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2014, Journal of Aerosol Science
A new hybrid analytical/numerical model that describes the formation of structured microparticles from evaporating microdroplets is presented. It is applicable when diffusion and surface recession are the main mechanisms of mass transport in the droplets. The model accounts for the transient nature of the solute concentration profiles during the evaporation process and thereby extends previously published models to particle formation processes in which the droplet surface recession rate is much faster than the diffusion in the droplets, i.e., in cases with large Péclet numbers. Furthermore, the model is useful when the initial concentration of solutes in the droplets is close to saturation. The model also predicts the dry particle diameter, assuming a spherical particle, particle density, and aerodynamic diameter. For hollow particles formed at large Péclet numbers the shell thickness can be approximated. The model is capable of predicting the radial distribution of the components in the final dry particle in the case of multi-component formulations. The results of the model were recast in a simple analytical form, which can be used in particle design without the need for numerical tools. Predictions of the model were found to be in good agreement with numerical and experimental results in the literature.
Drying Technology, 2009
Nanotechnologies in Russia, 2011
The physical and computational model of self-assembly in an evaporating microdrop of solution several hundreds of picoliters in volume is described as a further development of dissipative particle dynamics (DPD) methods used in systems with a changeable volume. The simulation results are compared with experiments on the aqueous solutions of polystyrene colloid particles.
New Journal of Physics, 2009
An efficient way to precisely pattern particles on solid surfaces is to dispense and evaporate colloidal drops, as for bioassays. The dried deposits often exhibit complex structures exemplified by the coffee ring pattern, where most particles have accumulated at the periphery of the deposit. In this work, the formation of deposits during the drying of nanoliter colloidal drops on a flat substrate is investigated numerically and experimentally. A finite-element numerical model is developed that solves the Navier-Stokes, heat and mass transport equations in a Lagrangian framework. The diffusion of vapor in the atmosphere is solved numerically, providing an exact boundary condition for the evaporative flux at the droplet-air interface. Laplace stresses and thermal Marangoni stresses are accounted for. The particle concentration is tracked by solving a continuum advection-diffusion equation. Wetting line motion and the interaction of the free surface of the drop with the growing deposit are modeled based on criteria on wetting angles. Numerical results for evaporation times and flow field are in very good agreement with published experimental and theoretical results. We also performed transient visualization experiments of water and isopropanol drops loaded with polystyrene microsphere evaporating on respectively glass and polydimethylsiloxane substrates. Measured evaporation times, deposit shape and sizes, and flow fields are in very good agreement with the numerical results. Different v velocity vector v = (u.v) V dimensionless velocity vector V = (U.V) X Concentration of particles [kg of particles/kg of solution] z axial coordinate [m] Z dimensionless axial coordinate [ 0 max, / r z ]
Advanced Powder Technology, 2018
Formation of structurized micro/nanoparticle aggregates in spray drying process is analyzed theoretically and experimentally. Colloids of mono-and bimodal particle size distribution are used as the precursors to demonstrate different patterns of particle self-organization inside the drying droplet. In case of monodisperse primary particles their self-organization in the final aggregate results in either a hollow or a full (packed) spherical structure. For primary particles with bimodal size distribution, either the layered structure of aggregates is formed (with smaller particles forming outer layer and the bigger particles captured inside) or the ordering of bigger particles on the aggregate surface is observed, depending on process parameters. Numerical investigations allow to predict and explain the conditions at which selfassembling of particles within powder aggregates takes place.
