Importance of flue gas cooling conditions in particulate matter formation during biomass combustion under conditions pertinent to pulverized fuel applications

Laboratory-scale experiments pertinent to pulverised fuel (PF) combustion are often carried out in drop-tube furnaces (DTFs) at air-fuel equivalence ratios and cooling rate for quenching flue gas that are much higher than those in PF boilers. This paper reports the effect of flue gas cooling conditions on the properties of PM with aerodynamic diameter of <10 µm (PM₁₀) from biomass combustion. This study considers four cooling rates (1000, 2000, 6000 and 20,000 °C/s) and two biomass feeding rates (0.05 and 0.25 g/min) that represents flue gases with significantly-different concentrations of inorganic vapours. The PSDs of PM₁₀ have a bimodal distribution with a fine mode within PM with aerodynamic diameter of <1 µm (PM₁) and a coarse mode within PM with aerodynamic diameter of 1–10 µm (PM_1–10). All experimental conditions produce PM₁₀ with similar PM₁ and PM_1–10 yields (～0.8 and ～1.6 mg/g_biomass, respectively) and similar coarse mode diameters (i.e. 6.863 µm). However, at a biomass feeding rate of 0.05 g/min, the fine mode diameter shifts from 0.022 to 0.077 µm when the cooling rate decreases from 20,000 to 1000 °C/s, indicating more profound heterogeneous condensation at a lower cooling rate. As the biomass feeding rate increases to 0.25 g/min, the fine mode diameter further shifts to 0.043 µm and at 20,000 °C/s but remained at 0.077 µm at 1000 °C/s though a clear shift of PSD to larger diameters is evident. These are attributed to enhanced heterogeneous condensation and coagulation of small particulates resulting from increased particle population density in hot flue gas. Chemical analyses show PM₁ contains dominantly volatile elements (i.e. Na, K and Cl) while PM_1–10 consists of mainly Ca. Similar trends are also observed for elemental PSDs and yields. It is also observed that slow cooling of hot flue gas leads to an increased yield of Cl in PM_1–10 due to enhanced chlorination of Ca species.     

Ash cenosphere fragmentation during pulverised pyrite combustion: Importance of cooling

This paper as the first time in the field reports the direct experimental evidence for demonstrating the important role of cooling in ash cenosphere fragmentation using a simple but unique combustion system. The combustion system used pulverised pyrite (38–45 µm) for combustion in drop-tube furnace under designed conditions (gas temperature: 1000 °C; residence time: 1.2 s), which produced dominantly ash cenosphere particles or fragments. The combustion products were quenched under various cooling conditions (represented by nominal cooling rates of 6400–11,800 °C/s) for sampling. The results show that increasing cooling rate from 6400 to 11,800 °C/s substantially intensifies ash cenosphere fragmentation. Such enhanced ash cenosphere fragmentation leads to a significant shift in the particle size distribution of ash collected in the cyclone (>10 µm) to much smaller sizes. It also produces considerably more particulate matter (PM) with aerodynamic sizes less than 10 µm (i.e., PM₁₀) that consists of dominantly PM with aerodynamic sizes between 1 and 10 µm (i.e., PM_1–10) and some PM with aerodynamic sizes less than 1 µm (i.e., PM₁). It is further noted that the PM₁ is mainly PM with aerodynamic sizes between 0.1 and 1 µm (i.e., PM_0.1–1) and to a considerably lesser extent PM with aerodynamic sizes less than 0.1 µm (i.e., PM_0.1). Chemical analyses further show that both ash and PM samples contain only Fe₂O₃, indicating that complete consumption of sulphur and full oxidation of iron have been achieved during pulverised pyrite combustion under the conditions.     

