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Explosion and combustion properties of alkylsilanes I : temperature-composition limits of explosion for methyl-,dimethyl-,trimethyl-,tetramethyl-,and vinylsilane at atmospheric pressure

The explosion limits of five alkylsilanes were determined as a function of temperature and composition at a pressure of 1 atmosphere. Over a fuel concentration range of 2 to 10 percent, the lowest temperatures (zero C) below which explosion did not occur for the five fuels studied were: tetramethylsilane (CHsub3)sub4Si, 450 degrees; trimethlysilane (CHsub3)sub3SiH, 310 degrees;dimethylsilane (CHsub3)sub2SiHsub2, 220 degrees; methylsilane CHsub3SiHsub3, 130 degrees; and vinylsilane Hsub2C=CH-SiHsub3, 90 degrees. Explosion limits for hydrocarbons analogous to these silanes fall in a temperature range of 500 degrees to 600 degrees C. Since the explosion temperatures of the alkylsilanes are lower than those of the hydrocarbons and since they decrease as hydrogen atoms are substituted for methyl groups, it was concluded that the Si-H bond is more readily susceptible to oxidation than the C-H bond.

Schalla, Rose L↗

Properties of Combustion Gases

New series of reports: First report lists data from combustion of ASTM Jet A fuel and dry air; second report presents tables and figures for combustion-gas properties of natural-gas fuel and dry air, and equivalent ratios.

Wear, J. D.↗

Methodology for Formulating Diesel Surrogate Fuels with Accurate Compositional, Ignition-Quality, and Volatility Characteristics

In this study, a novel approach was developed to formulate surrogate fuels having characteristics that are representative of diesel fuels produced from real-world refinery streams. Because diesel fuels typically consist of hundreds of compounds, it is difficult to conclusively determine the effects of fuel composition on combustion properties. Surrogate fuels, being simpler representations of these practical fuels, are of interest because they can provide a better understanding of fundamental fuel-composition and property effects on combustion and emissions-formation processes in internal-combustion engines. In addition, the application of surrogate fuels in numerical simulations with accurate vaporization, mixing, and combustion models could revolutionize future engine designs by enabling computational optimization for evolving real fuels. Dependable computational design would not only improve engine function, it would do so at significant cost savings relative to current optimization strategies that rely on physical testing of hardware prototypes. The approach in this study utilized the stateof- the-art techniques of 13C and 1H nuclear magnetic resonance spectroscopy and the advanced distillation curve to characterize fuel composition and volatility, respectively. The ignition quality was quantified by the derived cetane number. Two wellcharacterized, ultra-low-sulfur #2 diesel reference fuels produced from refinery streams were used as target fuels: a 2007 emissions certification fuel and a Coordinating Research Council (CRC) Fuels for Advanced Combustion Engines (FACE) diesel fuel. A surrogate was created for each target fuel by blending eight pure compounds. The known carbon bond types within the pure compounds, as well as models for the ignition qualities and volatilities of their mixtures, were used in a multiproperty regression algorithm to determine optimal surrogate formulations. The predicted and measured surrogate-fuel properties were quantitatively compared to the measured target-fuel properties, and good agreement was found. This paper is dedicated to the memory of our friend and colleague Jim Franz. Funding for this research was provided by the U.S. Department of Energy (U.S. DOE) Office of Vehicle Technologies, and by the Coordinating Research Council (CRC) and the companies that employ the CRC members. The study was conducted under the auspices of CRC. The authors thank U.S. DOE program manager Kevin Stork for supporting the participation of the U.S. national laboratories in this study.

Mueller, Charles J↗

Compatibility of alternative fuels with advanced automotive gas turbine and stirling engines. A literature survey

The application of alternative fuels in advanced automotive gas turbine and Stirling engines is discussed on the basis of a literature survey. These alternative engines are briefly described, and the aspects that will influence fuel selection are identified. Fuel properties and combustion properties are discussed, with consideration given to advanced materials and components. Alternative fuels from petroleum, coal, oil shale, alcohol, and hydrogen are discussed, and some background is given about the origin and production of these fuels. Fuel requirements for automotive gas turbine and Stirling engines are developed, and the need for certain reseach efforts is discussed. Future research efforts planned at Lewis are described.