Aerosol Science and Technology
Experimental studies of particle formation from solution droplets were conducted using a newly developed monodisperse spray drying process. Solutes beclomethasone dipropionate and caffeine were dissolved in ethanol, pressurized hydrofluoroalkane propellant 134a, and mixtures thereof. Solutions were atomized into monodisperse microdroplets using a custom droplet generator installed in a laboratory scale spray dryer, enabling drying and collection of the resulting monodisperse microparticles. The effects of droplet diameter, solution concentration, solvent composition, and drying rate on the physical properties of the dried particles were evaluated. Particle morphology and size were assessed using ultramicroscopy and image analysis of micrographs. Extent of crystallinity and polymorphism were investigated using Raman spectroscopy. The drying temperature was found to have a large effect on the morphology of amorphous beclomethasone dipropionate particles. Particles dried near room temperature were spheroidal to ellipsoidal with prevalent surface concavities and evidence of shell buckling; increasing the drying temperature for fixed droplet size and composition resulted in a transition to more spherical, smooth-surfaced particle morphologies. Crystalline caffeine microparticles were made up of assemblies of multiple crystallites. The measured length and breadth of these crystallites was found to be correlated with the time available for crystal nucleation and growth as calculated using a particle formation model. The results highlight the abilities and limitations of currently available particle formation models in elucidating the relationships between the size, composition, and evaporation rate of drying solution droplets and the physical properties of the resulting particles. The work demonstrates the suitability of monodisperse spray drying as an experimental technique for investigating the fundamentals of particle formation from solution droplets.
Interfacial Phenomena and Heat Transfer, 2017
A numerical study is carried out to analyze the effect of internal flow on the transport of diluted particles in a sessile droplet of water. We developed a numerical model that accounts for the flow and heat transfer as well as the transport of colloids in the droplet, heat conduction in the substrate and surrounding air, and vapor diffusion in the gas phase. The finite volume method is adopted to solve the problem and to predict how the colloids are distributed inside the droplet. The results show that the internal flow in the drop affects the distribution of the concentration of the solid particles during the evaporation. The outgoing radial flow tends to transport the particles to the edge of the drop toward the contact line, while the flow induced by thermo-capillarity, with its cellular pattern, tends to carry the particles from the edge toward the core of the droplet.
2007
In the PGSS process, a gas saturated solution is atomized through a nozzle and a spray is formed; afterwards, the gas (carbon dioxide) evaporates and droplets solidify.
Journal of Colloid and Interface Science, 2018
Hypothesis The deposition of particles from a volatile liquid drop atop a substrate is primarily governed by the advection and diffusion of the particles in the liquid. Colloidal particles may further coagulate and adsorb to the substrate during the deposition process. The external geometry and the internal composition of the particulate deposit are then determined by an interplay between these four mechanisms. Simulation We simulate the process of deposition by solving the governing transport equations. We explore the interplay between the different mechanisms mentioned above. In particular, we study the contribution of the diffusion of colloidal particles and aggregates to the morphology of the deposit, which was neglected in a previous study. Findings The rates of diffusion and coagulation of each specific aggregate are dependent on its size. Hence, the transport equation uniquely correlates to each population of aggregates. The overall transport problem, alongside the rates of particle and aggregate adsorption and liquid evaporation, determines the geometry of the deposit. Moreover, the local rate of particle coagulation determines the internal composition of the different aggregate populations in the deposit. Our results appear to be in qualitative agreement with previous experimental findings.
2011
Prokofiev for their time and effort in serving in my dissertation committee. I thank Prof. Maroudas for the opportunity to attend his group meetings which have always been a valuable learning experience. I would like to thank Prof. Prokofiev for his thoughtful criticism that provoked improvements in this work. I would also like to thank group members JoungMo Cho, Tracy Heckler, Jun Wang, Bing Mei and the recent members of the group for their company and help. I am thankful for having met some wonderful colleagues and friends in the department and outside. I am thankful for the company and help during my stay to Tejinder Singh, Mayur Valipa, Anurag Verma, Kedarnath Kolluri, Vivek Tomar, and George Sfyris. I would like to thank Prof. Yannis Kevrekidis who helped refine these ideas and gave useful suggestions and criticism which were invaluable to this work. I would like to acknowledge my thesis advisor Prof. Mountziaris, for being with me in this long journey. His company, always pleasant, also ensured that I kept on in this long journey and his patient attitude always kept me in good spirit. Thank you very much. My parents' love and many sacrifices afforded me this opportunity. I do not think I would ever be able to thank them, but I do hope to give them joy in the future. Thank you very much Amma and Accha.
