A bulk nanostructured alloy with the nominal composition Cu–30Zn–0.8Al wt.% (commercial designation brass 260) was fabricated by cryomilling of brass powders and subsequent spark plasma sintering ...(SPS) of the cryomilled powders, yielding a compressive yield strength of 950MPa, which is significantly higher than the yield strength of commercial brass 260 alloys (∼200–400MPa). Transmission electron microscopy investigations revealed that cryomilling results in an average grain diameter of 26nm and a high density of deformation twins. Nearly fully dense bulk samples were obtained after SPS of cryomilled powders, with average grain diameter 110nm. After SPS, 10vol.% of twins is retained with average twin thickness 30nm. Three-dimensional atom-probe tomography studies demonstrate that the distribution of Al is highly inhomogeneous in the sintered bulk samples, and Al-containing precipitates including Al(Cu,Zn)–O–N, Al–O–N and Al–N are distributed in the matrix. The precipitates have an average diameter of 1.7nm and a volume fraction of 0.39%. Quantitative calculations were performed for different strengthening contributions in the sintered bulk samples, including grain boundary, twin boundary, precipitate, dislocation and solid-solution strengthening. Results from the analyses demonstrate that precipitate and grain boundary strengthening are the dominant strengthening mechanisms, and the calculated overall yield strength is in reasonable agreement with the experimentally determined compressive yield strength.
To provide insight into the relationships between precipitation phenomena, grain size and mechanical behavior in a complex precipitation-strengthened alloy system, Al 7075 alloy, a commonly used ...aluminum alloy, was selected as a model system in the present study. Ultrafine-grained (UFG) bulk materials were fabricated through cryomilling, degassing, hot isostatic pressing and extrusion, followed by a subsequent heat treatment. The mechanical behavior and microstructure of the materials were analyzed and compared directly to the coarse-grained (CG) counterpart. Three-dimensional atom-probe tomography was utilized to investigate the intermetallic precipitates and oxide dispersoids formed in the as-extruded UFG material. UFG 7075 exhibits higher strength than the CG 7075 alloy for each equivalent condition. After a T6 temper, the yield strength (YS) and ultimate tensile strength (UTS) of UFG 7075 achieved 734 and 774MPa, respectively, which are ∼120MPa higher than those of the CG equivalent. The strength of as-extruded UFG 7075 (YS: 583MPa, UTS: 631MPa) is even higher than that of commercial 7075-T6. More importantly, the strengthening mechanisms in each material were established quantitatively for the first time for this complex precipitation-strengthened system, accounting for grain-boundary, dislocation, solid-solution, precipitation and oxide dispersoid strengthening contributions. Grain-boundary strengthening was the predominant mechanism in as-extruded UFG 7075, contributing a strength increment estimated to be 242MPa, whereas Orowan precipitation strengthening was predominant in the as-extruded CG 7075 (∼102MPa) and in the T6-tempered materials, and was estimated to contribute 472 and 414MPa for CG-T6 and UFG-T6, respectively.
The substantial uncertainty in the indirect effect of aerosol particles on radiative forcing in large part arises from the influences of atmospheric aerosol particles on (i) the brightness of clouds, ...exerting significant shortwave cooling with no appreciable compensation in the long wave, and on (ii) their ability to precipitate, with implications for cloud cover and lifetime. Predicting the ambient conditions at which aerosol particles may become cloud droplets is largely reliant on an equilibrium relationship derived by Köhler (1936). However, the theoretical basis of the relationship restricts its application to particles solely comprising involatile compounds and water, whereas a substantial fraction of particles in the real atmosphere will contain potentially thousands of semi-volatile organic compounds in addition to containing semi-volatile inorganic components such as ammonium nitrate. We show that equilibration of atmospherically reasonable concentrations of organic compounds with a growing particle as the ambient humidity increases has potentially larger implications on cloud droplet formation than any other equilibrium compositional dependence, owing to inextricable linkage between the aerosol composition, a particles size and concentration under ambient conditions. Whilst previous attempts to account for co-condensation of gases other than water vapour have been restricted to one inorganic condensate, our method demonstrates that accounting for the co-condensation of any number of organic compounds substantially decreases the saturation ratio of water vapour required for droplet activation. This effect is far greater than any other compositional dependence; more so even than the unphysical effect of surface tension reduction in aqueous organic mixtures, ignoring differences in bulk and surface surfactant concentrations.
