Negative Temperature Coefficient Regime Research Articles

Electrothermal Instabilities in Barium-Titanate-Based Ceramics

An electrothermal analysis for barium-titanate-based ceramics is presented, combining the Heywang–Jonker model for the electric resistivity with a heat dissipation mechanism based on natural convection and radiation in a one-dimensional model on the device level with voltage as the control parameter. Both positive-temperature-coefficient (PTC) and negative temperature coefficient (NTC) effects are accounted for through the double Schottky barriers at the grain boundaries of the material. The problem formulated in this way admits uniform and non-uniform multiple-steady-state solutions that do not depend on the external circuit. The numerical bifurcation analysis reveals that the PTC effect gives rise to several multiplicites above the Curie point, whereas the NTC effect is responsible for the thermal runaway (temperature blowup). The thermal runaway phenomenon as a potential thermal shock could be among the possible reasons for the observed thermomechanical failures (delamination fracture). The theoretical results for the NTC regime and the thermal runaway are in agreement with the experimental flash sintering results obtained for barium titanate, and 3% and 8% yttria-stabilized zirconia.

A shock tube study of the ignition delay time of DME/ammonia mixtures: Effect of fuel blending from high temperatures to the NTC regime

An experimental and chemical kinetic investigation has been conducted to understand the effect of dimethyl ether (DME) blending on the ignition delay time of ammonia (NH3) from high temperatures to the negative temperature coefficient (NTC) regime in a shock tube with the DME fractions of 0 %, 5 %, 25 %, 50 %, and 100 %, temperatures of 690–1810 K, pressures of 1.2 and 10 atm, and equivalence ratio of 1.0. Four representative literature chemical kinetic models were validated against our measurements, however none of the above models can provide reasonable predictions of the experimental data in the NTC regime. A chemical kinetic model was developed in this study, the model was also been validated by the ignition delay times, laminar flame speeds and specie profiles data of DME/ammonia mixtures in the literature. Experimental results show that the ignition delay times of NH3 can be obviously shorten by 5 % DME addition in both high temperature and the NTC region. Chemical kinetic analyses reveal that the addition of 5 % DME can rapidly generate OH radical through the reaction pathway of HO2 → H2O2 → OH at 1250 K. At 800 K, the blended DME can be rapidly consumed via the reaction pathway of R → RO2 → QOOH → OOQOOH to promote the production of OH radical in the early stage, thus lead to the reduced ignition delay time of DME/NH3 mixture.

Microgravity Spherical Droplet Evaporation and Entropy Effects.

Recent efforts to understand low-temperature combustion (LTC) in internal combustion engines highlight the need to improve chemical kinetic mechanisms involved in the negative temperature coefficient (aka cool flame) regime. Interestingly, microgravity droplet combustion experiments demonstrate this cool flame behavior, allowing a greater focus on chemistry after buoyancy, and the corresponding influence of the conservation of momentum is removed. In Experimental terms, the LTC regime is often characterized by a reduction in heat transfer losses. Novel findings in this area demonstrate that lower entropy generation, in conjunction with diminished heat transfer losses, could more definitively define the LTC regime. As a result, the simulation of the entropy equation for spherical droplet combustion under microgravity could help us to investigate fundamental LTC chemical kinetic pathways. To provide a starting point for researchers who are new to this field, this effort first provides a comprehensive and detailed derivation of the conservation of entropy equation using spherical coordinates and gathers all relevant information under one cohesive framework, which is a resource not readily available in the literature. Subsequently, the well-known d2 law analytical model is determined and compared to experimental data that highlight shortcomings of the law. The potential improvements in the d2 law are then discussed, and a numerical model is presented that includes entropy. The resulting codes are available in an online repository to ensure that other researchers interested in expanding this field of work have a fundamental starting point.

