AEROSOL CHARACTERISATION IN MEDIUM-SPEED DIESEL ENGINES OPERATING WITH HEAVY FUEL OILS

Aerosol measurements were carried out in medium-speed diesel engines to determine the aerosol characteristics and formation in four-stroke diesel engines equipped with turbocharger(s) burning heavy fuel and high ash-content heavy fuel oil. The mass size distributions are bimodal with a main mode at 60–90 nm and a second mode at 7–10 μm. The small mode particles are formed by nucleation of volatilized fuel oil ash species, which further grow by condensation and agglomeration. The large mode particles are mainly agglomerates of different sizes consisting of the small particles. The number size distributions peak at 40–60 nm, as also observed in the SEM micrographs. Agglomerates consisting of these primary spherical particles are also found. The TEM micrographs reveal that these particles consist of even smaller structures. Based on the mass and elemental size distributions evidence of high volatility of the fuel oil ash was found. The main effect on the aerosol size distributions was caused by the engine type and fuel oil properties.     

Zn2+-imprinted porous polymer beads: Synthesis,structure, and selective adsorption behavior for template ion

Zn²⁺-imprinted polymer was synthesized in porous spherical forms via a self-assembled complex between 2,2′-bipyridyl/4-vinylpyridine complexant/functional monomer and Zn²⁺ template ion. Diameters of particles ranged from 250 to 550 μm to enlarge the surface area and thus enhance the adsorption capacity. The presence/absence of the template ion in the preparation of the imprinted polymer was confirmed by EDX spectroscopy, and the physical structure of the particles was investigated using ESEM and BET analysis. The particle and the pore size were controlled by the cross-linker/monomer feed ratio. The adsorption capacity of the imprinted polymers was 210.61 μmol g^?1 for Zn²⁺, while those for Cu²⁺, Ni²⁺, and Pb²⁺, were 37.92 μmol g^?1, 33.02 μmol g^?1, and 9.70 μmol g^?1, respectively. This big discrepancy of the adsorption capacities illustrates the excellent separation selectivity of the imprinted polymers. The adsorption capacity decreased significantly at pH below 4.5, as the polymers are easily protonated. The imprinted particles lost only 10 % of their adsorption ability after 10 repeated uses.     

Monitoring the degradation of a solid oxide fuel cell stack during 10,000 h via electrochemical impedance spectroscopy

A 5-cell solid oxide fuel cell stack was tested during 10,000 h of continuous operation with simulated reformate gas as fuel (71 vol.% H₂, 20.7 vol.% CO₂ and 8.3 vol.% steam) under high fuel utilization (73%) and constant current load (0.5 A cm^?2 or 25 A) at 750 °C. In situ electrochemical impedance spectroscopy was used to monitor the evolution of ohmic and polarisation resistances of individual cells in the stack without interrupting the current load. Impedance spectra were recorded on each cell periodically (every 1000 h) or after uncontrolled incidents happened with the test setup. It has been found that the stack degradation is mainly attributed to the increased ohmic resistance, pointing to possible causes such as interconnect corrosion and reduced effective contact areas between cells and interconnects. The degradation rate during the first 5000 h was about 1% kh^?1, but increased afterwards up to 1.5% kh^?1 due to the impact of incidents. Both types of incidents (fuel supply fluctuations and overloading failure of the electronic load) were complicated by inhomogeneous fuel distribution among cells, leading to most probably partial re-oxidation of the anode, accelerating the stack degradation.     