Fundamental investigation into characteristics of particulate matter produced from rapid pyrolysis of biochar in a drop-tube furnace at 1300 °C

This paper reports the emission characteristics of leaf and wood biochar (LC500 and WC500) pyrolysis in a drop tube furnace at 1300 °C in argon atmosphere. The char yields at 1300 °C are ～ 65% and ～ 73% respectively for LC500 and WC500. Over 60% Mg, Ca, S, Al, Fe and Si are retained in char after pyrolysis at 1300 °C. The retentions of Na and K in the char from LC500 pyrolysis are lower than those in the char from WC500 pyrolysis due to release via enhanced chlorination as a result of much higher Cl content in LC500. Particulate matter (PM) with aerodynamic diameter of < 10 µm (i.e. PM₁₀) from LC500 and WC500 pyrolysis exhibits a bimodal distribution with a fine mode diameter of 0.011 µm and a coarse mode diameter of 4.087 µm. The PM₁₀ yield for LC500 pyrolysis is ～ 8.2 mg/g, higher than that of WC500 pyrolysis (～2.1 mg/g). Samples in PM_1-10 (i.e. PM with aerodynamic diameter 1 µm – 10 µm) are char fragments that have irregular shapes and similar molar ratio of (Na+K + 2Mg+2Ca)/(Cl+2S+3P) as the char collected in the cyclone. In PM₁ (i.e. PM with aerodynamic diameter < 1 µm), the main components in sample are inorganic species, and carbon only contributes to ～5% and ～8% the PM₁ produced from rapid pyrolysis of LC500 and WC500, respectively. Na, K and Cl are main inorganic species in PM₁, contributing ～ 98.8% and ～ 97.5% to all inorganic species. Na, K and Cl from rapid pyrolysis of biochar have a unimodal distribution with a mode diameter of 0.011 µm. In PM_1–10, Ca is the main inorganic specie, contributing to ～71.2% and ～65.3% to all inorganic species in PM_1–10 from pyrolysis of LC500 and WC500, respectively.     

Mechanistic investigation into particulate matter formation during air and oxyfuel combustion of formulated water-soluble fractions of bio-oil

This paper reports a systematic study on the formation of particulate matter with diameter of <10 µm (i.e., PM₁₀) during the combustion of two formulated water-soluble fractions (FWSFs) of bio-oil in a drop-tube-furnace (DTF) at 1400 °C under air or oxyfuel (30%O₂/70%CO₂) conditions. FWSF-1 was an organic-free calcium chloride solution with a calcium concentration similar to that in the bio-oil. FWSF-2 was formulated from the compositions of major organics in bio-oil WSF, doped with calcium chloride at the same concentration. The results suggest that similar to bio-oil combustion, the FWSF combustion produces mainly particulate matter with diameter of between 0.1 and 10 µm (i.e., PM_0.1–10). Since there are no combustibles in the organic-free FWSF-1, the PM is produced via droplet evaporation followed by crystallization, fusion and further reactions to form CaO (in air or argon) or partially CaCO₃ (under oxyfuel condition). With the addition of organics, FWSF-2 combustion produces PM₁₀ shifting to smaller sizes due to extensive break up of droplets via microexplosion. Sprays with larger droplet size produce PM₁₀ with increased sizes. The results show that upon cooling CaO produced during combustion in air can react with HCl gas to form CaCl₂ in PM_0.1. The predicted PSDs of PM₁₀ based on the assumption that one droplet produces one PM particle is considerably larger than experimentally-measured PSDs of PM₁₀ during the combustion of FWSFs, confirming that breakup of spray droplets takes place and such breakup is extensive for FWSF-2 when organics are present in the fuel.     

Effect of the torrefaction on the emission of PM10 from combustion of rice husk and its blends with a lignite

Torrefaction is a competitive biomass pretreatment technology. However, its impacts on particulate matter (PM) formation during biomass combustion and co-combustion with coal have little been investigated. This work provides new data on the formation of PM₁₀ (particulate matter with aerodynamic diameters less than or equal to 10 µm) from combustion of raw (RH), torrefied rice husk (TRH) and their blends with a lignite (SZ). All combustion experiments were carried out on a drop-tube furnace at 1300 °C and in air. The combustion-generated PM₁₀ was collected by a Dekati low pressure impactor and classified into 14 size fractions for further quantification and characterization. The results indicate that, compared with the RH, the TRH-derived PM₁₀₊ (particle size above 10?µm) contains more alkalis, leading to a decrease in the production of PM₁ (particle size below 1?µm). During co-combustion, fuel interactions promote the transformation of alkali chlorides to aluminosilicates. A considerable amount of water-soluble Ca and P in PM₁ transforms to PM_1–10 (particle size between 1–10?µm). As a result, the production of PM₁ (on an ash basis) decreases while that of PM_1–10 increases. Co-combustion of coal with torrefied rice husk is found to generate less PM₁ but more PM_1–10 than that with raw rice husk.     

