Multi-wavelength thermo-optical analysis (MW-TOA) and Raman spectroscopy are commonly used methods to study soot sampled on filters, in terms of carbon content, nanostructure, and absorption properties. In this work, these techniques were combined to study how these characteristic properties of soot change in premixed flames, 1) at various flame heights during soot maturation and 2) as a result of potassium addition to the fuel. It was found from MW-TOA that sampled soot showed decreasing organic carbon (OC) fraction and increasing elemental carbon (EC) fraction with flame height. During heat treatment, light absorption increased significantly in the immature sampled soot. Soot from all sampling heights reached similar MAC values at the end of the inert heating stage. In the immature soot, the initially high absorption & Aring;ngstr & ouml;m exponent (AAE) decreased significantly during heat treatment in MW-TOA due to evaporation of volatile OC and through carbonization, while in the mature soot the initially low AAE changed negligibly during heat treatment. Potassium (K) addition to the fuel/air-mixture resulted in lower soot absorption, lower EC fraction, a strong reduction of the nucleation size mode and a shift of the accumulation size mode toward smaller sizes. Despite the clear changes in soot properties from MW-TOA, Raman spectroscopic analysis showed relatively small differences with K addition.

In this study, Raman spectroscopy has been used to evaluate the evolution of the structural modification of soot during oxidation processes at various preset temperatures up to 700 °C. Two types of well-characterized mini-CAST soot, representing black soot and brown soot, were examined. The major difference between the signals from the two types of soot was the higher photoluminescence (PL) signal for brown soot compared with black soot, in addition to some variations in the first-order Raman signatures such as oxygenated groups and their evolutions during thermal oxidation treatment. An interesting observation was the increase in the PL signal for brown soot at increasing temperatures up to 150 °C probably due to the formation of small oxidized polycyclic aromatic hydrocarbon and defects, followed by a decrease in the PL signal until the soot was fully oxidized. We also demonstrated that brown soot is prone to oxidation in ex situ measurements, a factor that should be considered in the Raman analysis of soot.

Laser diagnostics has been one of the most powerful tools in advancing state-of-the-art combustion research over the last five decades. Prof. Marcus Aldén, one of the most well-known pioneers in this field, has contributed many influential original publications over more than 40 years of his research career. In this paper, we will review some selected contributions, with emphasis on optical techniques developed and applied by Marcus and the group in Lund under his leadership, which are expected to play important roles in facing the challenge of the transition to a carbon-neutral energy system.A brief biography of Marcus is presented in the introduction section, including a summary of his academic services and achievements. The following sections are organized into chapters on different well-recognized techniques, i.e., laser-induced fluorescence, Raman and Rayleigh scattering, thermographic phosphors, coherent anti-Stokes Raman spectroscopy, resonant four-wave mixing, and additional novel technical developments and approaches. The description often follows different categories, including technique development, activities using relatively mature techniques for studies of combustion phenomena, and applications of the most mature techniques in practical devices. The last part of the paper includes a short interview with Marcus for his comments, suggestions, and thoughts on the future challenges and opportunities in this field.This article, on the one hand, is an acknowledgment of the outstanding contribution of Marcus to the field of combustion research and, on the other hand, intends to provide a valuable review of laser diagnostics in combustion research.

Ex-situ Raman spectroscopy is a well-established method for the structural characterization of soot but necessitates a sampling step before analysis is made. This work studied the potential to perform Raman spectroscopic measurements of soot directly in the combustion exhaust gases, i.e., online Raman measurements. Two types of soot were produced from a Mini-CAST soot generator, one immature with high organic content and one mature with low organic content. Also, two different measurement configurations were used, a 90-degree and a backscattering configuration, as well as different polarization combinations of the laser radiation and the detected photons. Spectrally resolved Raman signals were successfully recorded and analyzed for the two soot types showing differences between the characteristic D and G peaks as well as the photoluminescence signal. Additionally, the Raman cross section was determined for both soot types and found to be higher for the immature soot. It was also found that a horizontally polarized laser excitation and a 90-degree collection angle had the best potential to reduce the interference from ambient gases. This study can be seen as a first step towards remote sensing of soot.

