3-pentanone fluorescence yield measurements and modeling at elevated temperatures and pressures

Measurements of 3-pentanone fluorescence quantum yield (FQY) over a wide range of temperatures and pressures in air and nitrogen bath gases are reported and a comprehensive FQY model in support of quantitative planar laser-induced fluorescence diagnostics at elevated pressures and temperatures is presented. Measurements were made of the FQY for 20 mbar of 3-pentanone in nitrogen and air for pressures between 1 and 25 bar in a high-pressure and high-temperature cell for excitation wavelengths of 248, 266, 277, and 308 nm. The measurements were performed in nitrogen from 298 to 745 K and in air from 298 to 567 K. The 3-pentanone FQY data were used to optimize FQY model parameters, including the oxygen and nitrogen quenching rates and vibrational relaxation cascade parameters for nitrogen and oxygen. This work introduces vibrational energy dependence for cascade parameters, as well as a nitrogen quenching rate. The new 3-pentanone FQY model agrees with the measurements within 10%, as well as with fluorescence signal measurements from optical internal combustion engines at pressures and temperatures up to 28 bar and 1100 K.     

Toluene LIF at elevated temperatures: implications for fuel–air ratio measurements

Toluene laser-induced fluorescence (LIF) was investigated for 266- and 248-nm excitation in the temperature range of 300–650 K in a nitrogen/oxygen bath gas of 1 bar total pressure with oxygen partial pressure in the range 0–400 mbar. Contrary to a popular assumption, the toluene LIF signal is not directly proportional to the fuel–air ratio (termed the FAR-LIF assumption) for many conditions relevant to reciprocating IC engines. With increasing temperature, a higher oxygen partial pressure is required to justify the FAR-LIF assumption. The required oxygen pressure becomes unrealistic (>5 bar) for T>670 K at 266-nm excitation and for T>625 K at 248-nm excitation. PACS 33.50.-j; 42.62.-b     

Fluorescence spectroscopy of anisole at elevated temperatures and pressures

Laser-induced fluorescence of anisole as tracer of isooctane at an excitation wavelength of 266 nm was investigated for conditions relevant to rapid compression machine studies and for more general application of internal combustion engines regarding temperature, pressure, and ambient gas composition. An optically accessible high pressure and high temperature chamber was operated by using different ambient gases (Ar, N₂, CO₂, air, and gas mixtures). Fluorescence experiments were investigated at a large range of pressure and temperature (0.2–4 MPa and 473–823 K). Anisole fluorescence quantum yield decreases strongly with temperature for every considered ambient gas, due to efficient radiative mechanisms of intersystem crossing. Concerning the pressure effect, the fluorescence signal decreases with increasing pressure, because increasing the collisional rate leads to more important non-radiative collisional relaxation. The quenching effect is strongly efficient in oxygen, with a fluorescence evolution described by Stern–Volmer relation. The dependence of anisole fluorescence versus thermodynamic parameters suggests the use of this tracer for temperature imaging in specific conditions detailed in this paper. The calibration procedure for temperature measurements is established for the single-excitation wavelength and two-color detection technique.     

Autoignition of surrogate fuels at elevated temperatures and pressures

Autoignition of Jet-A and mixtures of benzene, hexane, and decane in air has been studied using a heated shock tube at mean post-shock pressures of 8.5 ± 1 atm within the temperature range of 1000–1700 K with the objective of identifying surrogate fuels for aviation kerosene. The influence of each component on ignition delay time and on critical conditions required for strong ignition of the mixture has been deduced from experimental observations. Correlation equation for Jet-A ignition times has been derived from the measurements. It is found that within the scatter of experimental data dilution of n-decane with benzene and n-hexane leads to slight increase in ignition times at low temperatures and does not change critical temperatures required for direct initiation of detonations in comparison with pure n-decane/air mixtures. Ignition times in 20% hexane/80% decane (HD), 20% benzene/80% decane (BD) and 18.2% benzene/9.1% hexane/72.7% decane (BHD) mixtures at temperature range of T  1450–1750 K correlate well with induction time of Jet-A fuel suggesting that these mixtures could serve as surrogates for aviation kerosene. At the same time, HD, BD and BHD surrogate fuels demonstrate a stronger autoignition and peak velocities of reflected shock front in comparison with Jet-A and n-decane/air mixtures.     

