Lube oil chemistry influences on autoignition as measured in an ignition quality tester

Derived Cetane Numbers (DCNs) of engine lubricating oil/multicomponent 95 Research Octane Number (RON) gasoline surrogate mixtures were measured in an Ignition Quality Tester (IQT). Measurements separately assess the effects of calcium- and magnesium-based detergent additive fraction, oil viscosity, oil degradation, and base oil classification on mixture ignition propensity at conditions with relevance to low speed pre-ignition (LSPI) in gasoline engines. Testing of 0–25% (by mass) oil blended into a six-component surrogate mixture representing an unleaded “average” European gasoline blend is used to determine sensitivity of DCN responses to variations in the properties. With one exception, mixture DCNs were found to increase with lubricating oil content. Despite variation in calcium and magnesium concentrations, DCN responses for all oil blends indicate no statistically significant effect of either calcium or magnesium. Similarly, neither aging of nor peroxide addition to the oil yields significant DCN changes compared to untreated oils. However, a distinct response is found for variations in the base lubricant chemical structural properties. At 25% oil blending with gasoline surrogate, the measured DCNs (RONs) of different group base oils range from 19.6 (95.7) to 42.1 (46.2). The DCN increases with increasing base oil API Group Number (I through IV); however, mixture DCN was found to decrease for a 25% blend of Group V-B with the gasoline surrogate. Using quantitative ¹H NMR, the Group Number trend is interpreted to be a consequence of linear vs. branched character of the paraffinic base oil composition. Taken together, the present results indicate that at ASTM D6890 DCN test conditions, there is no significant ignition effect attributable to reasonable variations in the lubricant's calcium or magnesium content, viscosity, or degree of degradation. Instead, the isomeric character of the paraffinic base oil appears to be most significant in controlling lubricant autoignition properties relative to those of gasolines.     

Isolation of22Na for intense positron sources

A method of removing²²Na from Al via distillation is investigated. Distillation is rapid (≈10 minutes) and nearly quantitative. When the distilled vapor is directed by a flow of He gas the deposit may be localized fairly well and easily recovered with water.     

Ignition of non-premixed counterflow flames of octane and decane isomers

Ignition temperatures of non-premixed flames of octane and decane isomers were determined in the counterflow configuration at atmospheric pressure, a free-stream fuel/N₂ mixture temperature of 401 K, a local strain rate of 130 s^?1, and fuel mole fractions ranging from 1% to 6%. The experiments were modeled using detailed chemical kinetic mechanisms for all isomers that were combined with established H₂, CO, and n-alkane models, and close agreements were found for all flames considered. The results confirmed that increasing the degree of branching lowers the ignition propensity. On the other hand, increasing the straight chain length by two carbons was found to have no measurable effect on flame ignition for symmetric branched fuel structures. Detailed sensitivity analyses showed that flame ignition is sensitive primarily to the H₂/CO and C₁–C₃ hydrocarbon kinetics for low degrees of branching, and to fuel-related reactions for the more branched molecules.     

Elucidating NO coupling effects on ignition of toluene reference fuels by chemical functional group analysis