Validation of 14 used,re-calibrated and new TSI 3790 condensation particle counters according to the UN-ECE Regulation 83

Four new, four re-calibrated and six used TSI 3790 condensation particle counters (CPC) were checked using soot particles produced by a mini CAST generator. One of the re-calibrated CPC was also checked with Emery oil (PAO 4) particles (evaporation-condensation method) and its counting efficiencies were in agreement with the manufacturer’s calibration data which were determined with Emery oil particles (electrospray method). However, the counting efficiencies with the soot particles were lower indicating the importance of the calibration material (chemical composition, morphology). Since UN-ECE regulation 83 for light duty vehicles does not specify the material to be used, the validation (check) should be conducted with the same material used by the manufacturer or the differences between the materials should be taken into account. Two used CPCs showed a ～20% decrease in their counting efficiencies after 1.5 years of measuring engine exhaust aerosol. This drift could not be recognized by the status indicators of the instrument and could be attributed to a degradation of the CPC saturator (wick). Two CPCs also showed a non-linear response; a 7% difference was found between low (10 cm^?3) and high concentrations (10,000 cm^?3). A non-linear response (up to 40%) was also observed when the temperature difference between the saturator and the condenser was increased to decrease the cut-off size of the CPCs.     

Parameterizing the formation rate of new particles: The effect of nuclei self-coagulation

The study is based on the work of Lehtinen et al. (2007) [Lehtinen, K. E. J., Dal Maso, M., Kulmala, M., & Kerminen, V.-M. (2007). Estimating nucleation rates from apparent particle formation rates and vice versa: Revised formulation of the Kerminen–Kulmala equation. Journal of Aerosol Science, 38, 988–994] who derived formulae connecting “real” and “apparent” nucleation rates. The parameterization neglected self-coagulation of newly formed particles and clusters, however, and here we have extended the previous work to include the effects of the self-coagulation. Our main focus was on calculating the “apparent” nucleation rate, i.e. the rate at which particles appear at sizes larger than the critical cluster size, as a function of the “real” nucleation rate. The revised parameterization was comprehensively tested against an explicit aerosol dynamic model at diverse atmospheric conditions. It was found out that nuclei self-coagulation has importance to new particle formation when J_nuc/Q>10^?2 where J_nuc is the nucleation rate and Q is the production rate of condensable vapours. This corresponds to the nucleation rates ranging from >10 cm^?3 s^?1 (free troposphere) to >10⁴ cm^?3 s^?1 (polluted boundary layer) depending on the atmospheric conditions. In terms of the particle number concentration, the calculations performed with the explicit model and the predictions of revised parameterization were generally within an order of magnitude. Several issues related to applications in large-scale models were also discussed.     

Size distribution and sites of origin of droplets expelled from the human respiratory tract during expiratory activities

A new expiratory droplet investigation system (EDIS) was used to conduct the most comprehensive program of study to date, of the dilution corrected droplet size distributions produced during different respiratory activities.Distinct physiological processes were responsible for specific size distribution modes. The majority of particles for all activities were produced in one or more modes, with diameters below 0.8 μm at average concentrations up to 0.75 cm^?3. These particles occurred at varying concentrations, during all respiratory activities, including normal breathing. A second mode at 1.8 μm was produced during all activities, but at lower concentrations of up to 0.14 cm^?3.Speech produced additional particles in modes near 3.5 and 5 μm. These two modes became most pronounced during sustained vocalization, producing average concentrations of 0.04 and 0.16 cm^?3, respectively, suggesting that the aerosolization of secretions lubricating the vocal chords is a major source of droplets in terms of number.For the entire size range examined of 0.3–20 μm, average particle number concentrations produced during exhalation ranged from 0.1 cm^?3 for breathing to 1.1 cm^?3 for sustained vocalization.Non-equilibrium droplet evaporation was not detectable for particles between 0.5 and 20 μm, implying that evaporation to the equilibrium droplet size occurred within 0.8 s.     