High-Resolution Two-Dimensional Numerical Simulation of n-Heptane/Air Autoignition Under the Influence of Temperature Fluctuation

ABSTRACT High-resolution two-dimensional numerical simulations are performed to investigate n-heptane/air autoignition process under different initial temperatures with varied levels of temperature fluctuations. It is found that temperature fluctuation has an important impact on the autoignition process, and its effects depend on the initial mean temperature. When is located at the upper turning point of the negative temperature coefficient (NTC) regime, as the temperature fluctuation increases, the autoignition mode evolves from a single-stage ignition mode controlled by high-temperature chemistry (HTC) to a mode characterized by the coexisting of multi-stage and single-stage ignition. Both the first-stage heat release and ignition delay increase, but the overall heat release and the total ignition delay decrease. In the presence of a large temperature fluctuation, the low-temperature chemistry (LTC), and HTC reactions, single-stage and two-stage ignitions could coexist in the domain. Chemical explosive mode and sensitivity analyses are performed to identify the reaction mode and the key element reactions in the mutli-stage autoignition process. The temperature fluctuation has a significant promotion effect on the overall ignition except when is located at the lower turning point of the NTC regime. Overall, the NTC phenomenon is weakened under the influence of temperature fluctuation, approaching to zero temperature coefficient (ZTC) phenomenon.

Dual-camera high-speed imaging of n-hexane oxidation in a high-pressure shock tube

Shock tubes are widely used in the study of chemical kinetics. Its benefits rely on the almost ideal shock-heating process that provides high temperatures and pressures to a chemical system for a limited test time. Just like any reactor, shock tubes are not immune to non-ideal effects. The study of conditions that might deviate experiments from ideal conditions is thus of the utmost importance. High-speed imaging has been proven to be a powerful tool to analyze non-ideal / non-homogenous combustion in shock tubes. In this work, dual-camera high-speed imaging experiments were performed at 10, 15 and 20 bar in a high-pressure shock tube (HPST). An optical section was designed as an extension of the HPST which enabled simultaneous visualization from the endwall and the sidewall of the driven section of the shock tube. n-Hexane, a fuel with a negative temperature coefficient (NTC) behavior that has been identified as prone to non-homogenous ignition, is used as a test fuel. Reactive mixtures and thermodynamic conditions were selected to visually analyze ignition processes at the high-temperature, NTC and low-temperature regimes. Non-homogeneous ignition was observed mostly at the local maximum of the IDT, which is comprised by the high-temperature and NTC regions. Stoichiometric n-hexane mixture with high fuel loading (5% n-hexane) presented the highest deviation from constant volume chemical kinetic simulations. The inclusion of helium as a bath gas to mitigate preignition was tested and it showed to improve the susceptibility of the mixtures to develop reaction fronts. The modified Sankaran criterion for the identification of ignition regimes in shock tubes was tested and it showed an overall good agreement against the experimental observations.

Prediction of the developing detonation regime in a NTC-fuel/air mixture with temperature inhomogeneities under engine conditions

The developing detonation process resulting in superknock development under realistic engine conditions in the presence of low-temperature chemistry (LTC) is investigated using two-dimensional direct numerical simulations (DNS). A new model is proposed to predict the developing detonation regime under engine conditions. The prediction is validated against the DNS results. Dimethyl ether (DME) exhibiting a typical negative temperature coefficient (NTC) behavior is used as a fuel. In the presence of the NTC regime, the mean distance of dissipation elements of the ignition delay field, l¯DE, is considered as the characteristic length scale of hot spots to improve the predictive accuracy of the model. The model also accounts for the multi-dimensional effect resulting from the interaction and collision of multiple ignition kernels that is found to promote the onset of detonation and reduce the runup distance of detonation initiation as compared to that of 1D laminar detonation cases. The trasient mixture state is also incorporated in the model development. The model is demonstrated to accurately capture the developing detonation boundary that is consistent with the knock intensity level obtained from the statistical analysis of DNS dataset.

Experimental and model-based analysis of combustion and auto-ignition of gasoline and three surrogate fuels in a single-cylinder research engine operated under knocking conditions