Derived cetane number (DCN), Research and Motor Octane Numbers (RON and MON) have been fundamentally analyzed using Quantitative Structure-Property Relationship (QSPR) regression models with key chemical functional groups. Both RON and MON exhibit strong sensitivities to the abundances of (CH₂)_n and benzyl-type groups but lack sensitivity to the CH₃ group, most dominant in real gasolines. Residual and EGR gases contain NO_x known to synergize with fuel autoignition chemistry. Two TRF mixtures having high and low aromatic content but sharing the same RON and MON values were used to evaluate NO_x coupling effects. DCN measurements with NO addition were found to be strongly correlated with the abundance of the (CH₂)_n group. Similar experiments of 200 ppm NO in a Rapid Compression Machine show promotion (inhibition) of ignition for the high (low) aromatic TRF fuel. Kinetic modeling attributes the promotion to the NONO₂ interconversion reactions, NO + HO₂ = NO₂ + OH, CH₃ + NO₂ = CH₃O + NO and NO₂ + H = NO + OH. The inhibitive effect relates specifically to low temperature kinetics and high NO loading conditions, leading to the formation of meta-stable species (e.g. CH₃ + NO₂ (+M) = CH₃NO₂ (+M)) that decelerate the rate of conversion of HO₂ to more reactive OH radicals. The coupling of NO with real gasolines depends on chemical composition and temperature conditions not only encompassed by RON and MON criteria, but by the chemical functional group characteristics. The relevance of this finding to the significance of preferential vaporization of multi-component gasolines on low-speed pre-ignition (LSPI) is discussed. Within the context of chemical functional group distributions of five distillation cuts of a marketed ethanol-free gasoline determined by NMR spectroscopy, the analyses identify considerable variations of key functionalities with fuel distillation properties, indicating chemical kinetic autoignition behaviors that are dependent on preferential vaporization.     

Magneto-optical activity of crude oil and its heavy fractions

We have experimentally studied optical and magneto-optical spectra of solutions of crude oils of different origin and their heavy fractions in the visible spectral range. Magnetic circular dichroism of oil in the wavelength range ??550 nm has been revealed. We show that the shape of the spectra of this dichroism depends on the origin of crude oil, with the magnetic dichroism magnitude being proportional to the concentration of the oil in the solution. A comparison of the data of magneto-optical spectroscopy with electron paramagnetic resonance spectra and chemical composition of samples has allowed us to conclude that the observed magneto-optical activity is determined by the occurrence of VO²⁺ complexes in the oil samples. The revealed magneto-optical activity of crude oil can form the basis of a unique method of analysis of the composition and properties of oils of different origin and heavy fractions thereof.     

Ignition of non-premixed cyclohexane and mono-alkylated cyclohexane flames

Ignition temperatures of non-premixed cyclohexane, methylcyclohexane, ethylcyclohexane, n-propylcyclohexane, and n-butylcyclohexane flames were measured in the counterflow configuration at atmospheric pressure, a free-stream fuel/N₂ mixture temperature of 373 K, a local strain rate of 120 s^?1, and fuel mole fractions ranging from 1% to 10%. Using the recently developed JetSurf 2.0 kinetic model, satisfactory predictions were found for cyclohexane, methyl-, ethyl-, and n-propyl-cyclohexane flames, but the n-butylcyclohexane data were overpredicted by 20 K. The results showed that cyclohexane flames exhibit the highest ignition propensity among all mono-alkylated cyclohexanes and n-hexane due to its higher reactivity and larger diffusivity. The size of mono-alkyl group chain was determined to have no measurable effect on ignition, which is a result of competition between fuel reactivity and diffusivity. Detailed sensitivity analyses showed that flame ignition is sensitive primarily to fuel diffusion and also to H₂/CO and C₁–C₃ hydrocarbon kinetics.     

A multi-step reaction model for ignition of fully-dense Al-CuO nanocomposite powders

A multi-step reaction model is developed to describe heterogeneous processes occurring upon heating of an Al-CuO nanocomposite material prepared by arrested reactive milling. The reaction model couples a previously derived Cabrera-Mott oxidation mechanism describing initial, low temperature processes and an aluminium oxidation model including formation of different alumina polymorphs at increased film thicknesses and higher temperatures. The reaction model is tuned using traces measured by differential scanning calorimetry. Ignition is studied for thin powder layers and individual particles using respectively the heated filament (heating rates of 10³–10⁴ K s^?1) and laser ignition (heating rate ～10⁶ K s^?1) experiments. The developed heterogeneous reaction model predicts a sharp temperature increase, which can be associated with ignition when the laser power approaches the experimental ignition threshold. In experiments, particles ignited by the laser beam are observed to explode, indicating a substantial gas release accompanying ignition. For the heated filament experiments, the model predicts exothermic reactions at the temperatures, at which ignition is observed experimentally; however, strong thermal contact between the metal filament and powder prevents the model from predicting the thermal runaway. It is suggested that oxygen gas release from decomposing CuO, as observed from particles exploding upon ignition in the laser beam, disrupts the thermal contact of the powder and filament; this phenomenon must be included in the filament ignition model to enable prediction of the temperature runaway.     