Metallization of Fe0.94O at elevated pressures and temperatures observed by shock-wave electrical resistivity measurements

The electrical resistivity of Fe_0.94O (wüstite) has been measured under shock-wave conditions to pressures between 72 and 155 GPa (0.72 to 1.55 Mbar). The resistivity of FeO at these pressures is approximately 1 (+/-0.6) × 10^-6 ohm-m, as compared with 1.7(+/-0.3) × 10^-3 ohm-m at ambient conditions. The absolute value of the electrical resistivity and the increase in resistivity with pressure along the Hugoniot (i.e. the shock compression curve) are consistent with FeO becoming metallic at high pressures and temperatures.     

Burning velocity of methane-hydrogen mixtures at elevated pressures and temperatures

The effect of the initial pressure, temperature, and equivalence ratio on a number of combustion characteristics of methane-air mixtures with hydrogen additives in a closed vessel is experimentally studied. Experiments are conducted at 1, 5, and 10 atm and temperatures from 22 to 300°C. The hydrogen content in the fuel is 0, 10, and 20 vol %. The fuel equivalence ratio varies from 0.6 to 1.0. The limitations imposed by buoyancy on measurements of the laminar burning velocity by the constant-volume bomb method with recording of pressure-time histories are analyzed. It is shown that the laminar burning velocity can be appreciably increased by adding no less than 20 vol % of hydrogen to the fuel.     

Fluoranthene laser-induced fluorescence at elevated temperatures and pressures: implications for temperature-imaging diagnostics

The objective of this study is to develop a quantitative measurement of temperature from fluoranthene fluorescence under conditions with elevated temperatures and pressures. Absorption and fluorescence of fluoranthene are studied in a pressure and temperature range of 0.1–4 MPa and 473–873 K for the two excitation wavelengths of 266 and 355 nm. The influence of thermodynamic parameters such as pressure, temperature and gas composition is characterized in a high-pressure and high-temperature facility. When increasing the pressure, the vibrational relaxation mechanisms are favored, which involves an increase of the fluorescence quantum yield. Concerning the temperature effect, the fluorescence decreases with increasing temperature, this is explained by efficient radiative mechanisms of intersystem crossing. The quenching effect is strongly efficient in air, with a fluorescence evolution described by the Stern–Volmer relation. Over the temperature range studied, the fluorescence quantum yield decreases exponentially by two orders of magnitude. From the temperature dependence of fluoranthene fluorescence in different ambient gases for 266 and 355 nm excitation, the potential temperature measurements in homogeneously and inhomogeneously seeded systems are suggested: the single-color detection technique, the single-excitation two-color detection technique and the dual-excitation wavelength technique.     

Transported JPDF modelling and measurements of soot at elevated pressures

Accurate measurements and modelling of soot formation in turbulent flames at elevated pressures form a crucial step towards design methods that can support the development of practical combustion devices. A mass and number density preserving sectional model is here combined with a transported joint-scalar probability density function (JDPF) method that enables a fully coupled scalar space of soot, gas-phase species and enthalpy. The approach is extended to the KAUST turbulent non-premixed ethylene-nitrogen flames at pressures from 1 to 5 bar via an updated global bimolecular (second order) nucleation step from acetylene to pyrene. The latter accounts for pressure-induced density effects with the rate fitted using comparisons with full detailed chemistry up to 20 bar pressure and with experimental data from a WSR/PFR configuration and laminar premixed flames. Soot surface growth is treated via a PAH analogy and soot oxidation is considered via O, OH and O₂ using a Hertz-Knudsen approach. The impact of differential diffusion between soot and gas-phase particles is included by a gradual decline of diffusivity among soot sections. Comparisons with normalised experimental OH-PLIF and PAH-PLIF signals suggest good predictions of the evolution of the flame structure. Good agreement was also found for predicted soot volume statistics at all pressures. The importance of differential diffusion between soot and gas-phase species intensifies with pressure with the impact on PSDs more evident for larger particles which tend to be transported towards the fuel rich centreline leading to reduced soot oxidation.     

Fluorescence spectroscopy of naphthalene at high temperatures and pressures: implications for fuel-concentration measurements

Fluorescence of the S ₁→S ₀ transition of naphthalene vapour after laser excitation at 266 nm was studied in a heated cell. Experiments were carried out for temperature in the range 350–900 K, at pressure between 0.1 and 3.0 MPa and for oxygen molar fraction from 0 to 21%. The absorption cross section of naphthalene showed a non-monotonic dependence upon temperature, which may be attributed to the spectral structures present in the absorption spectrum of naphthalene. Under nitrogen atmosphere, naphthalene fluorescence bi-exponentially decreased by an order of magnitude as temperature increased, whereas it increased by about 10% with pressure. Strong influence of quenching by O₂ on naphthalene fluorescence was observed and Stern–Volmer plots were found to be linear for temperatures between 450 and 750 K. The dependence of naphthalene fluorescence on oxygen concentration suggests one to use this molecule for fuel-concentration measurements in turbulent flows.     