PM10 formation during the combustion of N2-char and CO2-char of Chinese coals

The formation of PM₁₀ (particles less than or equal to 10 μm in aerodynamic diameter) during char combustion in both air-firing and oxy-firing was investigated. Three Chinese coals of different ranks (i.e., DT bituminous coal, CF lignite, and YQ anthracite) were devolatilized at 1300 °C in N₂ and CO₂ atmosphere, respectively, in a drop tube furnace (DTF). The resulting N₂-chars and CO₂-chars were burned at 1300 °C in both air-firing (O₂/N₂ = 21/79) and oxy-firing (O₂/CO₂ = 21/79). The effects of char properties and combustion conditions on PM₁₀ formation during char combustion were studied. It was found that the formation modes and particle size distribution of PM₁₀ from char combustion whether in air-firing or in oxy-firing were similar to those from pulverized coal combustion. The significant amounts of PM_0.5 (particles less than or equal to 0.5 μm in aerodynamic diameter) generated from combustion of various chars suggested that the mineral matter left in the chars after coal devolatilization still had great contributions to the formation of ultrafine particles even during the char combustion stage. The concentration of PM₁₀ from char combustion in oxy-firing was generally less than that in air-firing. The properties of the CO₂-chars were different from those of the N₂-chars, which was likely due to gasification reactions coal particles experienced during devolatilization in CO₂ atmosphere. Regardless of the combustion modes, PM₁₀ formation in combustion of N₂-char and CO₂-char from the same coal was found to be significantly dependent on char properties. The difference in the PM₁₀ formation behavior between the N₂-char and CO₂-char was coal-type dependent.     

Emissions of PM10 from the co-combustion of high-Ca pyrolyzed biochar and high-Si coal under air and oxyfuel atmosphere

The single or co-combustion experiments of high-Ca pyrolyzed biochar and high-Si coal were carried out on a drop tube furnace (DTF) at 1300 °C under air and oxyfuel (CO₂:O₂=50:50, oxy50) conditions. The produced PM₁₀ (of an aerodynamic diameter of 10 µm or less) was analyzed to investigate the interactions during co-combustion. Due to the characteristics of the selected samples (low S and Cl), the PM₁ emissions including PM_0.1 and PM_0.1–1 are very low during single combustion, except for the PM_0.1–1 emission during the combustion of biochar under oxy50 condition because of the massive partitioning of Mg, Ca and Fe. The interaction during co-combustion was observed to mainly occur in the generation of PM_1–10, and also slightly occur in the formation of PM_0.1–1 under oxy50 condition. The capture of Mg, Ca, and Fe from biochar by the Si-containing minerals in coal under the oxy50 condition results in a slight decrease in PM_0.1–1 during co-combustion. The higher the proportion of coal blended, the more obvious the reduction of elements. As for the formation of PM_1–10 during co-combustion, high-melting minerals of biochar would weaken the coalescence of minerals in coal to cause more PM₁₀, while the large mineral grains of coal would capture the minerals in biochar to generate more PM₁₀₊. Under the competition of the above two types of interactions, the experimental value of PM_1–10 yields was almost consistent with the theoretically calculated value, except for blended ratio of 80:20 (coal: biochar, air) or 50:50 (oxy50) with prior interaction predominating.     

Mechanism on the contribution of coal/char fragmentation to fly ash formation during pulverized coal combustion

In this paper, the correlations between coal/char fragmentation and fly ash formation during pulverized coal combustion are investigated. We observed an explosion-like fragmentation of Zhundong coal in the early devolatilization stage by means of high-speed photography in the Hencken flat-flame burner. While high ash-fusion (HAF) bituminous and coal-derived char samples only undergo gentle perimeter fragmentation in the char burning stage. Simultaneously, combustion experiments of two kinds of coals were conducted in a 25?kW down-fired combustor. The particle size distributions (PSDs) of both fine particulates (PM_1-10) and bulk fly ash (PM₁₀₊) were measured by Electrical Low Pressure Impactor (ELPI) and Malvern Mastersizer 2000, respectively. The results show that the mass PSD of residual fly ash (PM₁₊) from Zhundong coal exhibits a bi-modal shape with two peaks located at 14?µm and 102?µm, whereas that from HAF coal only possesses a single peak at 74?µm. A hybrid model accounting for multiple-route ash formation processes is developed to predict the PSD of fly ash during coal combustion. By incorporating coal/char fragmentation sub-models, the simulation can quantitatively reproduce the measured PM₁₊ PSDs for different kinds of coals. The sensitivity analysis further reveals that the bi-modal mass distribution of PM₁₊ intrinsically results from the coal fragmentation during devolatilization.     

