Rory M. Power

The transition from liquid to solid-like behaviour in ultrahigh viscosity aerosol particles

For the first time, a measurement of the viscosity of microparticles composed of Newtonian fluids has been made over a range of 12 orders of magnitude (10−3 to 109 Pa s), extending from dilute aqueous solutions to the solid-like behaviour expected on approaching a glass transition. Using holographic optical tweezers to induce coalescence between two aerosol particles (volume <500 femtolitres), we observe the composite particle relax to a sphere over a timescale from 10−7 to 105 s, dependent on viscosity. The damped oscillations in shape illustrate the interplay of surface capillary forces and bulk fluid flow as the relaxation progresses. Viscosity values estimated from the extrapolation of measurements from macroscopic binary aqueous solutions of sucrose are shown to diverge from the microparticle measurements by as much as five orders of magnitude in the limit of ultrahigh solute supersaturation and viscosity. This is shown to be a consequence of the sensitivity of the viscosity to the composition of the particles, specifically the water content, and the often incorrect compositional dependence on water activity that are assumed to characterise aerosols and amorphous phases under dry conditions. For ternary mixtures of sodium chloride, sucrose and water, the measured viscosities similarly diverge from model predictions by up to three orders of magnitude. The Stokes–Einstein treatment for relating the diffusivity of water in sucrose droplets to the particle viscosity is found to depart from the measured viscosities by more than one order of magnitude when the viscosity exceeds 10 Pa s and up to six orders of magnitude at the highest viscosities accessed. Coalescence is shown to proceed with unit efficiency even up to the highest accessible viscosity. These measurements provide the first comprehensive account of the change in a material property accompanying a transition from a dilute solution to an amorphous semi-solid state using aerosol particles to probe the change in rheological properties.

Effect of crystallization kinetics on the properties of spray dried microparticles

ABSTRACT A droplet chain technique was used to study the influence of the crystallization process on the morphology of spray dried microparticles. A piezoceramic dispenser produced a chain of monodisperse solution droplets with an initial diameter in the range of 60–80 µm. Aqueous solutions of sodium nitrate were prepared in concentrations ranging from 5 mg/ml to 5⋅10−5 mg/ml. The solution droplets were injected into a laminar flow with gas temperatures varying from 25 to 150°C, affecting the droplet temperature and the evaporation rate, accordingly. Dried particles with diameters between 0.3 and 18 µm were collected. The properties of the collected microparticles were studied and correlated with a particle formation model which predicted the onset of saturation and crystallization. The model accounted for the dependence of the diffusion coefficient of sodium nitrate in water on droplet viscosity. The viscosity trend for sodium nitrate solutions was determined by studying the relaxation time observed during coalescence of two aqueous sodium nitrate droplets levitated in optical tweezers. The combination of theoretical derivations and experimental results showed that longer time available for crystallization correlates with larger crystal size and higher degrees of crystallinity in the final microparticles.

Observation of the binary coalescence and equilibration of micrometer-sized droplets of aqueous aerosol in a single-beam gradient-force optical trap.

The binary coalescence of aqueous droplets has been observed in a single-beam gradient-force optical trap. By measuring the time-dependent intensity for elastic scattering of light from the trapping laser, the dynamics of binary coalescence have been examined and the time scale for equilibration of a composite droplet to ambient conditions has been determined. These data are required for modeling the agglomeration of aqueous droplets in dense sprays and atmospheric aerosol. Elastic-light scattering from optically trapped particles has not been used previously to study the time-resolved dynamics of mixing. It is shown to offer a unique opportunity to characterize the binary coalescence of aqueous droplets with radii from 1 to 6 μm. The study of this size regime, which cannot be achieved by conventional imaging methods, is critical for understanding the interactions of droplets in the environment of dense sprays.

Toward optical-tweezers-based force microscopy for airborne microparticles

Optical tweezers have found widespread application in biological and colloidal physics for the measurement of pN forces over nanometer to micrometer length scales. Similar aerosol-phase measurements of interparticle force have not been reported in spite of the potential to better resolve particle coagulation kinetics. Various refractive index mismatches in the beam path as well as the need to explicitly account for gravity and inertial particle motion provide a number of challenges that must be overcome to make such measurements tractable. In this regard, we demonstrate schemes by which the particle position and trap stiffness may be unambiguously measured using bright-field microscopy with resolution comparable with analogous condensed-phase measurements. Moreover, some of the challenges of working with highly dynamic aqueous particles are introduced and exploited to observe size-dependent phenomena in aerosol optical tweezers. Notably, when combined with cavity-enhanced Raman spectroscopy, this provides a unique opportunity to explore trapping forces over a continuum of particle size and refractive index. It is expected that the methods developed will provide a basis for the measurement of pairwise interaction forces in aerosol optical tweezers while providing a probe of fundamental airborne particle trapping dynamics.

Probing the bulk viscosity of particles using aerosol optical tweezers.

