How the development of condensation particle counters is reforming our view on atmospheric nucleation

Aerosol particles deteriorate air quality, atmospheric visibility and our health. They affect the Earth s climate by absorbing and scattering sunlight, forming clouds, and also via several feed-back mechanisms. The net effect on the radiative balance is negative, i.e. cooling, which means that particles counteract the effect of greenhouse gases. However, particles are one of the poorly known pieces in the climate puzzle. Some of the airborne particles are natural, some anthropogenic; some enter the atmosphere in particle form, while others form by gas-to-particle conversion. Unless the sources and dynamical processes shaping the particle population are quantified, they cannot be incorporated into climate models. The molecular level understanding of new particle formation is still inadequate, mainly due to the lack of suitable measurement techniques to detect the smallest particles and their precursors. This thesis has contributed to our ability to measure newly formed particles. Three new condensation particle counter applications for measuring the concentration of nano-particles were developed. The suitability of the methods for detecting both charged and electrically neutral particles and molecular clusters as small as 1 nm in diameter was thoroughly tested both in laboratory and field conditions. It was shown that condensation particle counting has reached the size scale of individual molecules, and besides measuring the concentration they can be used for getting size information. In addition to atmospheric research, the particle counters could have various applications in other fields, especially in nanotechnology. Using the new instruments, the first continuous time series of neutral sub-3 nm particle concentrations were measured at two field sites, which represent two different kinds of environments: the boreal forest and the Atlantic coastline, both of which are known to be hot-spots for new particle formation. The contribution of ions to the total concentrations in this size range was estimated, and it could be concluded that the fraction of ions was usually minor, especially in boreal forest conditions. Since the ionization rate is connected to the amount of cosmic rays entering the atmosphere, the relative contribution of neutral to charged nucleation mechanisms extends beyond academic interest, and links the research directly to current climate debate.

A transmission electron microscopy and X-ray photoelectron spectroscopy study of annealing induced gamma-phase nucleation, clustering, and interfacial dynamics in reactively sputtered amorphous alumina thin films

Pure alpha-Al2O3 exhibits a very high degree of thermodynamical stability among all metal oxides and forms an inert oxide scale in a range of structural alloys at high temperatures. We report that amorphous Al2O3 thin films sputter deposited over crystalline Si instead show a surprisingly active interface. On annealing, crystallization begins with nuclei of a phase closely resembling gamma-Alumina forming almost randomly in an amorphous matrix, and with increasing frequency near the substrate/film interface. This nucleation is marked by the signature appearance of sharp (400) and (440) reflections and the formation of a diffuse diffraction halo with an outer maximal radius of approximate to 0.23 nm enveloping the direct beam. The microstructure then evolves by a cluster-coalescence growth mechanism suggestive of swift nucleation and sluggish diffusional kinetics, while locally the Al ions redistribute slowly from chemisorbed and tetrahedral sites to higher anion coordinated sites. Chemical state plots constructed from XPS data and simple calculations of the diffraction patterns from hypothetically distorted lattices suggest that the true origins of the diffuse diffraction halo are probably related to a complex change in the electronic structure spurred by the a-gamma transformation rather than pure structural disorder. Concurrent to crystallization within the film, a substantially thick interfacial reaction zone also builds up at the film/substrate interface with the excess Al acting as a cationic source. (C) 2015 AIP Publishing LLC.

Nucleation, growth, and control of ferroelectric-ferroelastic domains in thin polycrystalline films

The unique response of ferroic materials to external excitations facilitates them for diverse technologies, such as nonvolatile memory devices. The primary driving force behind this response is encoded in domain switching. In bulk ferroics, domains switch in a two-step process: nucleation and growth. For ferroelectrics, this can be explained by the Kolmogorov-Avrami-Ishibashi (KAI) model. Nevertheless, it is unclear whether domains remain correlated in finite geometries, as required by the KAI model. Moreover, although ferroelastic domains exist in many ferroelectrics, experimental limitations have hindered the study of their switching mechanisms. This uncertainty limits our understanding of domain switching and controllability, preventing thin-film and polycrystalline ferroelectrics from reaching their full technological potential. Here we used piezoresponse force microscopy to study the switching mechanisms of ferroelectric-ferroelastic domains in thin polycrystalline Pb 0.7Zr0.3TiO3 films at the nanometer scale. We have found that switched biferroic domains can nucleate at multiple sites with a coherence length that may span several grains, and that nucleators merge to form mesoscale domains, in a manner consistent with that expected from the KAI model. © 2012 American Physical Society.

Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

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Quantum Mechanics Insight into the Microwave Nucleation of SrTiO3 Nanospheres

An extensive investigation of strontium titanate, SrTiO3 (STO), nanospheres synthesized via a microwave-assisted hydrothermal (MAH) method has been conducted to gain a better insight into thermodynamic, kinetic, and reaction phenomena involved in STO nucleation and crystal growth processes. To this end, quantum chemical modeling based on the density functional theory and periodic super cell models were done. Several experimental techniques were employed to get a deep characterization of structural and optical features of STO nanospheres. A possible formation mechanism was proposed, based on dehydration of titanium and strontium clusters followed by mesoscale transformation and a self-assembly process along an oriented attachment mechanism resulting in spherical like shape. Raman and XANES analysis renders a noncentrosymmetric environment for the octahedral titanium, while infrared and first order Raman modes reveal OH groups which are unsystematically incorporated into uncoordinated superficial sites. These results seem to indicate that the key component is the presence of distorted TiO6 clusters to engender a luminescence property. Analysis of band structure, density Of states, and charge map shows that there is a close relationship among local broken symmetry, polarization, and energy split of the 3d orbitals of titanium. The interplay among these electronic and structural features provides necessary conditions to evaluate its luminescent properties under two energy excitation.