Equation of state and electrical resistivity of liquid mercury at elevated temperatures and pressures

Experimental results have been obtained for the density and electrical resistivity of liquid mercury as functions of the independent variables temperature (20°c–1000°c) and pressure (0–1000 bars). Basic equipment for both measurements consisted of a steel vessel containing an internal electrical resistance furnace and pressurized with argon gas. The equation of state was determined with an accuracy of about ±1/4% using Archimedes' method by employing a series of totally immersed radioactive sinkers whose rise or fall in the mercury was detected with a γ-ray counter external to the pressure vessel. The electrical resistivity was measured with an accuracy of about ±1/2% using a four-lead resistance cell fabricated in fused silica. The two measurements have also been combined to give electrical resistivity at constant volume.     

Non-contact sound velocities and attenuation measurements of several ceramics at elevated temperatures

Laser ultrasonic technique has been employed to carry out the sound velocities and attenuation measurements as a function of temperature in alumina, two kinds of silicon nitride and partially stabilized zirconia (PSZ) samples. Accuracy of the laser technique used has been checked in terms of the diffraction effect and reproducibility of the results. Results of attenuation at room temperature have been compared with quartz transducer technique. In PSZ, velocity behavior has become non-linear and also, a peak in attenuation has been observed around 500 degrees C. In one of the silicon nitride sample, which uses glassy sintering agent, attenuation has shown a sharp peak around 950 degrees C. Interestingly, when the experiment was repeated from 800 to 1000 degrees C, this anomalous attenuation peak has disappeared, leaving a background increasing towards higher temperatures.     

Ignition delay time measurements and modeling for gasoline at very high pressures

Ignition delay times (IDT) for high-octane-number gasolines and gasoline surrogates were measured at very high pressures behind reflected shock waves. Fuels tested include gasoline, gasoline with oxygenates, and two surrogate fuels, one dominated by iso-octane and one by toluene. RON/MON for the fuels varied from 101/94 to 106.5/91.5. Measurements were conducted in synthetic air at pressures from 30 to 250 atm, for temperatures from 700 to 1100 K, and equivalence ratios near 0.85. Results were compared with a recent gasoline mechanism of Mehl et al. (2017). IDT measurements of the iso-octane-dominated surrogate were very well reproduced by the model over the entire pressure and temperature range. IDT measurements for the toluene-dominated surrogate were also reproduced by the model to a lesser extent. By contrast, IDT measurements for the neat gasoline and gasoline with oxygenates, show excellent agreement with the trends of the Mehl et al. model only below 900 K. Above 900 K, the model returned IDT values for the two gasolines that were approximately 1.6× the measured values. Finally, we observed that IDT measurements for the toluene-dominated surrogate fuel and the two gasolines, near 70 atm and below 900 K, appeared to be shortened, possibly by non-homogeneous ignition or non-ideal gas processes. This dataset provides a critically needed set of IDT targets to test and refine boosted gasoline models at high pressures.     

Fluorescence spectroscopy of kerosene vapour at high temperatures and pressures: potential for gas turbines measurements

Laser-induced fluorescence spectroscopy of kerosene vapour was performed in a heated test cell operating between 450 and 900 K, at pressure from 0.1 to 3.0 MPa, for oxygen molar fraction between 0 and 21 %, with different laser excitation wavelengths (248, 266, 282 and 308 nm). Results show that, depending on the laser excitation scheme, kerosene fluorescence spectrum exhibits one or two fluorescence bands in the UV–visible range (attributed to aromatics naturally present in kerosene fuel). Fluorescence intensity of these bands decreases with increasing temperature, pressure and oxygen molar fraction. Different imaging strategies were derived from spectroscopic findings to simultaneously measure temperature and equivalence ratio fields in kerosene/air sprays, or flame structure and fuel spatial distribution in kerosene/air aeronautical combustors, by means of planar laser-induced fluorescence on kerosene vapour (K-PLIF).     

