Closing the ultrafine particle number concentration budget at road-to-ambient scale: Implications for particle dynamics

Freshly emitted vehicle exhaust particles are diluted quickly as they mix into ambient air, but the contribution of evaporation, coagulation, and/or nucleation of new particles to the number concentration has been the subject of some debate. We analyzed one-second time resolution size distribution data from an early morning field campaign, data collected at a time at which dilution has a smaller (but still dominant; ～70?80%) impact on particle concentrations. Because the plume is diluted over an hour, and a distance of 1500 m, we can constrain the processes with higher accuracy. We find that concentrations in the smaller size bins (5.6–23.7 nm) peak further downwind than the reference particles (42.1–562 nm), and decay significantly faster than larger particles particularly in the area 100?400 m downwind. Comparisons of the cumulative contributions of van der Waals enhanced coagulation, dry deposition, and dilution and the observed decay curves, imply that for up to the first 50–100 m there is nucleation and/or growth of particles smaller than 5.6 nm. In contrast, in the ～100–400 m region, some of the smaller particles evaporate. In the further downwind areas (>400 m) the particles all appear to decay at rates consistent with the sum of dilution, coagulation, and deposition. We also find that a dry deposition parameterization at the low end of those available in the literature is most consistent with the observational data.

© 2016 American Association for Aerosol Research     

Ring-opening metathesis polymerisable charged platinum(II) complexes: Towards enhanced phosphorescent quantum yields by aggregation in polymers

Phosphorescent copolymers bearing a covalently linked charged platinum(II) dye were prepared using ring-opening metathesis polymerisation (ROMP). Absorption, emission as well as dynamic light scattering measurements of these polyelectrolytes indicate the formation of red luminescent aggregates in solution with quantum yields up to 17% and luminescence decay times in the range of 250-300 ns. Neither the quantum yield nor lifetime of the luminescence is affected by the presence of oxygen. The resulting polymers are solution processible and exhibit good film-forming properties. In contrast, the mononuclear platinum species are poorly soluble and non-luminescent at room temperature in deaerated solution.     

Change in particle size distribution of aerosol undergoing condensational growth: alternative analytical solution for the low Knudsen number regime

Condensational growth of a polydisperse aerosol was studied employing the moment method of log-normal size distribution function. The previous analytical solution for the size distribution of a condensationally growing aerosol (Park et al., J. Aerosol. Sci. 32 (2001) 187) was extended to cover the low Knudsen number transition regime. In order to cover the transition regime, the harmonic mean method was used for obtaining the transition correction factors for mass and heat fluxes. Comparisons were made with the existing solution and good agreement was obtained.     

Evaluation of the Alphasense optical particle counter (OPC-N2) and the Grimm portable aerosol spectrometer (PAS-1.108)

We compared the performance of a low-cost (～$500), compact optical particle counter (OPC, OPC-N2, Alphasense) to another OPC (PAS-1.108, Grimm Technologies) and reference instruments. We measured the detection efficiency of the OPCs by size from 0.5 to 5 µm for monodispersed, polystyrene latex (PSL) spheres. We then compared number and mass concentrations measured with the OPCs to those measured with reference instruments for three aerosols: salt, welding fume, and Arizona road dust. The OPC-N2 detection efficiency was similar to the PAS-1.108 for particles larger than 0.8 µm (minimum of 79% at 1 µm and maximum of 101% at 3 µm). For 0.5-µm particles, the detection efficiency of the OPC-N2 was underestimated at 78%, whereas PAS-1.108 overestimated concentrations by 183%. The mass concentrations from the OPCs were linear (r ≥ 0.97) with those from the reference instruments for all aerosols, although the slope and intercept were different. The mass concentrations were overestimated for dust (OPC-N2, slope = 1.6; PAS-1.108, slope = 2.7) and underestimated for welding fume (OPC-N2, slope = 0.05; PAS-1.108, slope = 0.4). The coefficient of variation (CV, precision) for OPC-N2 for all experiments was between 4.2% and 16%. These findings suggest that, given site-specific calibrations, the OPC-N2 can provide number and mass concentrations similar to the PAS-1.108 for particles larger than 1 µm.

