety of fuels and different stoves are investigated for UFP emissions and PNSD. The combustion of LPG and alcohol (∼1011 particles per useful energy delivered, particles/MJd), and kerosene (∼1013 particles/MJd), produced emissions that were lower by 2-3 orders of magnitude than solid fuels (1014-1015 particles/MJd). Three different PNSD types-unimodal distributions with peaks ∼30-40 nm, unimodal distributions with peaks <30 nm, and bimodal distributions-were observed as the result of both fuel and stove effects. The fractions of particles smaller than 30 nm (F30) varied among the tested systems, ranging from 13% to 88%. The burning of LPG and alcohol had the lowest PM2.5 mass emissions, UFP number emissions, and F30 (13-21% for LPG and 35-41% for alcohol). Emissions of PM2.5 and UFP from kerosene were also low compared with solid fuel burning but had a relatively high F30 value of approximately 73-80%.

Predictive Model Development for Aviation Black Carbon Mass Emissions from Alternative and Conventional Fuels at Ground and Cruise.

The first order approximation (FOA3) currently employed to estimate BC mass emissions underpredicts BC emissions due to inaccuracies in measuring low smoke numbers (SNs) produced by modern high bypass ratio engines. The recently developed Formation and Oxidation (FOX) method removes the need for and hence uncertainty associated with (SNs), instead relying upon engine conditions in order to predict BC mass. Using the true engine operating conditions from proprietary engine cycle data an improved FOX (ImFOX) predictive relation is developed. Still, the current methods are not optimized to estimate cruise emissions nor account for the use of alternative jet fuels with reduced aromatic content. Here improved correlations are developed to predict engine conditions and BC mass emissions at ground and cruise altitude. This new ImFOX is paired with a newly developed hydrogen relation to predict emissions from alternative fuels and fuel blends. The ImFOX is designed for rich-quench-lean style combustor technologies employed predominately in the current aviation fleet.

An investigation of micro-hollow cathode glow discharge generated optical emission spectroscopy for hydrocarbon detection and differentiation.

The analytical utility of a micro-hollow cathode glow discharge plasma for detection of varied hydrocarbons was tested using acetone, ethanol, heptane, nitrobenzene, and toluene. Differences in fragmentation pathways, reflecting parent compound molecular structure, led to differences in optical emission patterns that can then potentially serve as signatures for the species of interest. Spectral simulations were performed emphasizing the CH (A(2)Δ-X(2)Π), CH (C(2)Σ-X(2)Π), and OH (A(2)Σ(+)-X(2)Π) electronic systems. The analytical utility of selected emission lines is demonstrated by a linear relationship between optical emission spectroscopy and parent compound concentration over a wide range, with detection limits extending down to parts per billion (ppb) levels.

XPS analysis of combustion aerosols for chemical composition, surface chemistry, and carbon chemical state.

Carbonaceous aerosols can vary in elemental content, surface chemistry, and carbon nano-structure. Each of these properties is related to the details of soot formation. Fuel source, combustion process (affecting formation and growth conditions), and postcombustion exhaust where oxidation occurs all contribute to the physical structure and surface chemistry of soot. Traditionally such physical and chemical parameters have been measured separately by various techniques. Presented here is the unified measurement of these characteristics using X-ray photoelectron spectroscopy (XPS). In the present study, XPS is applied to combustion soot collected from a diesel engine (running biodiesel and pump-grade fuels); jet engine; and institutional, plant, and residential oil-fired boilers. Elemental composition is mapped by a survey scan over a broad energy range. Surface chemistry and carbon nanostructure are quantified by deconvolution of high-resolution scans over the C1s region. This combination of parameters forms a distinct matrix of identifiers for the soots from these sources.

Nanocarbon nanofluids: morphology and nanostructure comparisons.

Reported here are experimental results of studies designed to identify the operable mechanisms responsible for the gains in thermal conductivity of nanofluids based on nanocarbons. Comparison of functionalized versus nonfunctionalized nanocarbons addresses the effect of interfacial fluid ordering. Comparison between graphitized and nongraphitized carbon black addresses the effect of long-range phonon propagation. Comparison between multi-walled nanotubes and carbon black addresses particle aggregation by comparing two very different, yet fixed, nanocarbon morphologies. Lastly, partial network formation, i.e., spatially distributed clustering, is addressed by varied concentrations of different nanocarbon morphologies.