Molecular dynamics simulation of methane in sodium montmorillonite clay hydrates at elevated pressures and temperatures

Computer simulation has been used to study the structure and dynamics of methane in hydrated sodium montmorillonite clays under conditions encountered in sedimentary basins. Systems containing approximately one, two, three and four molecuiar layers of water have followed gradients of 150 bar km^?1 and 30Kkm^?1, to a maximum burial depth of 6 km (900 bar and 460 K). Methane is coordinated to approximately 19 oxygen atoms, of which typically 6 are provided by the clay surface. Only in the three- and four-layer hydrates is methane able to leave the clay surface. Diffusion depends strongly on the porosity (water content) and burial deth self-diffusion coefficients are in the range 0.12 × 10^?9m²S^?1 < D < 12.65 × 10^?9m²s^?1 for water and 0.04 × 10^?9m²s^?1 < D < 8.64 × 10^?9m²s^?1 for methane. Bearing in mind that porosity decreases with burial depth, it is estimated that maximum diffusion occurs at around 3 km. This is in good agreement with the known location of methane reservoirs in sedimentary basins.     

Line parameter measurements and calculations of CO broadened by nitrogen at elevated temperatures

Measurements of the line strengths and collisional broadening widths of CO in a N₂ atmosphere were made from 300 to 600 K. The lines studied were the P(2), P(3), P(7), P(12), P(18), and P(22) lines of the fundamental band at 2100 cm^?1. The absorption spectra were parametrically fit to a Voigt lineshape model. The band strength was determined to be 250±8 cm^?2atm^?1. The broadening results are compared to Anderson-Tsao-Curnutte calculations and to other experimental studies. The possibility of using an equation of the form $\text{γ(T)=γ(T}{}_0\text{(}\text{T}{}_0\text{T}\text{)}{}^{\mathrm{n}}$ to extrapolate the temperature dependence of the half-widths to flame temperatures is discussed.     

Experimental and modeling study on the auto-ignition properties of ammonia/methane mixtures at elevated pressures

Ammonia (NH₃) is considered as a promising carbon free energy carrier for energy and transportation systems. However, its low flammability and high NO_x emission potential inhibit the implementation of pure NH₃ in these systems. On the other hand, methane is a favorable low emission fuel that can be used as a co-firing fuel in ammonia combustion to promote the reactivity and control the emission levels. However, knowledge of the ignition properties of NH₃/CH₄ mixtures at intermediate temperatures and elevated pressures is still scarce. This study reports ignition delay times of NH₃/CH₄/O₂ mixtures diluted in Ar or Ar/N₂ over a temperature range of 900–1100 K, pressures of 20 and 40 bar, and equivalence ratios of 0.5, 1.0, and 2.0. The results demonstrate that a higher CH₄ mole fraction in the fuel mixture increases its reactivity, and that the reactivity decreases with increasing the fuel-oxygen equivalence ratio. The most recent mechanisms of Glarborg et al. (2018) and Li et al. (2019) were compared against the experimental data for validation purposes. Both mechanisms can predict the measurements fairly well, and key elementary reactions applied in both mechanisms were compared. A modified mechanism is provided, which can reproduce the measurements with smaller discrepancies in most cases. Detailed modeling for emissions indicated that adding CH₄ to the fuel mixture increases the emission of NO_x.     

Thermodynamics of iron at extreme pressures and temperatures

A thermodynamic database on all iron phases (BCC, FCC, HCP and melt) has been created using thermochemical and equations of state data from experiments and theory. The database permits the calculation of the phase diagram of iron to physical conditions of the Earth's core (pressure of 365 GPa and temperature of 6453 K). If the inner core were all iron, its upper temperature would be 6453 (500) K. The average heat capacity of a pure iron HCP inner core is calculated as 29.4 J/mol/K with an entropy of 92 J/mol/K and a gruneisen parameter of 1.81.     

Constraints of two-colour TiRe-LII at elevated pressures

The main objective of this work is to investigate the influence of high-pressure conditions on the determination of primary particle size distributions of laser-heated soot particles using pyrometrically determined temperature decays. The method is based on time-resolved laser-induced incandescence measurements carried out at two different wavelengths (two-colour TiRe-LII). The LII signals are transferred into a particle ensemble averaged (effective) temperature using Planck’s thermal radiation formula. Assuming that all particles within the size distribution possess a unique temperature at the end of the laser pulse, the size distribution can be determined by numerically simulating the measured temperature decay. From our investigations, for pressures up to a few bars it is obvious that this strategy can be successfully applied if standard laser pulses of nano-second duration are used as an LII-excitation source. At higher pressures the time scales of heat conduction are decreased to such an extent that a unique temperature for all particles within the ensemble cannot be assumed at the end of the nano-second laser pulse. However, further investigations show that the presented two-colour TiRe-LII technique can be successfully adopted under technical high-pressure conditions as well, if the pulse duration of the TiRe-LII-excitation source is reduced into the pico-second range.