Reduction effect of co-firing of torrefied straw and bituminous coal on PM1 emission under both air and oxyfuel atmosphere

Straw sample was torrefied at 260 °C and 300 °C in N₂, respectively, to prepare torrefied straw named as T-260 and T-300, and the reduction effect of co-firing straw or torrefied straw and steam coal on PM₁ is investigated. The combustion experiments were conducted in a high temperature drop tube furnace (DTF) at 1400 °C to collect the inorganic PM₁₀ for further analysis. Combustion atmosphere was air for all cases and 50% O₂/50% CO₂ (OXY50) for coal, T-260 and their blends of 1:1 and 4:1. The results show that all three biomass fuels show obvious emission reduction of PM with aerodynamic diameters of ≤?0.3?µm (PM_0.3) under both mix ratios. Reduction ratios of co-firing are overall higher at mix ratio of 1:1 than 4:1, and co-firing of T-260 or T-300 with coal shows higher reduction ratio than co-firing of straw. The higher ash content in torrefied straw leads to higher contents of alkali and alkaline earth metals (AAEM), which will further react with both Si and S during co-firing and coagulate into particles of larger sizes, leading to higher reduction ratios of PM_0.3 and unconspicuous reduction effects in PM_0.3–1 emitted from co-firing. During co-firing in oxyfuel atmosphere, a higher combustion temperature compared to air leads to an intensitive gasification, may resulting in effective and even higher reduction ratio in PM_0.3.     

Volatile–char interactions: Roles of in situ volatiles with distinctly-different chemistry in determining char structure and reactivity

This study reports the roles of volatiles with distinctly-different chemistry in determining char reactivity and char structure during in situ volatile–char interactions under non-catalytic conditions. Volatiles were generated in situ from polyethylene (PE), double-acid washed biosolid (DAWB), polyethylene glycol (PEG) or cellulose and interacted with char prepared from DAWB that is free of catalytically-active inorganic species in a two-stage reactor at 1000 °C. The experimental results show that both H- and O-containing reactive species play different roles during in situ volatile–char interactions. It has been found that char reactivity decreases substantially after in situ volatile–char interactions. Results from Raman analysis of the char after in situ interactions with the PE volatiles show H-containing reactive species substantially enhance the condensation of the aromatic ring systems within the char, thus slightly decreasing the H content in char and also making char carbon structure considerably less reactive. It has also been found that the reactivity of char after in situ volatile–char interactions increases with increasing O/H molar ratio of volatiles. The results indicate that O-containing reactive species in volatiles can react with char to form CO complex oxides that mitigate the carbon structure from condensing into large aromatic ring systems, thus increasing O and H contents in char and enhancing char reactivity.     

Single particle ignition and combustion of pulverized pine wood,wheat straw,rice husk and grape pomace

This work examines the combustion behavior of single pulverized biomass particles from ignition to early stages of char oxidation. The biomass residues investigated were pine wood, wheat straw, rice husk and grape pomace. The biomass particles, in the size range 224–250 µm, were injected upward into a confined region with hot combustion products, produced by a flat flame McKenna burner, with a mean temperature of 1610 K and a mean O₂ concentration of 6.5 vol%. Temporally and spectrally resolved images of the single burning particles were recorded with an intensified charge-coupled device camera equipped with different band-pass spectral filters. Data are reported for CH*, C₂*, Na* and K* chemiluminescence, and thermal radiation from soot and char burning particles. The data on CH* and C₂* chemiluminescence and soot thermal radiation permits to identify important differences between the ignition delay time, volatiles combustion time and soot formation propensity of the four biomass residues, which are mainly affected by their volatile matter content. The Na* and K* emission signals follow the same trends of the CH* and C₂* emission signals until the end of the volatiles combustion stage, beyond which, unlike the CH* and C₂* emission signals, they persist owing to their release from the char burning particles. Moreover, during the volatiles combustion stage, the Na*/CH* and K*/CH* ratios present constant values for each biomass residue. The CH* and thermal radiation emission data suggest that all biomass char particles experienced heterogeneous oxidation at or immediately after the extinction of the homogeneous volatiles combustion.     

