Films of Graphene Nanomaterials Formed by Ultrasonic Spraying of Their Stable Suspensions

<div><p>Graphene, a two-dimensional carbon allotrope, exhibits excellent optoelectronic properties. The assembly of graphene into films provides a platform to deepen the study of its interaction with varying surfaces, to engineer devices, and to develop functional materials. A general approach to produce graphene films consists of preparing a dispersion and laying it on a substrate of choice, followed by solvent evaporation. Here, we report the preparation of stable suspensions of new types of graphene nanomaterials namely, graphene nanoflowers (GNFs) and multi-layer graphene (MLG) flakes, in ethanol, <i>N</i>,<i>N</i>-dimethylformamide (DMF), and <i>N</i>-methyl-2-pyrrolidone (NMP). Sprayable suspensions of both GNFs and MLG were prepared in DMF/ethanol, which showed high stability, without addition of any surfactant. The stable suspensions were used to deposit micrometer-thick MLG/GNF films on glass substrates. Calculations of initial droplet size and of timescale of droplet evaporation are performed and possible thermophoretic effects on droplet deposition discussed as well. Coating glass substrates with a methacrylic acid–methyl methacrylate (MA) copolymer prior to the deposition significantly improved the adhesion of the nanomaterials to the substrate. With the MA coating, a substrate coverage of nearly 100% was achieved at 14-min spraying time for 0.05 wt% GNF and 0.1 wt% MLG suspensions. Raman spectra of the GNF and MLG films reveal that the films were made of MLG in which the individual graphene layers rotated from each other as in turbostratic graphene. This work provides a general approach to prepare graphene nanomaterial suspensions and to create films for a variety of applications. The spraying process applied in the current work is highly scalable and allows control of film characteristics through process parameters.</p><p>Copyright 2015 American Association for Aerosol Research</p></div

Effective Density and Morphology of Particles Emitted from Small-Scale Combustion of Various Wood Fuels

The effective density of fine particles emitted from small-scale wood combustion of various fuels were determined with a system consisting of an aerosol particle mass analyzer and a scanning mobility particle sizer (APM-SMPS). A novel sampling chamber was combined to the system to enable measurements of highly fluctuating combustion processes. In addition, mass-mobility exponents (relates mass and mobility size) were determined from the density data to describe the shape of the particles. Particle size, type of fuel, combustion phase, and combustion conditions were found to have an effect on the effective density and the particle shape. For example, steady combustion phase produced agglomerates with effective density of roughly 1 g cm^–3 for small particles, decreasing to 0.25 g cm^–3 for 400 nm particles. The effective density was higher for particles emitted from glowing embers phase (ca. 1–2 g cm^–3), and a clear size dependency was not observed as the particles were nearly spherical in shape. This study shows that a single value cannot be used for the effective density of particles emitted from wood combustion

Real-Time Chemical Composition Analysis of Particulate Emissions from Woodchip Combustion

Residential wood combustion is one of the major sources of fine particles. The chemical composition of the particles plays a key role in both adverse health and environmental effects. It is important to understand how chemical composition of particulate emissions varies during different combustion processes and conditions. In this work, combustion of wood chips was studied in a moving step-grate burner in different combustion conditions (efficient, intermediate, and smoldering) in the laboratory. The particulate emissions were measured with an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-TOF-AMS). It was found that two phases were occurring frequently in the intermediate and smoldering combustion. Phase 1 took place when gaseous carbon monoxide (CO) was rapidly increasing after the new fuel addition. Phase 2 was a stable, burn-out period with low CO emissions until the new fuel addition and automatic removal of fuel leftovers from the grate. The analysis on the organic aerosol by positive matrix factorization (PMF) extracted out five factors: hydrocarbon-like organic aerosol (HOA), low-volatile-oxidized organic aerosol (LV-OOA), biomass burning organic aerosol (BBOA), and two additional factors of “polycyclic aromatic hydrocarbon (PAH) factor” and “aromatic factor”. PAH and LV-OOA were found to be forming mainly during phase 1. HOA showed similar behavior as a PAH factor and LV-OOA in a time series. BBOA was consistent with levoglucosan formation during the combustion and became higher during phase 2. The aromatic factor was mainly composed of fragment ions of <i>n</i>-butyl benzenesulfonamide compound, which was observed in both phases. To our knowledge, this is the first work to report the particulate organics of combustion aerosols and PAH distinguished by PMF. The results prove that the particulate organic emissions can be reduced efficiently when keeping combustion efficiency high. This may help in targeting the efforts on emission reduction better in the future

Experimental set-up and global omics analyses.

<p>(A) An 80 KW common-rail-ship diesel engine was operated with heavy fuel oil (HFO) or refined diesel fuel (DF). The exhaust aerosols were diluted and cooled with clean air. On-line real-time mass spectrometry, particle-sizing, sensor IR-spectrometry and other techniques were used to characterise the chemical composition and physical properties of the particles and gas phase. Filter sampling of the particulate matter (PM) was performed to further characterise the PM composition. Lung cells were synchronously exposed at the air-liquid-interface (ALI) to aerosol or particle-filtered aerosol as a reference. The cellular responses were characterised in triplicate at the transcriptome (BEAS-2B), proteome and metabolome (A549) levels with stable isotope labelling (SILAC and ¹³C₆-glucose). (B) Heatmap showing the global regulation of the transcriptome, proteome and metabolome.</p

Summary of the main HFO- and DF-particle exposure effects.

<p>The arrows indicate the direction of regulation for cellular functions derived from the most statistically significant enriched Gene Ontology terms from the transcriptome, proteome, and metabolome (details in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0126536#pone.0126536.s012" target="_blank">S2 Table</a>).</p><p>^x BEAS-2B up, A549 down</p><p>* BEAS-2B down, A549 up</p><p>Summary of the main HFO- and DF-particle exposure effects.</p

Chemical and physical aerosol characterisation.

<p>(A) The ship diesel engine was operated for 4 h in accordance with the IMO-test cycle. (B) Approximately 28 ng/cm² and 56 ng/cm² were delivered to the cells from DF and HFO, respectively, with different size distributions. The HFO predominantly contained particles <50 nm, and the DF predominantly contained particles >200 nm, both in mass and number. (C) Number of chemical species in the EA particles. (D) Transmission electron microscope (TEM) images and energy-dispersive X-ray (EDX) spectra of DF-EA and HFO-EA; heavy elements (black speckles, arrow); and contributions of the elements V, P, Fe and Ni in the HFO particles using EDX (* = grid-material). (E) Exemplary EA concentrations (right) and concentration ratios (left) for particulate matter-bound species. For all experiments, n = 3.</p

Effects of shipping particles on lung cells.

<p>The net effects from the particles were referenced against the gaseous phase of the emissions. (A) Number of the regulated components in the transcriptome shows more genes regulated by the DF than the HFO particles (in BEAS-2B cells). Similar results were observed for the proteome (B) and metabolome (C) (in A549 cells). (D) Meta-analyses for the transcriptome and proteome using the combined Gene Ontology (GO) term analysis of the 10% most regulated transcripts and proteins. Individual GO terms are listed in <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0126536#pone.0126536.s012" target="_blank">S2 Table</a>; the hierarchical pathways are indicated on the right. (E) Gene regulation of Wiki-pathway bioactivation; (F) gene regulation of Wiki-pathway inflammation; g, secreted metabolites; and h, metabolic flux measurements using ¹³C-labelled glucose. For all experiments, n = 3.</p