Cairelli, J.↗

Understanding Isomeric Effects on Properties of Aviation Fuels via a Group Contribution Method: Preprint

The molecular composition of aviation fuels, including conventional and sustainable aviation fuels (SAFs), significantly influences their performance, safety, and environmental impact. This study examines the effect of isomeric variation for compounds with the same carbon number and chemical family on key fuel properties, focusing on compounds commonly found in conventional jet fuels and SAFs. A group contribution method (GCM) is employed to predict thermophysical and combustion properties, providing an efficient analytical approach to evaluate the contributions of individual compounds to overall fuel mixture behavior. As part of this work, we introduce FuelLib, an open-source Python tool built around the GCM, to calculate individual compound and fuel mixture properties using various mixing rules. Our work evaluates whether the GCM can capture isomeric effects, that are often overlooked in traditional fuel property estimation. This is particularly important for SAFs, which often are composed of a more limited set of compound classes than conventional fuels, making isomeric differences more critical. Two-dimensional gas chromatography (GCxGC) data, which can be obtained from small fuel samples, provides weight percentages of compounds grouped by chemical family and carbon number rather than detailed information about individual compounds. As a result, assumptions must be made when decomposing GCxGC data into functional groups for GCM applications. Using GCxGC data, we show that the FuelLib tool can be used to predict the fuel properties of conventional jet fuels, with validation against experimental data. The provided tool enables researchers to predict fuel properties of candidate fuels and supports the design of new SAFs at both the component and mixture levels. This capability provides a foundation for studying fuel and combustion properties during SAF development, reducing reliance on costly experimental methods and advancing progress toward certification of new SAFs.The molecular composition of aviation fuels, including conventional and sustainable aviation fuels (SAFs), significantly influences their performance, safety, and environmental impact. This study examines the effect of isomeric variation for compounds with the same carbon number and chemical family on key fuel properties, focusing on compounds commonly found in conventional jet fuels and SAFs. A group contribution method (GCM) is employed to predict thermophysical and combustion properties, providing an efficient analytical approach to evaluate the contributions of individual compounds to overall fuel mixture behavior. As part of this work, we introduce FuelLib, an open-source Python tool built around the GCM, to calculate individual compound and fuel mixture properties using various mixing rules. Our work evaluates whether the GCM can capture isomeric effects, that are often overlooked in traditional fuel property estimation. This is particularly important for SAFs, which often are composed of a more limited set of compound classes than conventional fuels, making isomeric differences more critical. Two-dimensional gas chromatography (GCxGC) data, which can be obtained from small fuel samples, provides weight percentages of compounds grouped by chemical family and carbon number rather than detailed information about individual compounds. As a result, assumptions must be made when decomposing GCxGC data into functional groups for GCM applications. Using GCxGC data, we show that the FuelLib tool can be used to predict the fuel properties of conventional jet fuels, with validation against experimental data. The provided tool enables researchers to predict fuel properties of candidate fuels and supports the design of new SAFs at both the component and mixture levels. This capability provides a foundation for studying fuel and combustion properties during SAF development, reducing reliance on costly experimental methods and advancing progress toward certification of new SAFs.

33 ADVANCED PROPULSION SYSTEMS↗

Laboratory test methods for combustion stability properties of solid propellants

An overview is presented of experimental methods for determining the combustion-stability properties of solid propellants. The methods are generally based on either the temporal response to an initial disturbance or on external methods for generating the required oscillations. The size distribution of condensed-phase combustion products are characterized by means of the experimental approaches. The 'T-burner' approach is shown to assist in the derivation of pressure-coupled driving contributions and particle damping in solid-propellant rocket motors. Other techniques examined include the rotating-valve apparatus, the impedance tube, the modulated throat-acoustic damping burner, and the magnetic flowmeter. The paper shows that experimental methods do not exist for measuring the interactions between acoustic velocity oscillations and burning propellant.