Thresholds of secondary organic aerosol formation by ozonolysis of monoterpenes measured in a laminar flow aerosol reactor

The reactions of ozone with a series of monoterpenes (α-pinene, sabinene, limonene and myrcene) were investigated in a novel flow reactor dedicated to the investigation of secondary organic aerosol (SOA) formation. Rate constants for the gas phase reactions and nucleation thresholds were determined at T～296 K, P～764 Torr under dry conditions (dew point ≤?33 °C) and in absence of OH radicals scavenger and seed particles. Comparison with the literature as well as data from a simulation chamber showed good agreement. The experiments also show that the novel flow reactor improves the accuracy in evaluating the nucleation thresholds during the ozonolysis of monoterpenes and show that aerosol flow reactor is a useful tool to study the SOA nucleation step. Given as an upper limit, the nucleation thresholds obtained are (in molecule cm^?3/ppb): α-pinene, 3.9×10¹⁰/1.56; sabinene, 6.2×10⁹/0.26; limonene, 1.1×10¹⁰/0.43 and myrcene 2.1×10¹⁰/0.83.     

The effect of zinc substitution on the magnetism of magnesium ferrite nanostructures crystallized from borate glasses

Glasses in the system 51.7 B₂O₃/9.3 K₂O/1 P₂O₅/10.4 Fe₂O₃/(27.6–x) MgO/ x ZnO (with x=0, 5, 10, 13.8 and 20 mol%) were prepared by the conventional melt quenching method. The as prepared glass samples were thermally treated at 560 °C for 3 or 6 h. The effect of substituting MgO by ZnO in the glass network on the crystallized phase was studied. The resulting magnetic glass ceramics were characterized using X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and transmission electron microscopy (TEM) including energy dispersive X-ray analysis (EDX). The substitution of Mg by Zn resulted in a larger lattice parameter of the precipitated crystals, while the crystallite size does not change significantly. TEM micrographs, recorded from extracted particles, showed the formation of small aggregates with about 30 nm in diameter. These agglomerates contain crystals with sizes in the range from 7 to 9 nm. EDX measurements proved the incorporation of Zn²⁺ ions into the crystal phase. Room temperature magnetic measurements of the samples with up to 10 mol% ZnO showed hysteresis loops which are characteristic for super paramagnetic (SPM) behavior. A magnetic contribution was not detected for samples with higher ZnO concentrations. The maximum magnetization varied with the composition of the glass ceramics to a great extent.     

Preparation of sulfur-doped microporous carbons for the storage of hydrogen and carbon dioxide

Structurally well ordered, sulfur-doped microporous carbon materials have been successfully prepared by a nanocasting method using zeolite EMC-2 as a hard template. The carbon materials exhibited well-resolved diffraction peaks in powder XRD patterns and ordered micropore channels in TEM images. Adjusting the synthesis conditions, carbons possess a tunable sulfur content in the range of 1.3–6.6 wt.%, a surface area of 729–1627 m² g^?1 and a pore volume of 0.60–0.90 cm³ g^?1. A significant proportion of the porosity in the carbons (up to 82% and 63% for surface area and pore volume, respectively) is contributed by micropores. The sulfur-doped microporous carbons exhibit isosteric heat of hydrogen adsorption up to 9.2 kJ mol^?1 and a high hydrogen uptake density of 14.3 × 10^?3 mmol m^?2 at ?196 °C and 20 bar, one of the highest ever observed for nanoporous carbons. They also show a high CO₂ adsorption energy up to 59 kJ mol^?1 at lower coverages (with 22 kJ mol^?1 at higher CO₂ coverages), the highest ever reported for any porous carbon materials and one of the highest amongst all the porous materials. These findings suggest that S-doped microporous carbons are potential promising adsorbents for hydrogen and CO₂.     

Reforming of raw fuel gas from biomass gasification to syngas over highly stable nickel–magnesium solid solution catalysts