Light absorbing carbonaceous aerosols produced from combustion span over a range of physicochemical properties. Soot is the most recognized species in this category and its formation process involves gradual maturation from amorphous young soot with a high hydrogen-to-carbon-ratio toward mature soot aggregates. In this work, the optical response of a single particle soot photometer (SP2) to electrical mobility size selected soot of different maturity produced by a mini-CAST soot generator is investigated. The results show that for soot of a specific mobility diameter, the laser-induced incandescence (LII) signal appears earlier and with a higher LII peak height for increasing soot maturity. The experimental observations are supported by simulations using a numerical model for the LII process. Furthermore, the effect of systematically varying the SP2 laser power on the detection of soot of different maturity using LII is explored. This work can be seen as a step toward the aim of using the SP2 instrument to identify soot particles of different maturity in the atmosphere.

Optical properties of soot have been investigated with and without potassium chloride (KCl) salt added to the soot formation process in a premixed ethylene/air flame. A strong decrease in optical absorption efficiency of the soot was observed with increasing amounts of KCl added to the fuel based on the method of fluence curve analysis using laser-induced incandescence (LII). To understand the reason for this major change in absorption efficiency, probe sampling and subsequent structural analysis were performed using Raman spectroscopy and high-resolution transmission electron microscopy (HRTEM). Raman spectra indicated no significant difference between the nanostructure of soot from the two main cases; a reference case without addition of salt, and a case with addition of & SIM;600 ppm K. In the case of K addition, HRTEM showed slightly less compact nanostructure signified by somewhat shorter interlayer spacing, and significantly different polar ordering of carbon lamellae indicating smaller primary particles, thereby supporting previous TEM studies on soot sampled from the same flames showing smaller soot particle sizes with KCl addition. The impact on soot absorption properties from the observed differences is discussed. It is speculated that the main cause for the lower absorption with K addition is a quantum confinement effect due to reduction in soot particle size. & COPY; 2022 The Author(s). Published by Elsevier Inc. on behalf of The Combustion Institute. This is an open access article under the CC BY license ( http://creativecommons.org/licenses/by/4.0/ )

Online Raman scattering and in situ extinction measurement were combined in this work for qualitative and quantitative evaluations of various soot in the aerosol phase with different organic compounds.

Nephelometers are regularly used for air quality monitoring through scattering measurements of aerosols in the atmosphere. Less attention has been paid to the potential of estimating soot morphological parameters from nephelometer measurements in combination with scattering theory. In this work, we perform a fundamental laboratory study where an Ecotech Aurora 3000 nephelometer is used for measuring the scattering properties of soot with different characteristics. The nephelometer monitors the forward and backward scattering at three wavelengths (450 nm, 525 nm, and 635 nm) to retrieve information on the ratio of forward and backward scattering intensities, as well as the scattering wavelength dependence. An inverse scattering method, based on the Rayleigh-Debye-Gans theory, for determination of the equivalent fractal dimension (D-f) and radius of gyration (R-g) of soot particles from the experimental scattering data was developed. It is shown that the inverse method can estimate R-g and D-f when R-g < 185 nm and from the wavelength dependence, information on the relative amount of organic soot could be obtained. For validation, estimated parameters are compared with the morphological parameters of soot sampled from the mini-CAST soot generator and evaluated using transmission electron microscopy (TEM). Uncertainties and limitations of the procedure are discussed.

For accurate laser-induced incandescence (LII) measurements of soot properties it is of great importance to understand the nature of the physical processes involved during rapid laser heating. In this work, we investigate how well-characterized differently matured fresh soot from a soot generator responds to rapid laser heating. For this purpose, a double-pulse LII setup is used with 10 mu s time separation between the pulses using various combinations of two common LII wavelengths (532 and 1064 nm). Detection is performed at two wavelength bands for fluorescence analysis, and additionally elastic light scattering is used for mass loss analysis during heating. We investigate how the LII signal changes with pre-heating laser energy, specifically by fluence curve analysis to estimate the influence of thermal annealing, sublimation and laser-induced fluorescence interference. It is shown that extensive absorption enhancement occurs for all types of soot as the soot is thermally annealed, which is manifested through decreasing dispersion coefficient xi and an increasing absorption coefficient E(m,lambda). When comparing young and mature soot, a much larger impact of sublimation can be observed in the fluence curves of the mature soot. Also, we observe an enhanced contribution of laser-induced fluorescence for the young soot when performing LII measurements using 532 nm, which is suggested to originate from vaporized carbon fragments with an aromatic structure. This work further shows the potential of utilizing double-pulse arrangements for increasing the detectability of poorly absorbing soot, but also it highlights the impact of laser heating on soot, which may be important to avoid interferences when performing soot diagnostics.

