Combination of LII and extinction measurements for determination of soot volume fraction and estimation of soot maturity in non-premixed laminar flames

The measurement of soot and soot precursors is important for understanding the formation of soot particles in flames. In this paper, we use the difference between laser-induced incandescence (LII) and two-dimensional extinction measurements to assess the contribution of soot precursors to the extinction measurement. LII measurements are performed with a high spatial resolution of 100 µm to determine the soot volume fraction (f _V) in a laminar ethylene/air non-premixed flame at the standard Gülder conditions. While LII is specific to mature soot only, the extinction data represent attenuation due to mature and young soot (absorption and elastic scattering) and also absorption by soot precursors. The difference between the two measurements indicates the contribution of soot precursors and allows a determination of the maturity of soot. This is important knowledge for those using extinction techniques to measure soot concentration, as the contribution from soot precursors may lead to an overestimation of the mature soot concentration. Further, regions with high soot-precursor concentrations, which lead to soot formation, can be identified.     

High-Modulus Wholly Aromatic Fibers. II. Partially Ordered Polyamide-Hydrazides

Partially ordered polyarnide-hydrazides were produced by the poly condensation of diacid chlorides with aminobenz-hydrazides, the order that results being a consequence of the considerably more rapid reaction of a diacid chloride with the hydrazide group in competition with the aromatic amine group of the aminobenzhydrazide. Fibers were produced from a series of such polymers containing from 50 mole % meta-oriented phenylene rings to 100 mole % para-oriented ones. Fiber from the wholly para-oriented type of polymer exhibited very high strength and modulus: 12.5 and 468 g/den, respectively, at 4.3% elongation-to-break. Although the crystallinity and density observed for hot-drawn fibers of partially ordered completely para-oriented polyarnide-hydrazides were comparable to the crystallinity and density of fibers of the isomeric wholly ordered polymer, the partially ordered polymers were more readily spun to the ultra-high strength and high modulus type fibers, probably because their greater solubility made them easier to spin.     

High-Modulus Wholly Aromatic Fibers. I. Wholly Ordered Polyamide-Hydrazides and Poly-1,3,4-oxadiazole—Amides

Several completely ordered polyamide-hydrazide copolymers were prepared via low temperature poly condensation of aromatic diacid chlorides with symmetrical aromatic diamines containing preformed dihydrazide linkages. Highly crystalline, hot-drawn fibers of the polyamide-hydrazide containing only para-oriented phenylene units showed unusually high strength and exceptionally high initial modulus: 10.8 and 508 g/den, respectively, at 2.9% elongation-to-break. The as-spun fibers also exhibited rather high tensile strength and unusually high initial modulus: 8.2 and 291 g/den, respectively, at 9.4% elongation-to-break. The hot-drawn fiber retained considerable strength at elevated temperatures, exhibiting a tenacity of 1.4 g/den and an initial modulus of 169 g/den at 350°C. Heat-aging of the as-spun fiber at 185°C in air showed that 66% of the original tenacity, 41% of the elongation, and 86% of the modulus were retained even after 336 hr. Substitution of as little as 25 mole % meta-oriented phenylene rings for para-oriented ones resulted in loss of the ultra-high strength and modulus, giving tensile properties comparable to those of fibers from wholly aromatic polyamides of the meta-oriented type. Fibers from the polyamide-hydrazides containing 50 mole % meta-oriented rings showed similar properties. Although ordered oxadiazole-amide copolymers were obtained from diamines containing two preformed oxadiazole linkages separated by m-phenylene rings, fibers could not be spun from them. Fiber of an ordered oxadiazole-amide copolymer was obtained, however, by heat treatment of the wholly p-phenylene ordered poly amide-hydrazide copolymer precursor fiber. Such a fiber exhibited a tenacity of 15.3 g/den, 3.6% elongation-to-break, and 564 g/den initial modulus.     

Influence of polydisperse distributions of both primary particle and aggregate size on soot temperature in low-fluence LII

An improved aggregate-based low-fluence laser-induced incandescence (LII) model has been developed. The shielding effect in heat conduction between aggregated soot particles and the surrounding gas was modeled using the concept of the equivalent heat transfer sphere. The diameter of such an equivalent sphere was determined from direct simulation Monte Carlo calculations in the free molecular regime as functions of the aggregate size and the thermal accommodation coefficient of soot. Both the primary soot particle diameter and the aggregate size distributions are assumed to be lognormal. The effective temperature of a soot particle ensemble containing different primary particle diameters and aggregate sizes in the laser probe volume was calculated based on the ratio of the total thermal radiation intensities of soot particles at 400 and 780 nm to simulate the experimentally measured soot particle temperature using two-color optical pyrometry. The effect of primary particle diameter polydispersity is in general important and should be considered. The effect of aggregate size polydispersity is relatively unimportant when the heat conduction between the primary particles and the surrounding gas takes place in the free-molecular regime; however, it starts to become important when the heat conduction process occurs in the near transition regime. The model developed in this study was also applied to the re-determination of the thermal accommodation coefficient of soot in an atmospheric pressure laminar ethylene diffusion flame. PACS 44.05.+e; 61.46.Df; 65.80.+n     

The concept of 2D gated imaging for particle sizing in a laminar diffusion flame

In this work, time-resolved laser-induced incandescence (TiRe LII) has been employed to measure primary particle diameters of soot in an atmospheric laminar ethylene diffusion flame. The generated data set complements existing data determined in one single location and takes advantage of the good spatial resolution of the ICCD detection. Time resolution is achieved by shifting the camera gate along the LII decay. One key input parameter for the analysis of time-resolved LII is the local flame temperature. This was determined on a grid throughout the flame by coherent anti-Stokes Raman scattering. The accurate temperature data, in combination with other published data from this flame, are well suited for soot model validation purposes while we showed feasibility of a shifted gate approach to deduce 2D particle sizes in the chosen standard flame.     