A systematic analysis of knocking combustion at the knock limit in a single-cylinder research engine is conducted. Both experimental and numerical methods are used to investigate the physical phenomena involved in knocking combustion. While real gasoline fuel can be used directly in experimental studies, this is not feasible in numerical simulations. Here, surrogate fuels with a reduced number of components defined to match the desired properties, such as knock resistance, are employed. In this work, standard gasoline and three surrogate fuels are considered. Differences in composition complexity are covered by selecting isooctane and two toluene reference fuels (TRF) with ethanol addition, all of which exhibit negative temperature coefficient (NTC) behavior in which auto-ignition delay times increase with increasing temperature. Spark timing sweeps at two engine speeds show that the knock resistance of the fuels correlates with the respective research octane number (RON). Isooctane is found to have higher knock resistance and higher sensitivity to engine speed than standard gasoline. One of the two TRFs studied shows good agreement with gasoline in terms of combustion and knock characteristics. The lower knock resistance of the other TRF indicates a non-linear dependence between mixture composition and knock resistance. A strong relative increase in knock resistance at higher engine speeds suggests a possible influence of NTC behavior at lower engine speeds. In the subsequent model-based analysis, the fuel influence on combustion and auto-ignition is investigated, and the laminar burning velocities are found to correlate well with the observed heat durations. While auto-ignition may be triggered by a cool spot at the lower engine speed and at operating conditions within the NTC regime, auto-ignition at the higher engine speed is assumed to be initiated by hot spots. These different mechanisms for initiating auto-ignition were identified as a potential explanation for the different knock resistances observed.

A new skeletal kinetic model for methanol/ n-heptane dual fuels under engine-like conditions

In dual-fuel engines, diesel is typically used to initiate the ignition of methanol, resulting in a turbulent spray flame. However, the lack of skeletal or reduced mechanisms for methanol/n-heptane blends limits the further research of dual-fuel combustion. Therefore, a skeletal methanol/n-heptane mechanism including 52 species and 182 reactions was proposed based on the decoupling method. Firstly, it was validated by the recent experiments for blends and compared with several mechanisms. Good agreement between the predicted and measured results was obtained in terms of the ignition delay time, laminar flame speed, and species distributions for pure n-heptane and methanol as well as blends. The new mechanism shows improvements on the negative temperature coefficient (NTC) behavior and the low-temperature ignition for blends compared with other mechanisms. Secondly, the effect of methanol on n-heptane decomposition was investigated based on kinetic analysis. Results showed that methanol competes OH with n-heptane at low temperatures, mainly prolonging the second-stage ignition process. At high temperatures, more HO2 was produced via CH3OH→CH2OH→CH2O + HO2. The existence of methanol also removes the NTC regime toward lower temperatures at intermediate temperatures. Methanol/n-heptane dual fuels no longer exhibit NTC behaviors with high concentration methanol.

Investigation of Engine Combustion and Auto-ignition of a Multicomponent Surrogate Fuel with NTC Behavior Under Knocking Conditions

The occurrence of knocking combustion is limiting the efficiency of modern spark ignition engine operation. Thus, an understanding of the processes at the knock limit is required for further optimization of the combustion process. In this work, the combustion of a multicomponent Toluene Reference Fuel (TRF) in a single-cylinder research engine is investigated under knocking conditions. The fuel exhibits a negative temperature coefficient (NTC) regime for thermodynamic conditions relevant to the engine operation. A precursor model is used to capture the auto-ignition process. Under homogeneous conditions, a two-stage auto-ignition is observed. Inside the NTC regime, the temperature affects both first-stage and second-stage auto-ignition delay times. With a subsequently conducted multi-cycle engine LES, the effects of temperature stratification and turbulent flame propagation on the local auto-ignition process are investigated. It is observed, that the NTC behavior leads to a widespread two-stage auto-ignition. The knock intensity observed in the experiments is directly related to the mass consumed by auto-ignition. This is due to the fast consumption of the auto-ignited mass by the flame front. With that, the NTC behavior affects the local auto-ignition process in the unburned mixture while the flame propagation determines the knock intensity for the operating conditions at the knock limit.

Chemical kinetic interactions and sensitivity analyses for 2-ethylhexyl nitrate-doped PRF91 using a reduced mechanism