Strand, L. D.↗

Combustion gas properties. 2: Natural gas fuel and dry air

A series of computations has been made to produce the equilibrium temperature and gas composition for natural gas fuel and dry air. The computed tables and figures provide combustion gas property data for pressures from 0.5 to 50 atmospheres and equivalence ratios from 0 to 2.0. Only samples tables and figures are provided in this report. The complete set of tables and figures is provided on four microfiche films supplied with this report.

Wear, J. D.↗

Combustion gas properties. Part 3: Hydrogen gas fuel and dry air

A series of computations has been made to produce the equilibrium temperature and gas composition for hydrogen gas fuel and dry air. The computed tables and figures provide combustion gas property data for pressures from 0.5 to 50 atmospheres and equivalence ratios from 0 to 2.0. Only sample tables and figures are provided in this report.

Wear, J. D.↗

Combustion Gas Properties I-ASTM Jet a Fuel and Dry Air

A series of computations was made to produce the equilibrium temperature and gas composition for ASTM jet A fuel and dry air. The computed tables and figures provide combustion gas property data for pressures from 0.5 to 50 atmospheres and equivalence ratios from 0 to 2.0.

Jones, R. E.↗

Novel biofuel formulations for enhanced vehicle performance

This interdisciplinary research program at Michigan State University, in collaboration with Ford Motor Company, has explored the application of tailored or designed biofuels for enhanced vehicle performance and reduced emissions. The project has included a broad range of experimental research, from chemical and biological formation of advanced biofuel components to multicylinder engine testing of blended biofuels to determine engine performance parameters. In addition, the project included computation modeling of biofuel physical and combustion properties, and simulation of advanced combustion modes in model engines and in single cylinder engines. Formation of advanced biofuel components included the fermentation of five-carbon and six-carbon sugars to n-butanol and to butyric acid, two four-carbon building blocks. Chemical transformations include the esterification of the butyric acid produced to make butyrate esters, and the esterification of succinic acid with n-butanol to make dibutyl succinate (DBS) as attractive biofuel components. The conversion of standard biodiesel, made from canola or soy oil, from the methyl ester to the butyl ester (which has better fuel properties), and the ozonolysis of biodiesel and the raw oil to produce nonanoate fuel components were also examined in detail. Physical and combustion properties of these advanced biofuel components were determined during the project. Physical properties such as vapor pressure, heat of evaporation, density, and surface tension, and low temperature properties of cloud point and cold filter plugging point were examined for pure components and for blends of components with biodiesel and standard petroleum diesel. Combustion properties, particularly emission delay that is the key parameter in compression ignition engines, was measured in the MSU Rapid Compression Machine (RCM), an apparatus that was designed and constructed during the project simulating the compression stroke of an internal combustion engine under highly instrumented conditions. Simulation of and experimentation on combustion in single and multicylinder engines was carried out in detail throughout the project. The combustion behavior of biofuel blends neat and in petroleum were characterized in the MSU optical engine, in part to validate results obtained in the RCM and to provide data for comparison with simulations. Simulation of in- cylinder, low-temperature combustion included development of an extensive fuel injection model that included fuel spray breakup, evaporation, and ignition, along with prediction of cylinder temperature, pressure, and work produced. Single cylinder and multicylinder engine tests under advanced low-temperature combustion conditions conducted at Ford Motor Company validated experimental and simulation results obtained in the MSU engine and in MSU simulations. Single cylinder engine tests of an advanced biofuel containing biodiesel and dibutyl succinate, carried out under low-temperature combustion conditions, showed similar power generation and gas-phase emissions (CO, HC, NOx), but a reduction in particulates of as much as 60% relative to neat biodiesel and 95% relative to petroleum diesel at the same operating conditions. This remarkable finding suggests that biofuels may be able to play a role in eliminating the need for particulate removal systems in diesel vehicles. The multicylinder engine tests at Ford, carried out using butyl nonanoate as an advanced biofuel, also gave promising results, showing a strong decline in particulate emissions and simultaneously a modest decrease in NOx emissions relative to standard petroleum diesel at the same conditions. In summary, this project has shown that advanced biofuels and their blends are capable of maintaining performance while reducing emissions, particularly particulates (soot), in 3 compression ignition engines. The interdisciplinary nature of biofuel production and testing has identified fuel properties that are capable of producing such performance, thus providing direction for the implementation of renewable fuels for U.S. transportation. The testing and simulation studies have deepened our understanding of combustion 1) by advancing the rigor with which simulations can be carried out and 2) by illustrating that differences in biofuel and petroleum fuel properties can be used to predict differences in combustion behavior in engines. The future viability of biofuels for compression ignition (diesel) engines is now subject to economic (cost) uncertainty more so than to technical barriers, as the advanced biofuel blends developed here can improve cold-weather fuel properties, provide similar engine performance, and reduce emissions.