Elemental characterization and source identification of the near-road PM2.5 using EDXRF in Chengdu,China

To characterize the elemental composition and source apportionment of aerosols in roadside area, particulate matters with aerodynamic diameter less than 2.5 μm (PM_2.5) were collected in close proximity to a road from September 2017 to February 2018 in downtown Chengdu, China. An energy-dispersive X-ray fluorescence spectrometer was used to quantify elemental constituents (Al, Si, S, K, Mn, Fe, Ni, Cu, Zn, As, and Pb) of PM_2.5 and was calibrated by in-house standards instead of commercial standards. The constructed calibration curves exhibited good linearity with all correlation coefficients greater than 0.98. The proposed calibration method proved to be reliable for the subsequent elemental analyses due to the satisfactory performance of u-score and precision that were validated by the certified reference materials (#2783). The results revealed that average PM_2.5 concentrations of 92.2 ± 45.6 and 113.2 ± 60.3 μg/m³ were respectively observed in autumn and in winter. The major trace elements identified were K, S, and Fe and the minor contributions were from Cu and As. Most crustal elements showed decline in winter except for K, and most anthropogenic elements showed increase in winter except for Ni. Using rotation factor analysis and cluster analysis based on the elemental dataset, four potential sources were identified: road dust, vehicular emissions, coal and biomass burning, and industrial emissions. This research will provide a better understanding of traffic-related PM_2.5 composition, and this can be used in the mitigation and prevention programs.     

Measurements and modelling of oxy-fuel coal combustion

Oxy-fuel combustion is one of the most promising technologies to isolate efficiently and economically CO₂ emissions in coal combustion for the ready carbon sequestration. The high proportions of both H₂O and CO₂ in the furnace have complex impacts on flame characteristics (ignition, burnout, and heat transfer), pollutant emissions (NO_x, SO_x, and particulate matter), and operational concerns (ash deposition, fouling/slagging). In contrast to the existing literature, this review focuses on fundamental studies on both diagnostics and modelling aspects of bench- or lab-scale oxy-fuel combustion and, particularly, gives attention to the correlations among combustion characteristics, pollutant formation, and operational ash concerns. First, the influences of temperature and species concentrations (e.g., O₂, H₂O) on coal ignition, volatile combustion and char burning processes, for air- and oxy-firing, are comparatively evaluated and modelled, on the basis of data from optically-accessible set-ups including flat-flame burner, drop-tube furnace, and down-fired furnace. Then, the correlations of combustion-generated particulate/NO_x emissions with changes of combustion characteristics in both air and oxy-fuel firing modes are summarized. Additionally, ash deposition propensity, as well as its relation to the formation of fine particulates (i.e. PM_0.2, PM₁ and PM₁₀), for both modes are overviewed. Finally, future research topics are discussed. Fundamental oxy-fuel combustion research may provide an ideal alternative for validating CFD simulations toward industrial applications.     

Evaluation of the concentration of chemical elements in suspended particulate matter inside a small bronze and iron foundry industry,using a streaker sampler and EDXRF

The aim of this study was to determine and evaluate the temporal profiles of the concentration of chemical elements in the suspended particulate matter present inside a small bronze and an iron foundry industry. To collect the samples, we used a streaker sampler that separates particles with aerodynamic diameters smaller than 10 µm (PM₁₀) in two fractions: fine (particles with aerodynamic diameters less than 2.5 µm; PM_2.5) and coarse (between 2.5 µm and less than 10 µm; PM_10–2.5). The collection of samples was taken every 20 min during a total time of 8 and 5 h of molding and casting of bronze and iron, respectively. The samples collected in the form of strips on a filter (fine fraction) and an impactor (coarse fraction) were analyzed by the energy dispersive X‐ray fluorescence technique. In the excitation, an X‐ray tube with Mo target and Zr filter was used, operated at 30 mA/30 kV. For detecting the characteristic of X‐rays, a semiconductor Si(Li) detector was used, coupled to a multi‐channel spectrometer, with a 300 s excitation/detection time. The results of the temporal profiles of chemical element concentrations in coarse and fine fractions were discussed and compared with the maximum levels set by the Brazilian and international environmental agencies. Copyright © 2013 John Wiley & Sons, Ltd.     