Previous studies have shown that alkali salts influence combustion processes and soot formation, although the effects seem to vary across systems. Moreover, fundamental studies on the effect of potassium and sodium salts on formation of polycyclic aromatic hydrocarbons (PAH), which are precursors in soot formation, are scarce. Here, we report a study in which the effects on PAH formation due to the addition of alkali metal salts (KCl, KOH, K2CO3, NaCl and NaOH) to premixed ethylene–air flames were investigated. Different size classes of PAHs were probed using both spectral and 2D measurements of laser-induced fluorescence (PAH-LIF) using the excitation wavelengths 266 nm and 532 nm, while detecting the fluorescence emission at selected wavelength ranges. Elastic light scattering (ELS) measurements were also used to complement the fluorescence data. It was found that potassium and sodium salts do not significantly influence the formation of small PAHs (2–3 rings), while decreasing the concentration of larger PAHs at higher heights above burner (HAB). Another important result was that the anion in the salt (Cl−, OH−, CO32−) negligibly influences the PAH and soot formation processes after dissociation of the salts.

Previous studies have shown that addition of potassium chloride (KCl) reduces soot concentration and primary particle size. To improve the understanding of this phenomenon, this work focuses on investigating the influence of KCl addition on formation of polycyclic aromatic hydrocarbons (PAHs), assumed to be precursors of soot. The method used is laser-induced fluorescence (LIF), for which different size classes of PAHs can be probed using selected combinations of excitation and detection wavelengths. KCl solutions of different concentrations were aspirated into premixed ethylene-air flames, and spectral and 2D imaging PAH-LIF measurements were performed using laser excitation at 266 nm and 532 nm. PAHLIF spectra using 266 nm excitation showed a peak in the UV region at around 350 nm and a peak at around 550 nm in visible region, where the latter peak intensity increased strongly with flame height. The normalised PAH-LIF spectra obtained using 532 nm excitation showed no spectral change with flame height. The main results from this study showed that KCl addition, firstly, had negligible influence on the formation of smaller PAHs (measured using excitation at 266 nm and detection at similar to 320 nm), and secondly, decreased the formation of larger PAHs at increasing flame heights (measured using excitation at 532 nm and detection in the visible region). (c) 2021 The Author(s). Published by Elsevier Inc. on behalf of The Combustion Institute. This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ )

Laser-induced grating spectroscopy (LIGS) is for the first time explored in a configuration based on the crossing of two focused femtosecond (fs) laser pulses (800-nm wavelength) and a focused continuous-wave (cw) laser beam (532-nm wavelength). A thermal grating was formed by multi-photon absorption of the fs-laser pulses by [Formula: see text] with a pulse energy around 700 [Formula: see text]J ([Formula: see text] 45 TW/[Formula: see text]). The feasibility of this LIGS configuration was investigated for thermometry in heated nitrogen gas flows. The temperature was varied from room temperature up to 750 K, producing strong single-shot LIGS signals. A model based on the solution of the linearized hydrodynamic equations was used to extract temperature information from single-shot experimental data, and the results show excellent agreement with the thermocouple measurements. Furthermore, the fluorescence produced by the fs-laser pulses was investigated. This study indicates an 8-photon absorption pathway for [Formula: see text] in order to reach the [Formula: see text] state from the ground state, and 8 + 5 photon excitation to reach the [Formula: see text] state of the [Formula: see text] ion. At pulse energies higher than 1 mJ, the LIGS signal was disturbed due to the generation of plasma. Additionally, measurements in argon gas and air were performed, where the LIGS signal for argon shows lower intensity compared to air and [Formula: see text].