Holographic aerosol optical tweezers can be used to trap arrays of aerosol particles allowing detailed studies of particle properties and processes at the single particle level. Recent observations have suggested that secondary organic aerosol may exist as ultra-viscous liquids or glassy states at low relative humidity, potentially a significant factor in influencing their role in the atmosphere and their activation to form cloud droplets. A decrease in relative humidity surrounding a particle leads to an increased concentration of solute in the droplet as the droplet returns to equilibrium and, thus, an increase in the bulk viscosity. We demonstrate that the timescales for condensation and evaporation processes correlate with particle viscosity, showing significant inhibition in mass transfer kinetics using ternary sucrose/sodium chloride/water droplets as a proxy to atmospheric multi-component aerosol. We go on to study the fundamental process of aerosol coagulation in aerosol particle arrays, observing the relaxation of non-spherical composite particles formed on coalescence. We demonstrate the use of bright-field imaging and elastic light scattering to make measurements of the timescale for the process of binary coalescence contrasting the rheological properties of aqueous sucrose and sodium chloride aerosol over a range of relative humidities.

Optical manipulation of aerosol particle arrays

Aerosols play a crucial role in many areas of science, ranging from atmospheric chemistry and physics, to drug delivery to the lungs, combustion science and spray drying. The development of new methods to characterise the properties and dynamics of aerosol particles is of crucial importance if the complex role that particles play is to be more fully understood. Optical tweezers provide a valuable new tool to address fundamental questions in aerosol science. Single or multiple particles 1-15 μm in diameter can be manipulated over indefinite timescales using optical tweezing. Linear and non-linear Raman and fluorescence spectroscopies can be used to probe a particles composition and size. In this paper we will report on the latest developments in the use of holographic optical trapping (HOT) to study aerosols. Although widely used to trap and manipulate arrays of particles in the condensed phase, the application of HOT to aerosols is still in its infancy. We will explore the opportunities provided by the formation of complex optical landscapes for controlling aerosol flow, for comparing the properties of multiple particles, for performing the first ever digital microfluidic operations in the aerosol phase and for examining interparticle interactions that can lead to coalescence/coagulation. Although aerosol coagulation is the primary process driving the evolution of particle size distributions, it remains very poorly understood. Using HOT, we can resolve the time-dependent motion of trapped particles and the light scattering from particles during the coalescence process.

Micro-rheology and interparticle interactions in aerosols probed with optical tweezers

Using optical tweezers for micro-rheological investigations of a surrounding fluid has been routinely demonstrated. In this work, we will demonstrate that rheological measurements of the bulk and surface properties of aerosol particles can be made directly using optical tweezers, providing important insights into the phase behavior of materials in confined environments and the rate of molecular diffusion in viscous phases. The use of holographic optical tweezers to manipulate aerosol particles has become standard practice in recent years, providing an invaluable tool to investigate particle dynamics, including evaporation/ condensation kinetics, chemical aging and phase transformation. When combined with non-linear Raman spectroscopy, the size and refractive index of a particle can be determined with unprecedented accuracy <+/- 0.05%). Active control of the relative positions of pairs of particles can allow studies of the coalescence of particles, providing a unique opportunity to investigate the bulk and surface properties that govern the hydrodynamic relaxation in particle shape. In particular, we will show how the viscosity and surface tension of particles can be measured directly in the under-damped regime at low viscosity. In the over-damped regime, we will show that viscosity measurements can extend close to the glass transition, allowing measurements over an impressive dynamic range of 12 orders of magnitude in relaxation timescale and viscosity. Indeed, prior to the coalescence event, we will show how the Brownian trajectories of trapped particles can yield important and unique insights into the interactions of aerosol particles.

Analysis of optical trap mediated aerosol coalescence

The use of optical tweezers for the analysis of aerosols is valuable for understanding the dynamics of atmospherically relevant particles. However to be able to make accurate measurements that can be directly tied to real-world phenomena it is important that we understand the influence of the optical trap on those processes. One process that is seemingly straightforward to study with these techniques is binary droplet coalescence, either using dual beam traps, or by particle collision with a single trapped droplet. This binary coalescence is also of interest in many other processes that make use of dense aerosol sprays such as spray drying and the use of inhalers for drug delivery in conditions such as asthma or hay fever. In this presentation we discuss the use of high speed (~5000 frames per second) video microscopy to track the dynamics of particles as they approach and interact with a trapped aqueous droplet and develop this analysis further by considering elastic light scattering from droplets as they undergo coalescence. We find that we are able to characterize the re-equilibration time of droplets of the same phase after they interact and that the trajectories taken by airborne particles influenced by an optical trap are often quite complex. We also examine the role of parameters such as the salt concentration of the aqueous solutions used and the influence of laser wavelength.The use of optical tweezers for the analysis of aerosols is valuable for understanding the dynamics of atmospherically relevant particles. However to be able to make accurate measurements that can be directly tied to real-world phenomena it is important that we understand the influence of the optical trap on those processes. One process that is seemingly straightforward to study with these techniques is binary droplet coalescence, either using dual beam traps, or by particle collision with a single trapped droplet. This binary coalescence is also of interest in many other processes that make use of dense aerosol sprays such as spray drying and the use of inhalers for drug delivery in conditions such as asthma or hay fever. In this presentation we discuss the use of high speed (~5000 frames per second) video microscopy to track the dynamics of particles as they approach and interact with a trapped aqueous droplet and develop this analysis further by considering elastic light scattering from droplets as they undergo coalescence. We find that we are able to characterize the re-equilibration time of droplets of the same phase after they interact and that the trajectories taken by airborne particles influenced by an optical trap are often quite complex. We also examine the role of parameters such as the salt concentration of the aqueous solutions used and the influence of laser wavelength.