Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol: Part 1 – Evidence from measurements

Secondary Organic Aerosols (SOA) studied in previous laboratory experiments generally showed only slight hygroscopic growth, but a much better activity as a CCN (Cloud Condensation Nucleus) than indicated by the hygroscopic growth. This discrepancy was examined at LACIS (Leipzig Aerosol Cloud Interaction Simulator), using a portable generator that produced SOA particles from the ozonolysis of α-pinene, and adding butanol or butanol and water vapor during some of the experiments. The light scattering signal of dry SOA-particles was measured by the LACIS optical particle spectrometer and was used to derive a refractive index for SOA of 1.45. LACIS also measured the hygroscopic growth of SOA particles up to 99.6% relative humidity (RH), and a CCN counter was used to measure the particle activation. SOA-particles were CCN active with critical diameters of e.g. 100 nm and 55 nm at super-saturations of 0.4% and 1.1%, respectively. But only slight hygroscopic growth with hygroscopic growth factors ≤1.05 was observed at RH98%, the hygroscopic growth increased stronger than would be expected if a constant hygroscopicity parameter for the particle/droplet solution was assumed. An increase of the hygroscopicity parameter by a factor of 4–6 was observed in the RH-range from below 90% to 99.6%, and this increase continued for increasingly diluted particle solutions for activating particles. This explains an observation already made in the past: that the relation between critical super-saturation and dry diameter for activation is steeper than what would be expected for a constant value of the hygroscopicity. Combining measurements of hygroscopic growth and activation, it was found that the surface tension that has to be assumed to interpret the measurements consistently is greater than 55 mN/m, possibly close to that of pure water, depending on the different SOA-types produced, and therefore only in part accounts for the discrepancy between hygroscopic growth and CCN activity observed for SOA particles in the past

Influences of non-singular stresses on plane-stress near-tip fields for pressure-sensitive materials and applications to transformation toughened ceramics

In this paper, we investigate the effects of the non-singular stress ( T stress) on the mode I near-tip fields for elastic perfectly plastic pressure-sensitive materials under plane-stress and small-scale yielding conditions. The T stress is the normal stress parallel to the crack faces. The yield criterion for pressure-sensitive materials is described by a linear combination of the effective stress and the hydrostatic stress. Plastic dilatancy is introduced by the normality flow rule. The results of our finite element computations based on a two-parameter boundary layer formulation show that the total angular span of the plastic sectors of the near-tip fields increases with increasing T stress for materials with moderately large pressure sensitivity. The T stress also has significant effects on the sizes and shapes of the plastic zones. The height of the plastic zone increases substantially as the T stress increases, especially for materials with large pressure sensitivity. When the plastic strains are considered to be finite as for transformation toughened ceramics, the results of our finite element computations indicate that the phase transformation zones for strong transformation ceramics with large pressure sensitivity can be approximated by those for elastic-plastic materials with no limit on plastic strains. When the T stress and the stress intensity factor K are prescribed in the two-parameter boundary layer formulation to simulate the crack-tip constraint condition for a single-edge notch bend specimen of zirconia ceramics, our finite element computation shows a spear shape of the phase transformation zone which agrees well with the corresponding experimental observation.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/42782/1/10704_2004_Article_BF00018779.pd

Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol - Part 2: Theoretical approaches

We examine the hygroscopic properties of secondary organic aerosol particles generated through the reaction of α-pinene and ozone using a continuous flow reaction chamber. The water activity versus composition relationship is calculated from measurements of growth factors at relative humidities up to 99.6% and from measurements of cloud condensation nuclei activity. The observed relationships are complex, suggesting highly non-ideal behavior for aerosol water contents at relative humidities less than 98%. We present two models that may explain the observed water activity-composition relationship equally well. The first model assumes that the aerosol is a pseudo binary mixture of infinitely water soluble compounds and sparingly soluble compounds that gradually enter the solution as dilution increases. The second model is used to compute the Gibbs free energy of the aerosol-water mixture and shows that the aerosol behaves similarly to what can be expected for single compounds that contain a certain fraction of oxygenated and non-polar functional groups