33 ADVANCED PROPULSION SYSTEMS↗

Combustion gas properties of various fuels of interest to gas turbine engineers

A series of computations were made using the gas property computational schemes of Gordon and McBride to compute the gas properties and species concentration of ASTM-Jet A and dry air. The computed gas thermodynamic properties in a revised graphical format which gives information which is useful to combustion engineers is presented. A series of reports covering the properties of many fuel and air combinations will be published. The graphical presentation displays on one chart of the output of hundreds of computer sheets. The reports will contain microfiche cards, from which complete tables and graphs can be obtained. The extent of the planned effort and is documented samples of the many tables and charts that will be available on the microfiche cards are presented.

Jones, R. E.↗

Ignition and combustion of metallized propellants

An experimental program was conducted to investigate the ignition and combustion properties of a gelled, metallized fuel, A1/JP20, burned with gaseous oxygen, and to compare the results to the ignition and combustion properties of neat RP1. Both a Cstar efficiency and a specific impulse efficiency were calculated by comparing experimental values with those from a one-dimensional chemical equilibrium computer code. For most operating conditions, the efficiencies of the A1/JP10 were only 2 to 6 percent less than those of the neat RP1.

Galecki, Diane L.↗

Systematically derived thermodynamic properties for alkane oxidation

Key combustion properties, such as ignition delay time, show strong sensitivity to the thermochemistry of the main species in the standard radical oxidation pathway at low temperatures (600-1000K). Significant uncertainties persist in current estimates of thermodynamic properties, particularly for the larger species of relevance to common practical fuels. In this article, we use advanced computational schemes to evaluate thermodynamic properties for the fuel, fuel radical, peroxy, hydroperoxy-alkyl radical, and hydroperoxide species for a set of 17 fuels containing up to 9 carbon atoms, and with various degrees of branching in the alkane backbone. The procedure, termed STAR-1D, combines conformer sampling to find the minimum geometry, B2PLYP-D3/cc-pVTZ harmonic frequency evaluations, and omega B97X-D/cc-pVTZ one-dimensional torsional mapping. It includes two physically-based scaling routines: a frequency-dependent scaling to B2PLYP-D3/cc-pVTZ anharmonic frequencies and a scaling of one-dimensional omega B97X-D/ccpVTZ torsional profiles to reproduce the product of the B2PLYP-D3/cc-pVTZ frequencies in the harmonic limit. Substantive comparisons with existing experimental databases, together with careful examinations of key theoretical assumptions, are used to explore the accuracy of the predictions. These computationally intensive explorations of 195 species were facilitated by automated thermochemistry software. Further, high accuracy 0 K heats of formation from a separate study are used with the STAR-1D computations to generate NASA polynomial representations. In addition to their intrinsic value, the present results also provide a reliable database for the optimization of group additivity or machine learning schemes for scaling to larger combustion systems. Towards this end a complementary extensive conformational analysis is carried out for the medium sized species and the thermodynamic properties of the lowest energy hydrogen-bonded and non-hydrogen bonded conformers are contrasted for larger hydroperoxy-alkyl radical species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigation of structural, morphological, luminescent and thermal properties of combusted aluminium-based iron oxide