Cavitation based cleaner technologies for biodiesel production and processing of hydrocarbon streams: A perspective on key fundamentals,missing process data and economic feasibility – A review

The present review emphasizes the role of hydrodynamic cavitation (HC) and acoustic cavitation in clean and green technologies for selected fuels (of hydrocarbon origins such as gasoline, naphtha, diesel, heavy oil, and crude oil) processing applications including biodiesel production. Herein, the role of cavitation reactors, their geometrical parameters, physicochemical properties of liquid media, liquid oxidants, catalyst loading, reactive oxygen species, and different types of emulsification and formation of radicals, formation as well as extraction of formed by-products are systematically reviewed. Among all types of HC reactors, vortex diode and single hole orifices revealed more than 95 % desulfurization yield and a 20 % viscosity reduction in heavy oil upgrading, while multi-hole orifice (100 holes) and slit Venturi allowed obtaining the best biodiesel production processes in terms of high (%) yield, low cost of treatment, and short processing time (5 min; 99 % biodiesel; 4.80 USD/m³). On the other hand, the acoustic cavitation devices are likely to be the most effective in biodiesel production based on ultrasonic bath (90 min; 95 %; 6.7 $/m³) and desulfurization treatment based on ultrasonic transducers (15 min; 98.3 % desulfurization; 10.8 $/m³). The implementation of HC-based processes reveals to be the most cost-effective method over acoustic cavitation-based devices. Finally, by reviewing the ongoing applications and development works, the limitations and challenges for further research are addressed emphasizing the cleaner production and guidelines for future scientists to assure obtaining comprehensive data useful for the research community.     

A new deterministic complex network model with hierarchical structure

We introduce a new simple pseudo tree-like network model, deterministic complex network (DCN). The proposed DCN model may simulate the hierarchical structure nature of real networks appropriately and have the unique property of ‘skipping the levels’, which is ubiquitous in social networks. Our results indicate that the DCN model has a rather small average path length and large clustering coefficient, leading to the small-world effect. Strikingly, our DCN model obeys a discrete power-law degree distribution P(k)∝k^−γ, with exponent γ approaching 1.0. We also discover that the relationship between the clustering coefficient and degree follows the scaling law C(k)∼k⁻¹, which quantitatively determines the DCN's hierarchical structure.     

近红外原油快速评价技术预测常减压蒸馏装置侧线收率

常减压蒸馏装置侧线收率对于装置操作优化具有重要的实际意义,但缺乏可靠的预测方法。在近红外原油快速评价技术基础上,结合H/CAMS软件,建立了常减压侧线收率的有效预测方法。首先建立近红外光谱快速测定原油实沸点蒸馏收率的方法,在市售原油光谱数据库的基础上,添加广西石化常炼原油品种,采用拓扑法建立分析模型,验证结果表明,近红外分析方法预测的实沸点蒸馏收率与实际测定结果基本吻合。进一步通过H/CAMS软件将近红外原油快速评价技术得到的实沸点蒸馏收率转换为常减压蒸馏装置的侧线收率。将该方法得到的常减压装置石脑油、柴油、蜡油和渣油收率与炼厂生产报表中各个侧线的收率数据进行对比,7个月的对比数据表明,近红外原油快速评价技术预测的各个侧线生产收率能够反应实际生产收率的变化趋势。基于近红外分析方法预测常减压蒸馏装置侧线收率分析速度快,结果可靠,容易实现在线操作,可以为炼厂计划优化、原油调合等过程提供基础数据。     