Copyright © 2016 American Association for Aerosol Research     

Single molecule force spectroscopy of smart poly(ferrocenylsilane) macromolecules: Towards highly controlled redox-driven single chain motors

We investigated various stimuli-responsive poly(ferrocenylsilane) (PFS) polymers as model systems for the realization of molecular motors powered by a redox process. Covalently end-grafted PFS on gold, as well as PFS homopolymers and block copolymers in ultrathin films, were studied by AFM-based single molecule force spectroscopy (SMFS). Surface confined PFS macromolecules were chemically oxidized by addition of tetracyanoethylene or were completely and reversibly oxidized (and reduced) in situ by applying an electrochemical potential. Chemical oxidation was successful only for the block copolymers. The entropic elasticity of neutral PFS chains (Kuhn length I_K∼0.40 nm) was found to be larger than that of oxidized PFS chains (I_K∼0.65 nm) in the lower force regime. The elasticities could be reversibly controlled in situ by adjusting the applied potential in electrochemical SMFS experiments. For a single PFS macromolecule (DP=80) operating cycle, a work output and an efficiency of 3.4×10⁻¹⁹ J and ∼5%, respectively, were estimated based on the single chain experimental data.     

Characterizing the performance of two optical particle counters (Grimm OPC1.108 and OPC1.109) under urban aerosol conditions

The performance of Grimm optical particle counters (OPC, models 1.108 and 1.109) was characterized under urban aerosol conditions. Number concentrations were well correlated. The different lower cut-off diameters (0.25 and 0.3 μm) give an average difference of 23.5%. Both detect less than 10% of the total particle concentration (0.01–1 μm; Differential Mobility Analyzer), but in the respective size ranges, differences are <10%. OPC number size distributions were converted to mass concentrations using instrument-specific factors given by the manufacturer. Mass concentrations for OPC1.108 were 60% higher than for OPC1.109 and (in case of OPC1.109) much lower than those measured with an impactor in the relevant size range or a TSP filter. Using the C-factor correction suggested by the manufacturer, OPC1.109 underestimated mass concentrations by 21% (impactor) and by about 36% (TSP filter), which is in the range of comparability of co-located different mass concentration methods (Hitzenberger, Berner, Maenhaut, Cafmeyer, Schwarz, &; Mueller et al., 2004).     

A new miniature electrical aerosol spectrometer (MEAS): Experimental characterization

Design and theory of a new compact ultrafine particle sizing instrument, called the miniature electrical-mobility aerosol spectrometer (MEAS), was recently introduced [Ranjan, M., & Dhaniyala, S. (2007). A new miniature electrical spectrometer: Theory and design. Journal of Aerosol Science, 39, 950–963]. In the MEAS, electrostatic precipitation technique is used for both generation of sheath flow and classification of particles based on their electrical mobility. An electrometer-array, connected to the collection electrodes in the classifier section, is used to measure the number of particles collected in the different mobility channels, and these data are inverted using MEAS transfer functions to obtain particle number size distributions. Design of a prototype MEAS and the experimental approach to validate the performance of the individual components of the instrument are presented. Particle size distributions obtained from MEAS measurements compare well with those obtained using a scanning mobility particle sizer (SMPS; TSI 3936), validating theoretical calculations of instrument transfer functions. The operational limits of MEAS are determined from the calculation of error in the inverted size distribution as a function of total particle concentration. This analysis suggests that the designed MEAS can be used for applications such as personal and ambient monitoring under conditions of moderate to high particle concentrations.     

Preparation of lead (Pb) X-ray fluorescence reference materials for the EPA Pb monitoring program and the IMPROVE network using an aerosol deposition method

X-ray fluorescence (XRF) is a commonly used analytical method to quantify lead (Pb), a toxic element, in atmospheric aerosol. The commercially available reference materials used for calibrating XRF do not mimic the concentrations and filter materials of particulate matter (PM) monitoring networks. In this study, we described an aerosol deposition method to generate Pb reference materials (RMs) over a range of concentrations to serve several purposes for the US Environmental Protection Agency (EPA) and Interagency Monitoring of PROtected Visual Environments (IMPROVE) monitoring networks including laboratory auditing, federal equivalency method evaluation, and calibration and quality control of XRF instruments. The RMs were generated using a laboratory-built aerosol chamber equipped with a federal reference sampler at concentration levels ranging from 0.0125 to 0.70 μg/m³. XRF analysis at UC Davis was demonstrated to be equivalent to a US and EU reference method, inductively coupled plasma—mass spectrometry (ICP-MS), for measuring Pb on RMs following a methodology described in the United States and international standards. The Pb concentrations on subsets of the RMs were verified by three other XRF laboratories with different analyzers and/or quantification methods and were shown to be equivalent to the UC Davis XRF analysis. The generated RMs were demonstrated to have short and long-term stability, satisfying an additional requirement of reference materials.