Nanocomposites of aluminium integrated hematite {alpha}-Fe{sub 2}O{sub 3} are synthesized by combustion route using aqueous solutions of AR grade ferric trichloride and aluminium nitrate as precursors. The influence of aluminium incorporation on to the morphology, XPS, photoluminescence and thermal properties has been investigated. The FESEM and AFM micrographs depict that the samples are compact and have homogeneously distributed grains of varying sizes ({approx}20-60 nm). Chemical composition and valence states of constituent elements in hematite are analyzed by XPS. In room temperature photoluminescence (PL) study, we observed strong violet emission around 436 nm without any deep-level emission and a small PL FWHM indicating that the concentrations of defects are responsible for deep-level emissions. The specific heat and thermal conductivity study shows the phonon conduction behavior is dominant. We studied interparticle interactions using complex impedance spectroscopy. We report a new potential candidate for its possible applications in optoelectronics and magnetic devices. -- Graphical abstract: Frequency and temperature dependent interparticle interactions like grains, grain boundary effects using complex impedance spectroscopy of pure and 10 at% Al:Fe{sub 2}O{sub 3} have been studied. Display Omitted

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Production, fuel properties and combustion testing of an iso-olefins blendstock for modern vehicles

With the increasing pressure to decarbonize the transportation sector, exploring strategies that can reduce emissions from light-duty vehicles (LDV) has become critical. Bioblendstocks that allow for higher engine efficiency and fuel economy could complement vehicle electrification and help reach carbon neutrality by 2050. In this context, the potential of a mixture of iso-olefins as a bioblendstock was investigated for multimode boosted spark-ignition (SI)/advanced compression ignition (ACI) engine operation designed to achieve higher overall vehicle fuel economy. By establishing the relationship between the molecular structure of iso-olefins and research octane number (RON), octane sensitivity (S) (i.e., the difference between RON and motor octane number [MON]), and phi-sensitivity a dimethyl-hexenes rich olefins mixture (DMHROM) was identified as a preferred blendstock for SI/ACI combustion engines. Here, a pathway for DMHROM production from biomass-derived ethanol was developed and scaled up. More than 1 gallon of DMHROM blendstock was produced for fuel properties assessment including engine testing. Measurements in a Cooperative Fuel Research Engine showed that the DMHROM blendstock possesses a RON of 94 and S of 13.5, and blends synergistically. Rapid compression machine tests coupled with single-cylinder gasoline direct injection engine measurements demonstrated the 20 vol.% DMHROM blend has higher phi-sensitivity than an olefin-free gasoline base fuel and a typical California Reformulated Gasoline Blendstock for Oxygenate Blending (CARBOB) gasoline fuel. These results demonstrate the potential of DMHROM for improving gasoline fuel performance and quality for operation under ACI conditions. The effectiveness of the aftertreatment system in mitigating emissions was verified and showed that the pure DMHROM blendstock and 20 vol.% blend would not increase non-methane organic gases, NO x , and carbon monoxide (CO) emissions. The DMHROM blendstock was found to slightly decrease sooting tendency when added to a gasoline-base fuel (i.e., ~6% reduction at 20 vol.% blending level). Oxidation stability and lubricant compatibility were both confirmed for the 20 vol.% blend. Overall, these results demonstrate that dimethyl-hexenes have potential for improving engine efficiency and fuel economy while meeting emissions regulations and ASTM specifications for gasoline fuel.

09 BIOMASS FUELS↗