Distribution of foraminifera and other components in ODP Leg 188 sites

During Leg 188 of the Ocean Drilling Program (ODP), employing JOIDES Resolution, we drilled holes at three sites in the southern Indian Ocean in and near Prydz Bay, East Antarctica, between 28 January and 29 February 2000. The objectives of the voyage were to: - Core through sediments deposited when Antarctica underwent the transition from "greenhouse" to the modern "icehouse" state late in the Eocene or early in the Oligocene, at sites obtaining their sediment from the currently subglacial Gamburtsev Mountains that probably were the site of nucleation of the ice sheet (principally Site 1166); - Obtain a sediment record from times at which major changes in the ice sheet volume and characteristics took place as judged from oxygen isotope records, especially at ~23.7 Ma (Oligocene/Miocene boundary), 12-16 Ma (middle Miocene), and 2.7 Ma (late Pliocene) (mainly Site 1165); and - Sample through the upper Pliocene and Quaternary in an attempt to document fluctuations in the extent of the ice sheet over the continental shelf during the Quaternary (especially Site 1167). Paleogene foraminifer-bearing marine sections were not intersected, and thus discussion of marine sections is restricted to the Neogene. Foraminifers are not major contributors to Leg 188 chronostratigraphy but contribute to paleoenvironmental interpretation, to issues such as carbonate compensation depth (CCD) effects and source and history of sediment, and provide a basis for Sr and d18O studies. Chronostratigraphy for the various sections was compiled from diatoms, radiolarians, and paleomagnetism (Shipboard Scientific Party, 2001, doi:10.2973/odp.proc.ir.188.101.2001). Foraminifers were sporadic rather than continuous except in short intervals; however, the Neogene foraminifers from the region are very poorly known and the new records proved to be of significant value in paleoenvironmental interpretation. Only at Site 1167 did drilling intersect a section that yielded foraminifers virtually throughout. Other than for the very young section at each site, there is virtually no continuity of assemblages between sites and thus each section is treated here as separate and unrelated.

(Table 1) Pore-water composition of ODP Leg 126 sites

The Ocean Drilling Program Leg 126 sites may be classified into two categories depending on the presence (Group I: Sites 787, 792, and 793) or absence (Group II: Sites 788, 790, and 791) of steep concentration gradients. Shipboard X-ray diffraction analyses of bulk sediments from Group I sites revealed the presence of a number of diagenetic minerals (some of which are incompatible), but no systematic diagenetic zonation. The results of the chemical analyses of the pore waters from Group I have been used to estimate the activities of dissolved species. Thermodynamic analyses of the composition of the pore waters and the stability of authigenic minerals (gypsum, zeolites, feldspars, smectites, chlorites, and micas) show that the pore waters are close to equilibrium with most of the observed phases. Thus, only a small perturbation of the system (substitution in minerals and fluctuations in pore-water composition, in particular, in pH and SiO2 activity) will cause any of these phases to precipitate. Therefore, one would not expect mineralogical observations to show systematic vertical zonations at these sites. It is suggested that chlorites and high-temperature zeolites are not diagenetic sensu stricto, but were eroded from volcaniclastic highs. The absence of concentration gradients at the Group II sites has been analyzed in terms of reaction kinetics, hydrothermal advection, and temperature distribution. The absence of diagenetic imprints on the pore-water concentration profiles at these sites is probably caused by the slow nucleation of silica phases.

An investigation of nucleation events in a coastal urban environment in the southern hemisphere

The occurrence of and conditions favourable to nucleation were investigated at an industrial and commercial coastal location in Brisbane, Australia during five different campaigns covering a total period of 13 months. To identify potential nucleation events, the difference in number concentration in the size range 14-30 nm (N14-30) between consecutive observations was calculated using first-order differencing. The data showed that nucleation events were a rare occurrence, and that in the absence of nucleation the particle number was dominated by particles in the range 30-300 nm. In many instances, total particle concentration declined during nucleation. There was no clear pattern in change in NO and NO2 concentrations during the events. SO2 concentration, in the majority of cases, declined during nucleation but there were exceptions. Most events took place in summer, followed by winter and then spring, and no events were observed for the autumn campaigns. The events were associated with sea breeze and long-range transport. Roadside emissions, in contrast, did not contribute to nucleation, probably due to the predominance of particles in the range 50-100 nm associated with these emissions.

Size distribution and sites of origin of droplets expelled 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. That mode occurred during all respiratory activities, including normal breathing. A second mode at 1.8 µm was produced during all activities, but at lower concentrations.----- Speech produced particles in modes near 3.5 µm and 5 µm. The modes became most pronounced during continuous vocalization, suggesting that the aerosolization of secretions lubricating the vocal chords is a major source of droplets in terms of number.----- Non-eqilibrium 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.