The gasification of biomass to obtain a syngas provides a competitive means for clean energy from renewable resources. The feasibility of the process depends on the performance of catalyst for upgrading of the raw fuel gas from gasifier. The highly stable NiO–MgO catalyst (Ni / (Ni + Mg) = 15, atomic ratio) was prepared by co-precipitation method for the reforming of raw fuel gas. Its performance was investigated under practical conditions of biomass gasification. The Ni_0.03Mg_0.97O and Ni / MgO catalysts (Ni / (Ni + Mg) = 15, atomic ratio) were also prepared for comparison. The NiO–MgO catalyst exhibited excellent reducibility and highly stable activity for the reforming of raw fuel gas without pre-reduction. No deactivation and very little carbon deposition were observed during 100 h lifetime test. The results of characterization (H₂–TPR, TGA, XRD, XPS) indicated that the formation of nickel–magnesium solid solution inhibited the sintering of nickel particles for high temperature reaction. Due to Ni²⁺ ions diffusion, the Ni / Mg atomic ratio decreased gradually with increasing depth. The highly stable activity was attributed to the small nickel particles size, high dispersion of nickel particles in the solid solution structure, and the promotion by catalyst reducibility.     

Correlation between eletrokinetic mobility and ionic dyes adsorption of Moroccan stevensite

This study aims at establishing a correlation between the electrical charge of Moroccan stevensite particles and ionic dyes adsorption. The electrophoretic mobility, (U_e), of the stevensite particles in water, was measured at pH 2.5–12 by microelectrophoresis. At pH between 2.5 and 8, U_e remained constant (U_e = ? 1.6 10^? 8 m²/(V s)), as resulting from the permanent charge of the clay mineral planar surfaces. At pH > 8, the magnitude of electrophoretic mobility increased (U_e = ? 2.7 10^? 8 m²/(V s)) due to the deprotonation of silanol groups on the surfaces. The anionic Orange G adsorption at the clay mineral–water interface was negligible whereas the methylene blue cations were strongly adsorbed due to the electrostatic attraction.     

Local boron doping quantification in homoepitaxial diamond structures

The capability of transmission electron microscopy (TEM) using the high angle annular dark field mode (HAADF, also labelled Z-contrast) to quantify boron concentration, in the high doping range between 10¹⁹ cm^? 3 and 10²¹ cm^? 3, is demonstrated. Thanks to the large relative variation of atomic number Z between carbon and boron, doping concentration maps and profiles are obtained with a nanometer-scale resolution. A novel numerical simulation procedure allows the boron concentration quantification and demonstrates the high sensitivity and spatial resolution of the technique.     

A novel multi−wavelength photoacoustic spectrometer for the measurement of the UV–vis-NIR spectral absorption coefficient of atmospheric aerosols

A multi-wavelength photoacoustic instrument is described, which measures the wavelength dependent optical absorption coefficient (OAC) of soot or soot-containing aerosols in-situ in a range from the ultra-violet to the near-infrared region. The instrument combines a Nd:YAG disc laser (fundamental wavelength 1064 nm, harmonics at 532, 355 and 266 nm) and four photoacoustic detection cells, each purged with the same aerosol sample flow, while being irradiated with one of the four light beams. With the help of a supplementary optical arrangement to illuminate each detection cell with 532 nm light, the system is calibrated against OAC by purging the cells with known concentrations (and hereby known OAC values) of NO₂. This calibration eliminates differences in sensitivity of the detection PA cells and makes the measurement of OAC absolute.The minimum detectable OAC was determined to be 0.2 Mm^?1 at 1064 nm and 35.5 Mm^?1 at 266 nm, corresponding to a minimum detectable black carbon mass concentration of about 0.1–1 μg/m³, depending on the wavelength. Comparison measurements with artificially generated soot aerosols showed good agreement of the device with a reference instrument, based on a long path extinction cell (LOPES).     

Diffusion coefficient of carbon in Fe–Ni alloy during synthesis of diamond under high temperature and high pressure

Synthetic diamond particles were prepared under high temperature and high pressure using arrayed seeds. A dense Fe–Ni alloy shell covered each diamond seed during synthesis; the growth of diamond particles was controlled by the diffusion of carbon through the metallic shell. The diffusion coefficient of carbon through Fe–Ni melt at 1600 K and 5.5 GPa is about 5×10^?6 cm²/s, with an activation energy for diffusion of 336 kJ/mol.     