A numerical and experimental investigation about the chemical kinetic interactions between 2-ethylhexylnitrate (EHN) and PRF91 was performed in this study. Rapid compression machine experiments were conducted to investigate the effect of EHN on the autoignition reactivity of the fuel, and a reduced chemical kinetic mechanism was developed including an EHN sub-model. Experiments showed that the ignition delay decreases as the fuel is doped with EHN, but the effect of the doping level of EHN on the ignition is highly non-linear. Moreover, experiments showed that the EHN effectiveness is lowest during the transition between the low-temperature regime and the negative temperature coefficient (NTC) regime, and it rapidly increases as the temperature increases. Both detailed and (developed) reduced mechanisms were validated against the experimental results, allowing a more in-depth EHN-fuel chemistry study. Additionally, ignition delay sensitivity and EHN effectiveness sensitivity analyses were performed with the reduced mechanism to identify the reactions that control the interaction between EHN and the fuel. As the result, EHN thermal decomposition is only relevant for very low temperatures. The chemistry of EHN-doped fuel is more sensitive to intermediate temperature reactions than that of straight fuel, especially at lower temperatures, due to the effect of EHN on the NTC behavior of the fuel. Finally, the chemistry of EHN-doped fuel is very sensitive to NO2-to-NO reactions, especially at high temperatures, because these reactions transform the NO2 generated by EHN into NO, which is a very effective fuel reactivity enhancer.

The study of combustion characteristics for conventional and renewable Jet fuels at Low-to-intermediate temperatures in a rapid compression Machine

The combustion characteristics of jet fuels, including conventional (Jet-A1 and JP-5) and renewable (hydro-processed renewable jet, HRJ) jet fuels at low-to-intermediate temperatures were studied in a rapid compression machine (RCM). Compression pressures were varied at 10, 15, and 20 bar under a low temperature combustion regime (626 K-874 K). Fuel/oxidizer mixture conditions were created in order to investigate the auto-ignition delays responding to various equivalence ratios of 0.25 and 0.5. Longer auto-ignition delays were observed with a leaner fuel/oxidizer mixture (ϕ=0.25) by as much as 79.2% as compared to the richer mixture condition (ϕ=0.5). Doubling the compression pressures from 10 to 20 bar led to the reduction of the auto-ignition delays by as much as 58.8%. The negative temperature coefficient (NTC) regime was found to be strongly related to the changes in the equivalence ratio, where the NTC formation is clearly observed at lower equivalence ratio of 0.25 for all the tested fuels. In addition, the renewable jet fuel exhibited a shorter auto-ignition delay by as much as 54.5% as compared to Jet-A1 and JP-5 at equivalence ratio of 0.5. The higher hydrogen-to-carbon (H/C) ratio and lower concentration of cyclic molecules in the HRJ were among the reasons for the reactivity improvement compared to the petroleum jet fuels.

Experimental Investigation of the Pressure Dependence of Iso-Octane Combustion

Iso-octane is frequently used as a surrogate fuel or as a component in primary reference fuel blends when low-temperature combustion strategies in engines are investigated. To develop control strategies for these engines, the reaction kinetics of iso-octane must be known starting from the low temperatures and intermediate pressures before ignition to the high temperatures and pressures of combustion. This work adds new experimental data sets to the validation data for reaction mechanism development by investigating the oxidation of iso-octane in stoichiometric mixtures in a flow reactor at pressures of p = 1, 10, and 20 bar and 473K ≤ T ≤ 973 K. The experimental data are compared to simulations with recent reaction mechanisms [Atef et al., Combustion and Flame 178, (2017), Bagheri et al., Combustion and Flame 212, (2020), Cai et al., Proceedings of the Combustion Institute 37, (2018), Fang et al., Combustion and Flame 214, (2020)]. The comparison between experimental and simulated mole fractions as function of temperature show reasonable agreement for all investigated pressures. In particular, the experimentally observed onset of low-temperature reactivity above a certain pressure, the shift of the negative temperature coefficient (NTC) regime with increasing pressure to higher temperatures, and the acceleration of the high-temperature chemistry are captured well in the simulations. Deviations between experimental and simulated results are discussed in detail for the reactivity of iso-octane and some key intermediates such as 2,2,4,4-tetramethyl-tetrahydrofuran, iso-butene and acetone at low temperatures.