Highly luminescent europium(III) complexes with naphtoiltrifluoroacetone and dimethyl sulphoxide

The synthesis, luminescence properties, experimental determination and theoretical calculation of the emission quantum yield of Eu(NTA)₃.2L complexes, where NTA is naphtoiltri-fluroacetone and L denotes H₂O or DMSO (dimethyl sulphoxide), were reported. The compounds were characterized by elemental analysis (carbon, hydrogen and europium), thermal analysis, UV-visible absorption and photoluminescence spectroscopies. The experimental quantum yields were determined based on a method previously proposed by Bril and collaborators. The Eu(NTA)₃.2DMSO compound shows a high value for the Ω₂ intensity parameter (35.8 × 10^?20 cm²), reflecting the hypersensitive nature of the ⁵D₀ → ⁷F₂ transition and indicating that the lanthanide ion is in a highly polarizable chemical environment. The experimental quantum yield measured for that compound, 0.75, is one of the highest so far reported for solid-state europium complexes. The theoretical calculations of the quantum yield were carried out by solving an appropriate set of rate equations and by using empirical spectroscopic parameters and energy transfer rates. The theoretical results agree well with the experimental data for both complexes. The photostability of Eu(NTA)₃.2DMSO at 358K was evaluated in order to verify whether this complex can be applied as a phosphor for blue light emitting devices.     

Spectrally resolved light absorption properties of cooled soot from?a?methane flame

The optical properties of combustion-generated soot, crucial information for quantitative soot emission diagnostics and for climate modeling, have been determined for the particular case of cooled soot from a methane flame. Optical extinction measurements were performed over a wavelength range of 450–750 nm using a novel diffuse-light, spectrally resolved line-of-sight attenuation experiment, and quantified using extractive methods coupled with scanning and transmission electron microscopy in conjunction with a detailed uncertainty analysis. The absorption component of the total measured extinction was isolated by calculating the expected scattering contribution, according to the Rayleigh–Debye–Gans approximation for polydisperse fractal aggregates. In contrast to the large degree of scatter seen in data previously reported in the literature, a consistent trend of negligible variation of the soot absorption refractive index function E(m) with wavelength over the visible was observed (E(m)=0.35±0.03 at wavelengths of 450–750 nm). These new data are also cast in the form of dimensionless extinction, which is independent of the scatter correction, as well as mass absorption cross section, which is independent of the mass density of soot and is commonly used by atmospheric modelers.     

Sensitivity and relative error analyses of soot temperature and volume fraction determined by two-color LII

The sensitivity and relative sensitivity of soot temperature and soot volume fraction inferred from the two-color laser-induced incandescence technique to different variables were systematically investigated to quantitatively understand how the detection wavelengths affect the behavior of the detection system. The effects of signal shot noises on the derived soot temperature and soot volume fraction were also analyzed. The detection wavelengths are in general between about 400 nm for the lower band and near infrared for the upper one. Numerical calculations were conducted for seven detection wavelength selections commonly used in two-color laser-induced incandescence experiments reported in the literature. To achieve a better accuracy for soot temperature and volume fraction measurements, it is desirable to use a shorter lower detection wavelength and a longer upper detection wavelength in the spectral range of about 400 nm to near infrared. The lower detection wavelength has a stronger impact on the detection system performance than the upper one. The sensitivity and shot noise analyses are valuable tools to assess the relative performance of different detection wavelengths and should be used in combination with other considerations to design an optimal detection system in a two-color laser-induced incandescence experiment.     

Determining aerosol particle size distributions using time-resolved laser-induced incandescence

The particle size distribution within an aerosol containing refractory nanoparticles can be inferred using time-resolved laser-induced incandescence (TR-LII). In this procedure, a small volume of aerosol is heated to incandescent temperatures by a short laser pulse, and the incandescence of the aerosol particles is then measured as they return to the ambient gas temperature by conduction heat transfer. Although the cooling rate of an individual particle depends on its volume-to-area ratio, recovering the particle size distribution from the observed temporal decay of the LII signal is complicated by the fact that the LII signal is due to the incandescence of all particle size classes within the sample volume, and because of this, the particle size distribution is related to the time-resolved LII signal through a mathematically ill-posed equation. This paper reviews techniques proposed in the literature for recovering particle size distributions from TR-LII data. The characteristics of this problem are then discussed in detail, with a focus on the effect of ill-posedness on the stability and uniqueness of the recovered particle size distributions. Finally, the performance of each method is evaluated and compared based on the results of a perturbation analysis. PACS  44.05.+e; 47.70.Pq; 78.70.-g; 65.80.+n; 78.20.Ci