Production of hydrogen and MWCNTs by methane decomposition over catalysts originated from LaNiO3 perovskite

LaNiO₃ type perovskite was prepared by the “self-combustion” method and was used as catalyst precursor for the methane decomposition reaction at 600 and 700 °C. CH₄ conversion reaches 80% at 700 °C and 65% at 600 °C using pure CH₄. The yield of CNT and H₂ were 2.2 g_CNT g^?1 h^?1 and 8.2 L g^?1 h^?1 at 700 °C respectively after 4 h of reaction. When the reaction is prolonged to 22 h the catalytic activity decreases but the catalyst is still active, the production of hydrogen reaches 63.5 L (STP) per gram of catalyst and the production of MWCNT was equal to 17 g per gram of catalyst.Multi-wall carbon nanotubes were characterized by X-ray diffraction (XRD), surface area (BET), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric analysis (TGA) and Raman spectroscopy. TEM micrographs showed that MWCNT longer than 20 μm were formed with inner diameters ranging from 5 to 16 nm and outer diameters up to about 40 nm.The results obtained here clearly show that the use of the perovskite LaNiO₃ as catalytic precursor is very effective for the simultaneous production of carbon nanotubes and hydrogen.     

Ce0.9Gd0.1O1.95 supported La0.6Sr0.4Co0.2Fe0.8O3−δ cathodes for solid oxide fuel cells

Lanthanum-based iron- and cobalt-containing perovskite has a high potential as a cathode material because of its high electro-catalytic activity at a relatively low operating temperature in solid oxide fuel cells (SOFCs) (600–800). To enhance the electro-catalytic reduction of oxidants on La_0.6Sr_0.4Co_0.2Fe_0.8O_3?δ (LSCF), Ga doped ceria (Ce_0.9Gd_0.1O_1.95, GDC) supported LSCF (15LSCF/GDC) is successfully fabricated using an impregnation method with a ratio of 15 wt% LSCF and 85 wt% GDC. The cathodic polarization resistances of 15LSCF/GDC are 0.015 Ω cm², 0.03 Ω cm², 0.11 Ω cm², and 0.37 Ω cm² at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. The simply mixed composite cathode with LSCF and GDC of the same compositions shows 0.05 Ω cm², 0.2 Ω cm², 0.56 Ω cm², and 1.20 Ω cm² at 800 °C, 750 °C, 700 °C, and 650 °C, respectively. The fuel cell performance of the SOFC with 15LSCF/GDC shows maximum power densities of 1.45 W cm^?2, 1.2 W cm^?2, and 0.8 W cm^?2 at 780 °C, 730 °C, and 680 °C, respectively. GDC supported LSCF (15LSCF/GDC) shows a higher fuel cell performance with small compositions of LSCF due to the extension of triple phase boundaries and effective building of an electronic path.     

Exposure to welding particles in automotive plants

This work presents a monitoring study designed to evaluate workers' exposure to particles in several body shops within automotive plants. Concentrations in the proximity of welding activities were measured by a Fast Mobility Particle Sizer, several Condensation Particle Counters, a Nanoparticle Surface Area Monitor and a laser photometer, as well as by several gravimetric samplers. Average concentrations were found to be 1×10⁵ part cm^?3, 3×10³ μm² cm^?3 and 0.4 mg m^?3 for number, surface area and PM₁ concentration, respectively (worst case). Very high concentrations, particularly for surface area, were observed in locations with a high density of manual resistance welding activities or close to oxyacetylene welding activities. Welding emission factors in the automotive plants were also evaluated and in the most critical body shop, the overall welding activities led to emission factors of 2.8×10¹⁵ part min^?1, 7.0×10⁶ μm² min^?1 and 7.9 g min^?1 for number, surface area and PM₁ concentrations, respectively. Finally, particle concentration characterization, along with air exchange ratio measurements in the body shop, showed that the indoor concentrations and, hence, worker particle exposure can be reduced through the use of local exhaust ventilation.     