The reactions of propanal/acetone with hydroperoxyl radicals: A theoretical and modeling study

Propanal (C2H5CHO) and acetone (CH3COCH3), the C3 carbonyl compound isomers, are the main byproducts of bio-alcohol combustion. In this work, the reaction rate coefficients between propanal/acetone and hydroperoxyl radicals (HO2) over 500–2000 K and 0.01–100 atm were obtained by the RRKM/master equation method based on high-level quantum chemical calculations. The competition relationship among the H-abstraction, HO2 addition, addition-dissociation reaction pathways and their temperature and pressure dependence were explored. The results show that for propanal + HO2, the aldehydic H-abstraction reaction is highly favored over the addition-dissociation and other abstraction channels, while for acetone + HO2, the H-abstraction reaction is comparable with those of addition-dissociation reactions at low temperature. At temperatures ≤ 700 K and pressures ≥ 1 atm, collisional stabilization of the peroxy-alcohol radical is the dominant channel. To reveal the impact of the studied reactions on model predictions, the rate coefficients of various reaction channels calculated in this work and those of peroxy-alcohol radicals + HO2 from the literature were incorporated into a recently proposed low-temperature mechanism of propanal. The results show that the aldehydic H-abstraction reaction of propanal by HO2 greatly contributes to the combustion behavior in the negative temperature coefficient regime. The peroxy-alcohol radical favors its decomposition channel with temperatures ranging from 500 to 900 K at 1 atm in a JSR. Modified Arrhenius representations of the calculated rate coefficients are given and should be valuable for the future development of low-temperature oxidation mechanisms for aldehydes, ketones, and alcohols.

On the controlling mechanism of the lower turning point in the negative temperature coefficient regime

In this study, a comprehensive computational investigation is conducted to observe the negative temperature coefficient (NTC) behavior of the explosion limit of propane explored with detailed chemical kinetics, to find on the controlling mechanism of the lower turning point in the negative temperature coefficient region. The results show that the global behavior of the lower turning point exhibits distinct thermodynamic and chemical kinetic characteristics under different equivalence ratios from those thermodynamic and chemical kinetic characteristics under different inert gas ratios. Further chemical analyses demonstrate that the lower turning point is determined by the competition between chain termination reactions and chain branching/propagation reactions in the low-temperature reactions. Therefore, the ratio of the hydroxyl radical (OH) production rate to the total production rate of the alkyl radical (R) is constructed, which captures the turnover state of the lower turning point in the NTC regime.

A comprehensive experimental and kinetic modeling study of 1-hexene

It is important to understand the low-temperature chemistry of 1-hexene as it is used as a representative alkene component in gasoline surrogate fuels. Ignition delay times (IDTs) of 1-hexene measured in rapid compression machines (RCMs) can be used to validate its low-temperature chemistry. However, volume history profiles are not available for published RCM IDT data. This has restricted the validation of the low-temperature chemistry of 1-hexene at engine-relevant conditions (i.e. at low temperatures and high pressures). Thus, new RCM IDT data with associated volume history profiles are needed. In this study, both an RCM and a high-pressure shock tube (ST) are employed to measure IDTs of 1-hexene at equivalence ratios of 0.5, 1.0 and 2.0 in ‘air’ and at pressures of 15 and 30 atm. A cool-flame (first stage) and total (second stage) ignition was observed in the RCM experiments. Moreover, carbon monoxide and water versus time histories produced during 1-hexene oxidation at highly diluted conditions were measured in a ST. A new detailed chemical kinetic model describing 1-hexene oxidation is proposed and validated using these new measured data together with various experimental data available in the literature. The kinetic model can predict well the auto-ignition behavior and oxidation processes of 1-hexene at various conditions. The rate constants and branching ratio for hydroxyl radical addition to the double bond of 1-hexene are particularly important and discussed based on the experimental and theoretically calculated results from previous studies as well as validation results from jet-stirred reactor (JSR) species profiles. Flux and sensitivity analyses are performed to determine the important reaction classes for 1-hexene oxidation and show that the reactions associated with hydroxy radical addition to the double bond contribute most to the low-temperature reactivity of 1-hexene. In the negative temperature coefficient (NTC) regime, the isomerization of hexenyl-peroxy radicals promotes fuel reactivity due to its associated chain branching pathways.

Extreme Low-Temperature Combustion Chemistry: Ozone-Initiated Oxidation of Methyl Hexanoate.