Identification of elemental composition of PM2.5 collected in Makkah,Saudi Arabia,using EDXRF

Makkah city, Saudi Arabia, represents the most attractive place for religious tourism for Muslims all over the world. More than 15 million visitors come to the city per year, especially during Hajj (pilgrimage) and Ramadan seasons. Due to the lack of air quality assessment data for Makkah, measurement of different pollutants in Makkah is of great interest. In the present work, airborne particulate matter with aerodynamic diameter equal to or less than 2.5 µm (PM_2.5) has been collected from two different sites in the city, namely the Grand mosque and Al‐Shraie, from December 2012 to January 2014 covering the different seasons of the year. The average mass concentrations at the sites are comparable, 48 ± 28 µg/m³ and 53 ± 27 µg/m³ for the Grand mosque and Al‐Shraie sites, respectively. For quantitative elemental analysis, energy dispersive X‐ray fluorescence (EDXRF) spectrometry was used. Twenty elements (Si, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Ga, Se, Br, Rb, Sr and Pb) were quantified in the PM_2.5 samples. Fortunately, the obtained results of Pb and S are below the maximum allowance level of European commission for air quality. However, the average concentration of Ni in both sites is close to the maximum allowance level 20 ng/m³ and the Ni concentration reaches 25 ng/m³ at Grand mosque site during August 2013. Based on the Positive Matrix Factorization (PMF) analysis, four source factors were found, some signalling mixed sources, showing the main influence from mineral dust, anthropogenic/industrial sources and a marine source. Copyright © 2017 John Wiley & Sons, Ltd.     

Investigating particle and volatile evolution during pulverized coal combustion using high-speed digital in-line holography

Devolatilization is an important process in pulverized coal combustion because it affects the ignition, volatile combustion, and subsequent char burning and ash formation. In this study, high-speed digital in-line holography is employed to visualize and quantify the particle and volatile evolution during pulverized coal combustion. China Shanxi bituminous coal particles sieved in the range of 105–154 µm are entrained into a flat flame burner through a central tube for the study. Time-resolved observations show the volatile ejection, accumulation, and detachment in the early stage of coal combustion. Three-dimensional imaging and automatic particle extraction algorithm allow for the size and velocity statistics of the particle and stringy volatile tail. The results demonstrate the smaller particle generation and coal particle swelling in the devolatilization. It is found that the coal particles and volatiles accelerate due to the thermal buoyancy and the volatiles move faster than the coal particles. On average, smaller particles move faster than the larger ones while some can move much slower possibly because of the fragmentation.     

Formation of Mg2Ni nanofibres in a Mg-based metal matrix composite

A Mg–Mg₂Ni nano-eutectic and MgO-reinforced Mg-based metal matrix composite (Mg-MMC) was synthesized by in-situ reactions. When a Mg-rich sample containing 20?wt%?NiO is sintered at 420°C, MgO, Ni and Mg₂Ni are formed in the Mg matrix. When a sample molten at 550°C is furnace-cooled to room temperature, a lamellar two-phase Mg–Mg₂Ni eutectic is formed, with the Mg₂Ni lamella about 1.5?µm thick. Proeutectic Mg together with the MgO formed in situ act as heterogeneous nuclei for the growth of the Mg–Mg₂Ni eutectic. Quenching the molten sample to room temperature results in a lamellar two-phase eutectic containing Mg₂Ni nanofibres. In the eutectic grown at the Mg grain, the Mg₂Ni nanofibres with a diameter of about 25?nm are bent, whereas in the eutectic grown at the MgO grain, the Mg₂Ni nanofibres with a diameter of about 30?nm are long and straight, while the Mg phase of this eutectic is oxygen enriched. The differences in morphologies between the two Mg–Mg₂Ni eutectics are ascribed to the growth rates of Mg and Mg₂Ni, which differ in the eutectic grown at the Mg grain, but remain similar when growth takes place at the MgO grain.     