Numerical study of the effect of gas flow in low pressure inductively coupled Ar/N<Subscript>2</Subscript> plasmas

The effect of gas flow in low pressure inductively coupled Ar/N₂ plasmas operating at the rf frequency of 13.56 MHz and the total gas pressure of 20 mTorr is studied at the gas flows of 5–700 sccm by coupling the plasma simulation with the calculation of flow dynamics. The gas temperature is 300 K and input power is 300 W. The Ar fractions are varied from 0% to 95%. The species taken into account include electrons, Ar atoms and their excited levels, N₂ molecules and their seven different excited levels, N atoms, and Ar⁺, N⁺, N₂ ⁺, N₄ ⁺ ions. 51 chemical reactions are considered. It is found that the electron densities increase and electron temperatures decrease with a rise in gas flow rate for the different Ar fractions. The densities of all the plasma species for the different Ar fractions and gas flow rates are obtained. The collisional power losses in plasma discharges are presented and the effect of gas flow is investigated.     

Ignition delay of fatty acid methyl ester fuel droplets: Microgravity experiments and detailed numerical modeling

Recent optical engine studies have linked increases in NO_x emissions from fatty acid methyl ester combustion to differences in the premixed autoignition zone of the diesel fuel jet. In this study, ignition of single, isolated liquid droplets in quiescent, high temperature air was considered as a means of gaining insight into the transient, partially premixed ignition conditions that exist in the autoignition zone of a fatty acid methyl ester fuel jet. Normal gravity and microgravity (10⁻⁴ m/s²) droplet ignition delay experiments were conducted by use of a variety of neat methyl esters and commercial soy methyl ester. Droplet ignition experiments were chosen because spherically symmetric droplet combustion represents the simplest two-phase, time-dependent chemically reacting flow system permitting a numerical solution with complex physical submodels. To create spherically symmetric conditions for direct comparison with a detailed numerical model, experiments were conducted in microgravity by use of a 1.1 s drop tower. In the experiments, droplets were grown and deployed onto 14 μm silicon carbide fibers and injected into a tube furnace containing atmospheric pressure air at temperatures up to 1300 K. The ignition event was characterized by measurement of UV emission from hydroxyl radical (OH*) chemiluminescence. The experimental results were compared against predictions from a time-dependent, spherically symmetric droplet combustion simulation with detailed gas phase chemical kinetics, spectrally resolved radiative heat transfer and multi-component transport. By use of a skeletal chemical kinetic mechanism (125 species, 713 reactions), the computed ignition delay period for methyl decanoate (C₁₁H₂₂O₂) showed excellent agreement with experimental results at furnace temperatures greater than 1200 K.     

Initiation of Gas Discharges in Plasma Displays Assisted by Electron Emission of Thin Insulators

At present many efforts are done for the development of colour plasma displays (PD). One main problem is to secure a reliable ignition, provided by a suitable concentration of starting particles in the discharge cells (priming). In this paper a new priming method is proposed using the exoelectron emission (EEE) of thin insulators. The influence of the EEE on the ignition behaviour of ac PD cells is investigated and compared with direct measurements of the afteremission of MgO, Al₂O₃ and MgAl₂O₄. Auger electron spectroscopy (AES), residual gas mass spectra and Ar⁺ etching are additionally used methods.     

Influence of ignition condition on the growth of silicon thin films using plasma enhanced chemical vapour deposition

The influences of the plasma ignition condition in plasma enhanced chemical vapour deposition (PECVD) on the interfaces and the microstructures of hydrogenated microcrystalline Si (μc-Si:H) thin films are investigated. The plasma ignition condition is modified by varying the ratio of SiH₄ to H₂ (R_H). For plasma ignited with a constant gas ratio, the time-resolved optical emission spectroscopy presents a low value of the emission intensity ratio of Hα to SiH^* (I_Hα/I_SiH^*) at the initial stage, which leads to a thick amorphous incubation layer. For the ignition condition with a profiling R_H, the higher I_Hα/I_SiH^* values are realized. By optimizing the R_H modulation, a uniform crystallinity along the growth direction and a denser μ c-Si:H film can be obtained. However, an excessively high I_Hα/I_SiH^* may damage the interface properties, which is indicated by capacitance-voltage (C-V) measurements. Well controlling the ignition condition is critically important for the applications of Si thin films.     