Synthesis methods, microscopy characterization and device integration of nanoscale metal oxide semiconductors for gas sensing.

A comparison is made between SnO(2), ZnO, and TiO(2) single-crystal nanowires and SnO(2) polycrystalline nanofibers for gas sensing. Both nanostructures possess a one-dimensional morphology. Different synthesis methods are used to produce these materials: thermal evaporation-condensation (TEC), controlled oxidation, and electrospinning. Advantages and limitations of each technique are listed. Practical issues associated with harvesting, purification, and integration of these materials into sensing devices are detailed. For comparison to the nascent form, these sensing materials are surface coated with Pd and Pt nanoparticles. Gas sensing tests, with respect to H(2), are conducted at ambient and elevated temperatures. Comparative normalized responses and time constants for the catalyst and noncatalyst systems provide a basis for identification of the superior metal-oxide nanostructure and catalyst combination. With temperature-dependent data, Arrhenius analyses are made to determine activation energies for the catalyst-assisted systems.

Physical and chemical characterization of residential oil boiler emissions.

The toxicity of emissions from the combustion of home heating oil coupled with the regional proximity and seasonal use of residential oil boilers (ROB) is an important public health concern. Yet scant physical and chemical information about the emissions from this source is available for climate and air quality modeling and for improving our understanding of aerosol-related human health effects. The gas- and particle-phase emissions from an active ROB firing distillate fuel oil (commonly known as diesel fuel) were evaluated to address this deficiency. Ion chromatography of impactor samples showed that the ultrafine ROB aerosol emissions were approximately 45% (w/w) sulfate. Gas chromatography-mass spectrometry detected various n-alkanes at trace levels, sometimes in accumulation mode particles, and out of phase with the size distributions of aerosol mass and sulfate. The carbonaceous matter in the ROB aerosol was primarily light-adsorbing elemental carbon. Gas chromatography-atomic emission spectroscopy measured a previously unrecognized organosulfur compound group in the ROB aerosol emissions. High-resolution transmission electron microscopy of ROB soot indicated the presence of a highly ordered primary particle nanostructure embedded in larger aggregates. Organic gas emissions were measured using EPA Methods TO-15 and TO-11A. The ROB emitted volatile oxygenates (8 mg/(kg of oil burned)) and olefins (5 mg/(kg of oil burned)) mostly unrelated to the base fuel composition. In the final analysis, the ROB tested was a source of numerous hazardous air pollutants as defined in the Clean Air Act Amendments. Approximations conducted using emissions data from the ROB tests show relatively low contributions to a regional-level anthropogenic emissions inventory for volitile organic compounds, PM2.5, and SO2 mass.

Carbon nanostructure examined by lattice fringe analysis of high-resolution transmission electron microscopy images.

The dimensions of graphitic layer planes directly affect the reactivity of soot towards oxidation and growth. Quantification of graphitic structure could be used to develop and test correlations between the soot nanostructure and its reactivity. Based upon transmission electron microscopy images, this paper provides a demonstration of the robustness of a fringe image analysis code for determining the level of graphitic structure within nanoscale carbon, i.e., soot. Results, in the form of histograms of graphitic layer plane lengths, are compared to their determination through Raman analysis.

Application of laser-induced incandescence to the detection of carbon nanotubes and carbon nanofibers.

Laser-induced incandescence applied to a heterogeneous, multielement reacting flow is characterized by temporally resolved emission spectra, time-resolved emission at selected detection wavelengths, and fluence dependence. Two-pulse laser measurements are used to further probe the effects of laser-induced changes on the optical signal. Laser fluences above 0.6 J/cm2 at 1064 nm initiate laser-induced vaporization, yielding a lower incandescence intensity, as found through fluence-dependence measurements. Spectrally derived temperatures show that values of excitation laser fluence greater than this value lead to superheated plasmas with temperatures well above the vaporization point of carbon. The temporal evolution of the emission signal at these fluences is consistent with plasma dissipation processes, not incandescence from solidlike structures. Two-pulse laser experiments reveal that other material changes are produced at fluences below the apparent vaporization threshold, leading to nanostructures with different optical and thermal properties.