In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and ...particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.
Key Points
Particulate organic nitrate is ubiquitous in Europe
The 34 to 44 percent of fine particulate nitrate is organic
Nighttime chemistry is a dominant source of particulate organic nitrates
We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at ...room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl−, Br−, NO3−, HSO4−, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.
Aerosol-cloud interactions constitute the largest source of uncertainty in global radiative forcing estimates, hampering our understanding of climate evolution. Recent empirical evidence suggests ...surface tension depression by organic aerosol to significantly influence the formation of cloud droplets, and hence cloud optical properties. In climate models, however, surface tension of water is generally assumed when predicting cloud droplet concentrations. Here we show that the sensitivity of cloud microphysics, optical properties and shortwave radiative effects to the surface phase are dictated by an interplay between the aerosol particle size distribution, composition, water availability and atmospheric dynamics. We demonstrate that accounting for the surface phase becomes essential in clean environments in which ultrafine particle sources are present. Through detailed sensitivity analysis, quantitative constraints on the key drivers - aerosol particle number concentrations, organic fraction and fixed updraft velocity - are derived for instances of significant cloud microphysical susceptibilities to the surface phase.
A large fraction of atmospheric organic aerosol (OA) originates from natural emissions that are oxidized in the atmosphere to form secondary organic aerosol (SOA). Isoprene (IP) and monoterpenes (MT) ...are the most important precursors of SOA originating from forests. The climate impacts from OA are currently estimated through parameterizations of water uptake that drastically simplify the complexity of OA. We combine laboratory experiments, thermodynamic modeling, field observations, and climate modeling to (1) explain the molecular mechanisms behind RH‐dependent SOA water‐uptake with solubility and phase separation; (2) show that laboratory data on IP‐ and MT‐SOA hygroscopicity are representative of ambient data with corresponding OA source profiles; and (3) demonstrate the sensitivity of the modeled aerosol climate effect to assumed OA water affinity. We conclude that the commonly used single‐parameter hygroscopicity framework can introduce significant error when quantifying the climate effects of organic aerosol. The results highlight the need for better constraints on the overall global OA mass loadings and its molecular composition, including currently underexplored anthropogenic and marine OA sources.
Plain Language Summary
The interaction of airborne particulate matter (“aerosols”) with water is of critical importance for processes governing climate, precipitation, and public health. It also modulates the delivery and bioavailability of nutrients to terrestrial and oceanic ecosystems. We present a microphysical explanation to the humidity‐dependent water uptake behavior of organic aerosol, which challenges the highly simplified theoretical descriptions used in, e.g., present climate models. With the comprehensive analysis of laboratory data using molecular models, we explain the microphysical behavior of the aerosol over the range of humidity observed in the atmosphere, in a way that has never been done before. We also demonstrate the presence of these phenomena in the ambient atmosphere from data collected in the field. We further show, using two state‐of‐the‐art climate models, that misrepresenting the water affinity of atmospheric organic aerosol can lead to significant biases in the estimates of the anthropogenic influence on climate.
Key Points
Phase separation effects explain differences in water affinity of biogenic secondary organic aerosol (SOA) at subsaturation and supersaturation
Laboratory data for monoterpene and isoprene SOA are representative of field observations with corresponding gas‐phase organic profiles
Importance of organic aerosol‐water interactions for global climate is governed by highly uncertain organic aerosol budgets
The physical and mechanical characteristics of cryomilled Al 5083-boron carbide (Al-B4C) metal matrix composites (MMCs) render them both scientifically interesting as well as technologically ...important. Trimodal architectures (containing three components, nano/ultrafine grains, coarse grains and ceramic reinforcements) allow for multiple degrees of freedom in the design of the microstructures that can be engineered, for example, to achieve combinations of strength, ductility and damage resistance that are not attainable with conventional materials. Various manufacturing strategies have been formulated to fabricate trimodal MMCs. Among these, cryomilling, which involves mechanical milling in a cryogenic liquid slurry (e.g., nitrogen), has been widely studied because in addition to minimizing recovery during the formation of nanocrystalline grains, it facilitates the incorporation of reinforcement particles in the metal matrix. In this study, novel trimodal composites reinforced with faceted, submicron (~500nm), commercially-available B4C with varying volume fractions of coarse grain phase (0–30%) were fabricated. Within this class of engineering materials ultimate tensile strengths of 620–760MPa and tensile elongations of 1.8–3.7% are observed. The microstructural features are investigated in depth, the strengthening mechanisms quantitatively evaluated and the mechanisms for enhancing strength and/or ductility are discussed.