Characterization of particles packing in alumina green tape

Aqueous alumina slurry was prepared with a commercial powder of elongated particles, which has the aspect ratio ranging from 1 to 3.5 with the mean of 1.6, to examine the effect of forming conditions on the particle alignment in green tapes. The slurry appeared pseudoplastic with a yield stress, but showed no thixotropic behavior. Its flow curve fitted very well to the Herschel–Bulkley model approximation, which suggested shear-thinning constant of 0.54. Polarized microscopy with the liquid immersion technique was applied to examine the particle orientation through the direction along the tape thickness. In the absence of coquette flow, randomly oriented particles were noted in the tape. At the top surface, particles were aligned with their long-axes (a-axis) along the casting direction. The variation in the degree of orientation was 6.8 ± 1.2. In the area near the Mylar carrier, a-axis of particle made an angle to the carrier surface with the degree of orientation about 5.8 ± 1.0. As the combination of pressure flow and coquette flow, tape cast with casting velocity of 2.5 and 91.5 cm/min, which respectively resulted in shear rate of 1.38 and 50.8 s^?1, were observed. The orientation was significant near the top surface and was higher than that above the carrier surface. The a-axis of particles above the carrier surface was inclined to the surface at low shear rate (1.38 s^?1), but was nearly parallel at high shear rate (50.8 s^?1). Nevertheless, the orientation varies with the location in the tape prepared at the shear rate of 50.8 s^?1.     

The effect of fast neutron irradiation on the performance of synthetic single crystal diamond particle detectors

Diamond is known for its extreme hardness which may allow it to operate as a particle detector in high fluence environments even after absorption of large radiation doses. We present a study of the deterioration of the charge collection efficiency (CCE) due to neutrons produced by ²³⁵U fission, with irradiation fluences up to 1 × 10¹⁶ n cm^?2. The planar devices were fabricated by thermal evaporation of Au onto approx. 300 μm thick high purity chemical vapour deposited diamond produced by Element Six Ltd., UK. The detector performance was investigated as a function of bias voltage at room temperature using ²⁴¹Am α-particles and minimum ionising particles (MIPs) of a ⁹⁰Sr source. At low fluences up to 2 × 10¹³ n cm^? 2, the detectors reach the initial saturated signal amplitude after irradiation. However, the signal is less stable and deteriorates due to polarisation. This effect can be reduced by initial priming with X-rays. No peak could be distinguished in the detector response in the unprimed state after 10¹⁶ n cm^? 2 with bias voltages up to 1000 V (equivalent to 32 kV cm^?1). However, a peak at about 18% CCE could be recovered after priming.     

A novel miniature inverted-flame burner for the generation of soot nanoparticles

Lab-scale soot nanoparticle generators are used by the aerosol research community to study the properties of soot over a broad range of particle size distributions, and number and mass concentrations. In this study, a novel miniature inverted-flame burner is presented and its emitted soot particles were characterized. The burner consisted of two co-annular tubes for fuel and co-flow air and the flame was enclosed by the latter. The fuel used was ethylene. A scanning mobility particle sizer (SMPS) and an aerodynamic aerosol classifier (AAC) were used to measure mobility and aerodynamic size distribution of soot particles, respectively. Particle morphology was studied using transmission electron microscopy (TEM). The elemental carbon (EC) and organic carbon (OC) content of the soot were measured using thermal-optical analysis (TOA). The burner produced soot particles with mobility diameter range of 66–270?nm, aerodynamic diameter range of 56–140?nm, and total concentration range of 2?×?10⁵–1?×?10⁷?cm^?3. TEM images showed that most soot particles were sub-micron soot aggregates. Some soot superaggregates, typically larger than 2?µm in length, were observed and their abundance increased with ethylene flow rate. TOA showed that the concentration of EC in the generated soot increased with ethylene flow rate, and the soot was observed to have high EC fraction at high ethylene flow rates. The miniature inverted-flame burner was demonstrated to produce soot nanoparticles over a range of concentrations and sizes with high EC content, making it a practical device to study soot nanoparticle properties in different applications.

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