The accelerating chemical effect of ozone addition on the oxidation chemistry of methyl hexanoate [CH3(CH2)4C(═O)OCH3] was investigated over a temperature range from 460 to 940 K. Using an externally heated jet-stirred reactor at p = 700 Torr (residence time τ = 1.3 s, stoichiometry φ = 0.5, 80% argon dilution), we explored the relevant chemical pathways by employing molecular-beam mass spectrometry with electron and single-photon ionization to trace the temperature dependencies of key intermediates, including many hydroperoxides. In the absence of ozone, reactivity is observed in the so-called low-temperature chemistry (LTC) regime between 550 and 700 K, which is governed by hydroperoxides formed from sequential O2 addition and isomerization reactions. At temperatures above 700 K, we observed the negative temperature coefficient (NTC) regime, in which the reactivity decreases with increasing temperatures, until near 800 K, where the reactivity increases again. Upon addition of ozone (1000 ppm), the overall reactivity of the system is dramatically changed due to the time scale of ozone decomposition in comparison to fuel oxidation time scales of the mixtures at different temperatures. While the LTC regime seems to be only slightly affected by the addition of ozone with respect to the identity and quantity of the observed intermediates, we observed an increased reactivity in the intermediate NTC temperature range. Furthermore, we observed experimental evidence for an additional oxidation regime in the range near 500 K, herein referred to as the extreme low-temperature chemistry (ELTC) regime. Experimental evidence and theoretical rate constant calculations indicate that this ELTC regime is likely to be initiated by H abstraction from methyl hexanoate via O atoms, which originate from thermal O3 decomposition. The theoretical calculations show that the rate constants for methyl ester initiation via abstraction by O atoms increase dramatically with the size of the methyl ester, suggesting that ELTC is likely not important for the smaller methyl esters. Experimental evidence is provided indicating that, similar to the LTC regime, the chemistry in the ELTC regime is dominated by hydroperoxide chemistry. However, mass spectra recorded at various reactor temperatures and at different photon energies provide experimental evidence of some differences in chemical species between the ELTC and the LTC temperature ranges.

An experimental and kinetic modeling study of gas-phase autoignition of n-Pentadecane at low-to-high temperatures and elevated pressures

In this study, low-to-high temperature oxidation of n-pentadecane (nC15H32) is investigated in a rapid compression machine and a heated shock tube. The experiments are conducted at equivalence ratios of Φ = 0.5–2.0 with air as an oxidizer for the fuel-lean condition while diluted fuel mixtures for other equivalence ratios. A temperature range of 650–1450 K is investigated at a pressure of 6 and 10 bar in a rapid compression machine and a heated shock tube while a temperature range of 900–1350 K is investigated at a pressure of 15 bar in a heated shock tube. The fuel showed a two-stage ignition behavior which is a typical characteristic of large hydrocarbons and a negative temperature coefficient regime. The dependence of ignition delay times on pressure, equivalence ratio, and oxygen mole fraction are separately presented and discussed. The experimental results revealed the sensitivity of ignition delay times to all these factors. The available experimental data of C10-C16 n-alkanes are compared which showed a small effect of chain length on the oxidation of alkanes. An updated reaction mechanism is presented after revising the rate constants of various reaction classes. The kinetic modeling predictions are compared and noticeable improvements are observed in the performance of the updated mechanism especially at low temperatures. The flux analysis is carried out to observe the fuel consumption along major low-temperature pathways. The sensitivity analysis is then performed to analyze the performance of the updated mechanism. To our knowledge, this is the first study on the autoignition of n-pentadecane.

Role of low-temperature oxidation in non-uniform end-gas autoignition and strong pressure wave generation

This study highlights the importance of heat release rate in low-temperature oxidation (LTO) on non-uniform end-gas autoignition and strong pressure wave generation, which are substantially relevant to knocking combustion. The simulations are conducted using the compressible Navier–Stokes equations with detailed transport and chemical kinetics models in a one-dimensional constant-volume reactor. Four fuel/air stoichiometric mixtures, n-butane, i-octane, n-heptane, and dimethyl ether (DME)/air mixtures, are simulated. The results show that larger knocking intensities are produced with n-heptane and DME in their negative temperature coefficient (NTC) regimes because of the stronger non-uniformity of end-gas autoignition. The non-uniformity of end-gas autoignition is enhanced by a pressure wave disturbance that is caused by the rapid temperature rise of the end-gas region in LTO. In particular, the high heat release rate with the DME/air mixture generates a distinct pressure wave disturbance in the reactor, which considerably enhances the non-uniformity of end-gas autoignition through the reflection of the wave at the wall. In contrast, the heat release rate in the n-heptane case is milder than that in the DME case, and therefore, the knocking intensity in the n-heptane case is smaller compared to that of DME due to less enhancement of the non-uniform end-gas autoignition. No large knocking intensities are produced with n-butane and i-octane, which have weak NTC, because of the absence of a temperature rise in LTO. Thus, this study concludes that the high heat release rate in LTO and the generated pressure wave disturbance play a significant role in the generation of large knocking intensities through the enhancement of non-uniform end-gas autoignition.