In this paper we present improved methods for discriminating and quantifying primary biological aerosol particles (PBAPs) by applying hierarchical agglomerative cluster analysis to multi-parameter ...ultraviolet-light-induced fluorescence (UV-LIF) spectrometer data. The methods employed in this study can be applied to data sets in excess of 1 × 106 points on a desktop computer, allowing for each fluorescent particle in a data set to be explicitly clustered. This reduces the potential for misattribution found in subsampling and comparative attribution methods used in previous approaches, improving our capacity to discriminate and quantify PBAP meta-classes. We evaluate the performance of several hierarchical agglomerative cluster analysis linkages and data normalisation methods using laboratory samples of known particle types and an ambient data set. Fluorescent and non-fluorescent polystyrene latex spheres were sampled with a Wideband Integrated Bioaerosol Spectrometer (WIBS-4) where the optical size, asymmetry factor and fluorescent measurements were used as inputs to the analysis package. It was found that the Ward linkage with z-score or range normalisation performed best, correctly attributing 98 and 98.1 % of the data points respectively. The best-performing methods were applied to the BEACHON-RoMBAS (Bio–hydro–atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen–Rocky Mountain Biogenic Aerosol Study) ambient data set, where it was found that the z-score and range normalisation methods yield similar results, with each method producing clusters representative of fungal spores and bacterial aerosol, consistent with previous results. The z-score result was compared to clusters generated with previous approaches (WIBS AnalysiS Program, WASP) where we observe that the subsampling and comparative attribution method employed by WASP results in the overestimation of the fungal spore concentration by a factor of 1.5 and the underestimation of bacterial aerosol concentration by a factor of 5. We suggest that this likely due to errors arising from misattribution due to poor centroid definition and failure to assign particles to a cluster as a result of the subsampling and comparative attribution method employed by WASP. The methods used here allow for the entire fluorescent population of particles to be analysed, yielding an explicit cluster attribution for each particle and improving cluster centroid definition and our capacity to discriminate and quantify PBAP meta-classes compared to previous approaches.
The metabolic end products of the large bowel microbiota contribute significantly to human health. After weaning to solid foods, some of the most important of these are the short chain fatty acids ...(SCFA) produced by the fermentation of undigested dietary components and endogenous secretions. The main SCFA are acetate, propionate and butyrate which have numerous documented effects promoting large bowel function. Of the major acids, butyrate seems especially important. It is a major metabolic fuel for colonocytes and promotes a normal phenotype in these cells, potentially lowering the risk of diseases such as colo-rectal cancer. Imbalances in the microbiota are thought to predispose to large bowel dysfunction and probiotics are being developed to correct this. However, most commercial products contain bacteria (lactobacilli and bifidobacteria) which are dominant species in milk-fed infants but have limited roles in adults. Prebiosis is defined usually by the specific stimulation of these bacteria. However, the end products of most probiotics do not include butyrate or propionate which raises questions about their effectiveness in promoting bowel health in adults. Resistant starch (RS) is a dietary fibre component and its fermentation generally favours butyrate production. Dietary RS intakes and faecal butyrate levels are high in populations at low risk of diet-related large bowel diseases. Conversely, RS intakes and faecal butyrate levels are very low in high risk groups. This raises the possibility that greater RS consumption could be of health benefit. RS is not regarded widely as a prebiotic but (according to the accepted definition) most forms show the requisite features in stimulating specific bacteria, giving raised total SCFA and butyrate levels and a consequent benefit to the host. Current efforts to improve public health through increasing RS consumption could be facilitated by greater recognition of its prebiotic role.
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