Elemental composition of fine particulate matter (PM2.5) in Skopje,FYR of Macedonia

Aerosol samples were collected at an urban background site in Skopje, Former Yugoslavic Republic of Macedonia, during four measurement campaigns from December 2006 to October 2007. An impactor was used to collect particulate matter (PM_2.5) aerosol particles and the samples were analyzed for the concentrations of particulate mass, black carbon (BC), and 17 elements. The 12‐h average PM_2.5 concentrations varied in the range 10–140 µg m^?3 with the highest concentrations measured during wintertime pollution episodes and during the summer period. Pair‐wise correlations and crustal enrichment were studied and the data set was analyzed by factor analysis and positive matrix factorization. Major aerosol components were identified as mineral dust (main observed tracers Si, K, Ca, Ti, Fe, Sr, and Rb), combustion (BC, S, K, V, and Ni), traffic‐related aerosol (Pb and Zn), and secondary sulfate combined with mineral dust. Combustion sources dominated during wintertime and were likely due to heavy oil combustion, biomass burning, and other industrial activities within the city area. Mineral dust was observed throughout the year, but the concentrations peaked during the unusually hot and dry summer of 2007. It is concluded that Skopje suffers from serious air pollution due to central and residential heating, the transport sector, and industrial activities within the city, and contributions from mineral dust increase the PM_2.5 concentrations under dry periods. Topography and meteorological conditions aggravate the problems and make the air quality comparable with the conditions in other highly polluted cities in Southern Europe and worldwide. Copyright © 2011 John Wiley & Sons, Ltd.     

Hybrid Al + Al3Ni metallic foams synthesized in situ via laser engineered net shaping

A hybrid, Al?+?Al₃Ni metallic foam was synthesized in situ via laser engineered net shaping (LENS®) of Ni-coated 6061 Al powder in the absence of a foaming agent. During LENS® processing, the Ni coating reacted with the Al matrix, resulting in the simultaneous formation of a fine dispersion of Al₃Ni, and a high volume fraction of porosity. As a reinforcement phase, the intermetallic compound formed particles with a size range of 1–5?µm and a volume fraction of 63%, with accompanying 35–300?µm pores with a 60% volume fraction. The microstructure of the as-deposited Al?+?Al₃Ni composite foams was characterized using SEM, EDS, XRD and TEM/HRTEM techniques. The evolution of the microstructure was analyzed on the basis of the thermal field present during deposition, paying particular attention to the thermodynamics of the Al₃Ni intermetallic compound formation as well as discussing the mechanisms that may be responsible for the observed porosity. The mechanical behavior of the as-deposited material was characterized using compression and microhardness testing, indicating that the yield strength and hardness are 190?MPa and 320 HV, respectively, which represents an increase of over three times higher than that of annealed Al6061, or similar to heat-treated Al6061 fully dense matrix, and much higher than those of traditional Al alloy foams, and with a low density of 1.64?g/m³.     

In situ sensor for cycle-resolved measurement of temperature and mole fractions in IC engine exhaust gases

We present a multi-species mole fraction and temperature sensor for in situ exhaust gas diagnostic of internal combustion (IC) engines. The sensor is based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) and incorporates four optical channels - two miniature White cells and two double-traversal cells - with base lengths of 6?cm. It has been demonstrated at a hot air test stand and in the exhaust manifold of a single-cylinder research engine, with measured temperatures of up to 1000?K. Stable operation was achieved with absorption lengths of up to 192?cm (test stand) and 97?cm (engine). Employing time-division multiplexed detection, six species were measured simultaneously in the engine exhaust, at wavelengths ranging from 1.4?µm to 5.2 µm: water vapor (H₂O), carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nitrogen dioxide (NO₂) and nitric oxide (NO). The effective measurement rate was as high as 1?kHz, and cycle-to-cycle variations were clearly detected. We show the correlation of the air-fuel equivalence ratio with the spectroscopically measured mole fraction of each species. At a cycle-resolved rate, detection limits for the legally regulated species NO and NO₂ were 1?ppm and 4?ppm, respectively. The sensor is intended to help improve the understanding of IC engine emission behavior during fast transients.