Studying the influence of single droplets on fuel/air ignition in a high-pressure shock tube.

The interaction of fuel and lubricant droplets with gaseous fuel/air mixtures close to autoignition is relevant in the context of unwanted early autoignition in spark-ignition internal combustion (IC) engines. To study the influence of droplets on the ignition of fuel/air mixtures independent from the in-cylinder pressure/temperature history, the shock-tube technique in combination with an injection system was established, which enables the generation and injection of single droplets or droplet clusters of n-dodecane and lubricant base oil behind reflected shock waves at pressures and temperatures representative for the compression phase of IC engines. Injected droplets were imaged by high-repetition-rate laser-induced fluorescence. The ignition process was observed by imaging in the visible and UV simultaneously through the shock-tube end wall with a combination of color- and UV-sensitive high-repetition-rate cameras. It was found that the amount and composition of the injected liquid are important factors determining the extent of the interference with the ongoing autoignition of the premixed fuel/air bath gas. For a stoichiometric mixture of primary reference fuels (PRF95) in air, the droplets significantly accelerate ignition especially in the negative temperature coefficient regime at around 760 K. The comparison of the timing of local ignition and the occurrence of volumetric ignition indicates that only in cases where the surrounding gas is close to autoignition, the droplets can trigger early autoignition. This required temporal and spatial coincidence might explain the high level of randomness of early autoignition in engines.

Decreased mixture reactivity and hot flame speed in the products of diffusion-affected autoignitive cool flames in the NTC regime

Cool flames propagating in autoignitive mixtures may be characterized as deflagrations or spontaneous ignition fronts depending on the relative importance of diffusion. In this paper, it is shown that, for certain thermochemical conditions in the negative temperature coefficient (NTC) regime, including at the Engine Combustion Network’s (ECN’s) baseline Spray A conditions, the cool flame products’ reactivity and hot flame speed can vary significantly from one cool flame propagation regime to the other. Simulations of steady one-dimensional cool flames in fixed-length inflow-outflow domains are performed. By varying the inflow velocity and controlling accordingly the domain length, isolated cool flames ranging from spontaneous ignition fronts to deflagrations are obtained. Towards the deflagration regime, the increasingly important contribution from diffusion (mostly heat conduction) promotes intermediate or high temperature fuel oxidation channels at the expense of low-temperature chain branching. As a result, the cool-flame products’ composition and temperature are significantly affected, with the product-side’s mixture reactivity and hot flame speed significantly reduced. Qualitatively similar results obtained with four chemical kinetics mechanisms and two transport models (mixture-averaged and unity Lewis number) are presented. More specifically, in a lean n-heptane–air mixture (equivalence ratio of 0.7) at 650 K and 1 atm, the time to second stage ignition is increased by a factor of up to 6 following a cool flame deflagration as opposed to a spontaneous ignition. The peak heat release rate is also reduced by a factor of more than five. With n-dodecane–oxidizer mixtures (equivalence ratios of 0.7 to 1.3) at the ECN’s baseline Spray A conditions, the role of diffusion on cool-flame products is observed to increase the remaining time to second stage ignition by a factor of up to 2.5, reduce hot flame speed by up to 30% and decrease peak heat release rate by a factor of up to five. These effects are shown to lead to a significant alteration of the double cool-hot flame ignition and stabilization. This is in part due to the fact that the cool flames are found to be as fast, and faster than hot flames at these conditions, such that a deflagrative cool flame can play a significant role on both ignition and flame stabilization. Finally, it is found that the effect of diffusion on chemical pathways and peak heat release rate can be even more significant at the baseline Spray A conditions in rich mixtures beyond the NTC regime.