Copyright © 2016 American Association for Aerosol Research     

Ammonium phosphate slurry rheology and particle properties—The influence of Fe(III) and Al(III) impurities, solid concentration and degree of neutralization

Ammonium phosphate slurries are produced from impure phosphoric acid that contains Fe(III), Al(III) and Mg(II) ions. The insolubility of these metal ions and the onset of solid formation determined as a function of pH or mole ratio (MR) of ammonia to phosphoric acid were consistent with the trend for the pH of formation of the first hydrolysis product that decreases in the following order: Fe(III)<Al(III)<Mg(II). The hydrolysis products of Fe(III) formed at pH>2.0 or MR>0.5 initiate ammonium phosphate crystallization, reduce the size of particles formed and generate attractive interparticle forces. Similarly, the Al(III) hydrolysis products formed later at pH>2.6 MR>0.7), will also initiate further crystallization, adsorb on particles and produce attractive forces. The attractive forces and the high number concentration of particle—particle interactions are responsible for the increased viscosity and non-Newtonian flow behavior displayed at increasing Fe(III) and Al(III) concentration. Mg(II) ions are not hydrolyzed at MR<1.0 so its effect on rheology is negligible and its effect at MR<1.0 is also small as its concentration is much smaller than that of Fe(III) and Al(III) ions. The change in slurry viscosity with the degree of neutralization is also explained in terms of particle size distribution, solubility and solids concentration variations.     

Kinetic study of calcite particle (powder) thermal decomposition: Part I

In the first step of the firing cycle used to manufacture white-firing wall tile bodies, the calcium carbonate that is added, as a source of CaO, to the clay raw materials mixture used to form these bodies needs to decompose. In order to study the kinetics of this process, a representative rate equation of the chemical reaction step of calcium carbonate thermal decomposition is needed.There is a disparity of opinions regarding the reaction order of this chemical reaction step. For this reason, it was decided to obtain a rate equation for this chemical decomposition step, using the same type and size calcite particles that are usually added to these clay mixtures in industrial practice.The present paper proposes a rate equation for this chemical reaction step. With this rate equation and the application of the “Uniform Conversion Model”, an expression has been derived that relates the fractional calcium carbonate conversion, in the studied calcite particles, to residence time and operating temperature. The equation satisfactorily fits the experimental results obtained under isothermal conditions in the studied temperature range for particles smaller than 100 μm.The calcite particles studied are highly porous aggregates (smaller than 1.1 mm) of very small single crystals (smaller than 20 μm). The experiments were conducted in the 850–950 °C temperature range.     

Silicoaluminophosphate number eighteen (SAPO-18): a new microporous solid acid catalyst

SAPO-18, which has a microporous framework structure related to, but crystallographically distinct from, that of the solid acid catalyst SAPO-34, was synthesized hydrothermally from a silicoaluminophosphate gel containing N,N-diisopropylethylamine as a structuredirecting template. Although both materials have similar Si/(Si + Al + P) ratios, the content of Brønsted acid sites in SAPO-18 is considerably less than that in SAPO-34. As catalysts for methanol conversion to light olefins, SAPO-18 and SAPO-34 have closely similar initial activity and selectivity, but the lifetime of SAPO-18 is distinctly superior to that of SAPO-34.     

The self-assembled nanophase particle (SNAP) process: a nanoscience approach to coatings

In the corrosion protection of aluminum-skinned aircraft, surface pretreatment and cleaning are critical steps in protecting aerospace alloys from corrosion. Our recent discovery of a revolutionary new method of forming functionalized silica nanoparticles in situ in an aqueous-based sol–gel process, and then crosslinking the nanoparticles to form a thin film, is an excellent example of a nanoscience approach to coatings. This coating method is called the self-assembled nanophase particle (SNAP) process.

The SNAP coating process consists of three stages: (1) sol–gel processing; (2) SNAP solution mixing; (3) SNAP coating application and cure. Here, we report on key parameters in the ‘sol–gel processing’ and the ‘coating application and cure’ stages in the GPTMS/TMOS system. The SNAP process is discussed from the formation of the nanosized macromolecules to the coating application and curing process.

The ‘sol–gel processing’ stage involves hydrolysis and condensation reactions and is controlled by the solution pH and water content. Here, the molar ratio of water to hydrolysable silane is a key factor. SNAP solutions have been investigated by NMR, IR, light scattering, and GPC to identify molecular condensation structures formed as a function of aging time in the solution. In moderate pH and high water content solutions, hydrolysis occurs rapidly and condensation kinetic conditions are optimized to generate nanophase siloxane macromolecules.

In the ‘SNAP solution mixing’ stage, crosslinking agents and additives are added to the solution, which is then applied to a substrate by dip-coating to form the SNAP coating. The chemical structure and morphology of the films have been characterized using X-ray diffraction (XRD), time-of-flight secondary ion mass spectrometry (TOF-SIMS) and atomic force microscopy (AFM). SNAP films are amorphous but exhibit nanostructured assembly of siloxane oligomers at a separation of about 1.8 nm as well as molecular level ordering of O–Si–O species. The surface analytical data indicate that the films retain the basic chemical arrangement of the siloxane macromolecules/oligomers and crosslinking process creates a network of siloxane oligomers tethered together. Results of these analyses are then used to construct a model of the SNAP coating. Results of these analyses are discussed in detail.     