Isotope-analytical results of a study of gas generation in L/ILW

The paper presents the results of a long-term measurement series using hermetic containers to make more precise quantitative estimation of the generation rates and radioactivity of the gas in a drum of low and intermediate level radioactive waste (L/ILW) packages. Development of special preparation lines and isotope-analytical measurements of the headspace gas samples were performed in the ATOMKI. Stable isotope measurements were executed from the CO₂ and CH₄ fractions by stable isotope ratio mass spectrometer. Noble gas (He) measurements were done by noble gas mass spectrometer. The tritium content of the vapour, H₂ and CH₄ fractions was measured in H₂O chemical form by a low background liquid scintillation counter. The ¹⁴C content of the CO₂ and CH₄ fractions of the headspace gas samples was measured by a low background gas proportional counter system.     

Theoretical integrated intensities for the 2ν2 and 2ν2-ν2 bands of HCN and DCN

Dipole moment functions, both perpendicular and parallel to the molecular axis, are calculated from the SCF and MRD-CI results of a previous study for the normal ν₂ bending vibrations of HCN and DCN. Vibrationally averaged dipole moments and the infrared transition matrix elements are then obtained from the dipole moment functions and vibrational wave functions. MRD-CI results, with known experimental values in parentheses, for HCN are 〈0|μ|0〉 = ?2.954(?2.985) D, 〈1|μ|1〉 = ?2.915(±2.942) D, 〈0|μ|1〉 = 0.148(0.147) D, 〈0|μ|2〉 = ?0.027 D, 〈1|μ|2〉 = 0.210 D. Calculated absolute intensities at 1 atm and 0°C for the (02⁰0) ← (000), (02⁰0) ← (010), and (02²0) ← (010) bands of HCN are 25 (40 ± 10 as estimated from spectra), 8.5, and 17.0 atm^?1 cm^?2, respectively. Results for DCN are also reported.     

Laser spark ignition of a jet diffusion flame

In this work we report preliminary results on the laser ignition of a jet diffusion flame with jet flow rates ranging from 35 (Re=1086) to 103 cm³/s (Re=3197). The laser spark energy of about 4 mJ was used for all the tests. The relative amounts of fuel and air concentrations at the laser focus have been estimated using a variant of laser-induced breakdown spectroscopy. The ignition and the flame blow out times were measured using the time-resolved OH emission. Ignition times in the range from 3 to about 10 ms were observed depending on the experimental conditions and they increased towards the rich as well as the lean sides. The early time and late-time OH emissions indicate that chemical reactions during the initial stage of the blast wave expansion are not immediately responsible for the ignition. The ultimate fate of an ignition depends on the reactions at later times which determines whether the gas could undergo a transition from hot plasma to a propagating flame.     

Laser-triggered quasi-monoenergetic ion beams at a moderate intensity and pulse duration

Plasma produced by short laser pulses from thin homogeneous foils with light and heavy ions is capable of generating quasi-monoenergetic light ions. This happens for the tail of light ions near the front of heavy ions. It was found that this effect is well pronounced for a moderate laser intensity (～10¹⁸ W/cm²) and pulse duration (～1 ps) by using a 2D particle-in-cell simulation of the laser interaction with thin CD₂ foils. Quasi-monoenergetic deuterons form a jet from the rear side of the foil with the energy ～1 MeV. The conversion efficiency to these quasi-monoenergetic ions is 10^?3.