Constraining the climate impact of particulate brown carbon (BrC) will require identification of formation mechanisms and isolation of its different components to allow for source apportionment. For fresh combustion aerosols, the light absorption characteristics and the Absorption angstrom ngstrom Exponent (AAE) are principally controlled by the combustion conditions in which the particles formed and evolved. We investigated the influence of combustion temperatures on the BrC or black carbon (BC) emission characteristics for a miniCAST soot generator (propane fuel) and a modern heavy-duty diesel engine (petroleum diesel and two renewable diesel fuels). Changes in the AAE, mass spectral signatures, and thermal-optical characteristics were studied. We show that changing operating parameters to gradually reduce the combustion temperatures in these two fundamentally different combustion devices result in a regression from BC dominated to BrC dominated particle emissions. The regression toward BrC was associated with: (1) an increasing mass fraction of particulate non-refractory polycyclic aromatic hydrocarbons (PAHs), (2) an increasing fraction of refractory organic carbon, (3) more curved soot nanostructures and shorter fringe lengths, and (4) increased signal from (refractory) large carbon fragments in IR laser-vaporization aerosol mass spectra. Based on these results we argue that fresh BrC dominated combustion aerosols are attributed to primary emissions from low temperature combustion, highlighting the influence of refractory constituents and soot nanostructure. Higher temperatures favor the growth of conjugated polyaromatic structures in the soot, a progression hypothesized to control the evolution from BrC to BC character of the emitted aerosols.

This paper reports the first Computational Fluid Dynamics (CFD) model developed for biomass pyrolysis oil spray combustion using Finite-Rate Chemistry (FRC) approach. To make the CFD calculations feasible, a reduced mechanism for modeling the combustion of biomass Fast Pyrolysis Oil (FPO) based on the POLIMI 1412 mechanism and a model for eugenol oxidation was developed. The reduced mechanism consisted of 200 reactions and 71 species. This level of complexity was found to be a good tradeoff between predictive power and computational cost such that the reduced model could be used in CFD modeling. The predictive power of the reduced mechanism was demonstrated via 0D (adiabatic, premixed, constant pressure reactor), 1D (laminar counterflow flame) and 3D (CFD of a methane-air flat-flame piloted FPO spray flame) calculations. Results from CFD were compared against experimental data from non-intrusive optical diagnostics. The reduced model was successfully used in CFD calculations—the computational cost was approximately 2 orders of magnitude higher than that of a simplified model. Using the reduced mechanism, the concentration of pollutants, minor combustion products, and flame radicals could be predicted—this is added capability compared to already existing models. The CFD model using the reduced mechanism showed quantitative predictive power for major combustion products, flame temperature, some pollutants and temperature, and qualitative predictive power for flame radicals and soot.

The immersion freezing ability of soot particles has in previous studies been reported in the range of low/insignificant to very high. The aims of this study were to: (i) perform detailed physico-chemical characterisation of freshly produced soot particles with very different properties, (ii) investigate the immersion freezing ability of the same particles, and (iii) investigate the potential links between physico-chemical particle properties and ice-activity. A miniCAST soot generator was used to produce eight different soot samples representing a wide range of physico-chemical properties. A continuous flow diffusion chamber was used to study each sample online in immersion mode over the temperature (T) range from −41 to −32 °C, at a supersaturation of about 10% with respect to liquid water. All samples exhibited low to no heterogeneous immersion freezing. The most active sample reached ice-activated fractions (AF) of 10−3 and 10−4 at temperatures of 1.7 and 1.9 K , respectively, above the homogeneous freezing temperature. The samples were characterized online with respect to a wide range of physico-chemical properties including effective particle density, optical properties, particle surface oxidation and soot maturity. We did observe indications of increasing immersion freezing ice-activity with increasing effective particle density and increasing particulate PAH fraction. Hence, those properties, or other properties co-varying with those, could potentially enhance the immersion freezing ice-activity of the studied soot particle types. However, we found no significant correlation between the physico-chemical properties and the observed ice-nucleating ability when the particle ensemble was extended to include previously published results including more ice-active biomass combustion soot particles. We conclude that it does not appear possible in general and in any straightforward way to link observed soot particle physico-chemical properties to the ice-nucleating ability using the online instrumentation included in this study. Furthermore, our observations support that freshly produced soot particles with a wide range of physico-chemical properties have low to insignificant immersion freezing ice-nucleating ability.

Previous studies have shown that injector aging adversely affects the diesel engine spray formation and combustion. It has also been shown that the oxygenated fuel additive tripropylene glycol monomethyl ether (TPGME) can lower soot emissions. In this study, the effects of injector aging and TPGME on the late cycle oxidation of soot were investigated using laser diagnostic techniques in a light-duty optical diesel engine at two load conditions. The engine was equipped with a quartz piston with the same complex piston geometry as a production engine. Planar laser-induced incandescence (LII) was used to obtain semiquantitative in-cylinder two-dimensional (2D) soot volume fraction (f(v)) distributions using extinction measurements. The soot oxidation rate was estimated from the decay rate of the in-cylinder soot concentration for differently aged injectors and for cases with and without TPGME in the fuel. The aged injector produced higher soot concentrations than the new injector at both load conditions. The aged injector also showed higher soot oxidation rates than the new injector at the low load condition. TPGME resulted in lower soot concentrations at both load conditions and faster oxidation rates, especially at mid load conditions.