Thermosensitive poly(allylamine)-g-poly(N-isopropylacrylamide): synthesis, phase separation and particle formation

Grafting of poly(N-isopropylacrylamide) (PNIPAAm) having carboxylic groups at one end onto poly(allylamine) (PAH) in the presence of water soluble carbodiimide has yielded PAH-g-PNIPAAm copolymers with grafting ratios of 50, 29 and 18, respectively. These thermosensitive copolymers exhibit a lower critical solution temperature (LCST) at 34 °C at a temperature increase cycle regardless of their grafting ratios, a temperature identical to that of PNIPAAm-COOH oligomers. Temperature cycling reveals completely reversible polymer aggregation and dissolution above and below the LCST, respectively. Much smaller particle sizes are observed by scanning force microscopy and transmission electron microscopy compared to dynamic light scattering. A porous sphere model is suggested to depict the structure of the particles formed above the LCST, by which the dependence of the particle sizes on their grafting ratios is interpreted taking into account the surface tension and the spatial aggregation distance. Finally, to demonstrate the capability of the copolymers being used as thermosensitive polyelectrolytes, assembly onto multilayers is conducted and the increase of layer thickness is confirmed by small angle X-ray scattering and ellipsometry characterizations.     

Towards continuous junction (CJ) organic electronic devices: Fast and clean post-polymerization modification by oxidation using dimethyldioxirane (DMDO)

An advanced design concept for organic electronic devices relying on functional polymers is presented. The concept aims at realizing a gradual transition from an electron-donating to an electron-accepting material in a specific post-polymerization modification step. Hence, this approach facilitates a straight forward fabrication compared to conventional multi-layer architectures. The synthesis via microwave-assisted Cu(I)-catalyzed azide–alkyne cycloaddition of the reactive polymers based on sulfur, selenium and tellurium as active sites is presented; full characterization of model compounds and polymers is provided. Additionally, a reliable procedure for post-polymerization oxidation applying dimethyldioxirane is developed. Photophysical and electrochemical characteristics of the novel polymers reveal the feasibility but also the challenges of the continuous junction concept.     

Towards a protocol for solution structure determination of copper(II) proteins: the case of Cu(II)Zn(II) superoxide dismutase

We have developed an optimized protocol to solve the solution structure of copper(II) proteins. After assignment, proton-proton NOEs are used for the shell where 1H spectra are conveniently observed. In a shell closer to the metal ion, 13C NMR spectra with band-selective homonuclear decoupling provide the assignment of all nuclei except for those of the metal ligands. A convenient method for the measurement of 13C longitudinal-relaxation rates (R1) of carbonyls and carboxylate moieties is proposed. 1H NOEs and 1H and 13C R1 data are sufficient to produce a good/reasonable solution structure, as demonstrated for a monomeric species of superoxide dismutase, a 153-residue protein.     

玻璃纤维无捻粗纱(GBT 18369--2001)2

3.2线密度 本标准规定线密度的允差C类为±8%,变异系数≤6%;W类为±5%,变异系数为5%.试验验证如表2所示.     

Computer-controlled Raman microspectroscopy (CC-Raman): A method for the rapid characterization of individual atmospheric aerosol particles

The ability of an atmospheric aerosol particle to impact climate by acting as a cloud condensation nucleus (CCN) or an ice nucleus (IN), as well as scatter and absorb solar radiation is determined by its physicochemical properties at the single particle level, specifically size, morphology, and chemical composition. The identification of the secondary species present in individual aerosol particles is important as aging, which leads to the formation of these species, can modify the climate relevant behavior of particles. Raman microspectroscopy has a great deal of promise for identifying secondary species and their mixing with primary components, as it can provide detailed information on functional groups present, morphology, and internal structure. However, as with many other detailed spectroscopic techniques, manual analysis by Raman microspectroscopy can be slow, limiting single particle statistics and the number of samples that can be analyzed. Herein, the application of computer-controlled Raman (CC-Raman) for detailed physicochemical analysis that increases throughput and minimizes user bias is described. CC-Raman applies automated mapping to increase analysis speed allowing for up to 100 particles to be analyzed in an hour. CC-Raman is applied to both laboratory and ambient samples to demonstrate its utility for the analysis of both primary and, most importantly, secondary components (sulfate, nitrate, ammonium, and organic material). Reproducibility and precision are compared to computer controlled-scanning electron microscopy (CCSEM). The greater sample throughput shows the potential for CC-Raman to improve particle statistics and advance our understanding of aerosol particle composition and mixing state, and, thus, climate-relevant properties.

© 2017 American Association for Aerosol Research