Two-wavelength and two-color laser-induced incandescence (2 λ –2C-LII) was used to study the absorption properties of three types of cold soot of different maturity from a mini-CAST soot generator. LII fluence curve analysis allowed for estimating absorption wavelength dependence in terms of dispersion coefficients ξ by the use of two excitation wavelengths (532 and 1064 nm). The estimated ξ (based on E ( m, λ ) ∝ λ 1−ξ ) spanned from ~ 1.2 for the mature soot, up to 2.3 for the young soot. The results for the mature soot showed good agreement with previous measurement using multi-wavelength extinction. For the young soot, however, some discrepancy was observed suggesting a weaker wavelength dependence (lower ξ ) from the LII fluence analysis. Furthermore, an estimation of the E ( m, λ ) for the different types of soot was done from the experimental fluence curves with temperature analysis in the low-fluence regime and simulations using an LII model. Additionally, uncertainties and limitations were discussed. Finally, it should be pointed out that caution has to be taken when interpreting 2 λ -LII results to obtain quantitative absorption properties of less mature soot, which may be influenced by thermal annealing during the laser pulse and by absorption from non-refractory species externally/internally mixed with the soot.

Raman spectroscopy is widely used for characterization of carbon-based materials including light-absorbing carbonaceous (LAC) matter. However, information on polarization properties of these materials are generally lacking, and often the polarization characteristics of experiments are not presented in the literature thereby giving uncertainty to presented data. In this work, the polarization properties of various LACs are studied using Raman spectroscopy. The Raman spectra have been compared while varying the relative polarization, particularly the relative direction of the electric field between the incident light and the detected scattered light. Specifically, the intensity ratio between the D-1 and G peaks (I-D1/I-G) was analyzed in parallel and perpendicular polarization configurations for samples taken from a sooting flame, in the exhaust of a soot generator and carbon blacks. In this work, the parallel and perpendicular polarization configurations mean that the polarization of the detected scattered light is parallel and orthogonal, respectively, to the linearly polarized incident light. It was found that the (I-D1/I-G) ratio decreased in the more ordered carbonaceous structures when changing the polarization configuration from parallel to perpendicular. Additionally, based on the depolarization ratios (D-p < 0.75), the prominent Raman peaks of LAC were found to originate from totally symmetric vibrations. For the G peak, the depolarization ratio was measured to be in the range 0.46-0.56 for all LAC materials.

We report thermometry and new Raman linewidth data using a novel method for time-domain rotational coherent anti-Stokes Raman spectroscopy (RCARS) on single-shot basis. The coherences are generated by two fs pulses and probed by a ns pulse. The resulting signal is detected using a combined spectrograph/streak camera setup with high spectral and temporal resolution. Rotational CARS spectrograms of nitrogen (N-2), ethylene (C2H4), ethane (C2H6), and argon (Ar) are demonstrated at ambient condition. Self-broadened N-2-N-2 S-branch Raman linewidths were measured on single-shot basis and show excellent agreement with literature values. Furthermore, Raman linewidths of N-2 S-branch perturbed by C2H4 and C2H6 were measured for the first time. The time-resolved approach was also utilized to separate complex spectra from a mixture of species through their difference in coherence lifetimes. Since the Raman coherences decay much faster for both ethane and ethylene than for nitrogen, pure nitrogen spectra could be obtained by analyzing only the temporal tail of the signal. Moreover, a model for time-resolved RCARS of N-2 was developed, which employs the single-shot measured Raman linewidths to calculate the corresponding spectro-temporally resolved spectrograms at different temperatures. The model was used to evaluate the temperature from single-shot data of an N-2/C2H6 mixture, showing very high accuracy. The demonstrated method constitutes an essential improvement for single-shot thermometry as it does not require pre-knowledge about collider species concentrations and their impact on linewidths. (c) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

Exhaled respiratory particles during singing and talking