Journal of Fluid Mechanics
Froth flotation by small air bubbles has been traditionally used in industry to capture fine minerals and other hydrophobic particles. This method, however, is not efficient for capturing very small particles. The present work is motivated by a new agglomeration process that overcomes this lack of efficiency. It consists of mixing a particle suspension and saltwater-filled droplets covered with semi-permeable oil layers. This paper investigates the two-particle dynamics of a solid particle and a semi-permeable spherical drop that expands due to osmosis in an external, pure extensional flow field. A dimensionless engulfment parameter measures the relative effects of droplet growth and convective flow. The computational results from numerical integration determine a transient collision efficiency, which describes the influence of hydrodynamic interactions and osmotic flow on particle capture. The results show that drop expansion, which decays slowly with time, greatly increases particle capture rates, especially for small particles. Moreover, as the engulfment parameter increases, there is a transition from flow-dominated capture to expansion-dominated capture. For the case of a non-expanding droplet, we provide a numerical solution for the transient pair distribution function, which enables us to explain the transient particle-capture rate in terms of the microstructure of the suspension. Furthermore, we derive an analytical expression for the initial collision efficiency at zero times, which agrees with our numerical data. The numerical results for non-expanding droplets at long times show increasing collision efficiency as the permeability increases and when the size ratio is near unity, in agreement with previous steady-state calculations.
Drying Technology, 2013
The particle size of the primary particles is an important parameter influencing the drying behavior of droplets. In this work the influence of the particle size on the drying kinetics and the grain properties has been analyzed for droplets containing silica, microparticles and their mixtures. The presence of microparticles has been found to increase the drying rate and the shrinkage of the droplet. The drying curves have been modeled using the REA model. Finally, different suspensions were dried in a pilotscaled spray dryer in order to prove the influence of the particle size obtained in the levitator tests.
Chemical Engineering Science, 2020
Spray drying allows tuning the physical properties of the resulting powders widely. However, targeted process design is complicated by the interplay between process characteristics and the non-ideal physical properties exhibited by multicomponent mixtures, such as pharmaceutical formulations. This work presents a mechanistic model describing the drying of single droplets. The model includes heat and mass balances, non-ideal vapour-liquid equilibria, and population balances describing the evolution of particulates within the drying droplet. The model is applied to (up to) ternary mixtures of solvents, polymers and solutes, and predicts properties of the drying droplet such as the time of shell formation and the size of the particle obtained after drying. A comparison with experimental data from single droplet drying experiments carried out at defined relative vapour saturation and temperature shows that the model can be used to predict shell formation (as well as other properties) for the systems studied here.
Physics of Fluids, 2022
Colloidal droplets are used in a variety of practical applications. Some of these applications require particles of different sizes. These include medical diagnostic methods, the creation of photonic crystals, the formation of supraparticles, and the production of membranes for biotechnology. A series of earlier experiments had shown the possibility of particle separation near the contact line, depending upon their size. A mathematical model has been developed to describe this process. Bi-dispersed colloidal droplets evaporating on a hydrophilic substrate are taken into consideration. A particle monolayer is formed near the periphery of such droplets due to the small value of the contact angle. The shape of the resulting deposit is associated with the coffee ring effect. The model takes into account both particle diffusion and transfers caused by capillary flow due to liquid evaporation. Monte Carlo simulations of such particle dynamics have been performed at several values of the particle concentration in the colloidal solution. The numerical results agree with the experimental observations, in which small particles accumulate nearer to the contact line than do the large particles. However, the particles do not actually reach the contact line but accumulate at a small distance from it. The reason for this is the surface tension acting on the particles in areas, where the thickness of the liquid layer is comparable to the particle size. Indeed, the same mechanism affects the observed separation of the small and large particles.
International Journal of Heat and Mass Transfer, 1995
Evaporation of a liquid droplet containing small solid particles (slurry droplets) is analyzed in a quasi-steady approximation. The developed model takes into account effects of compressibility and filtration of a gas-vapor mixture within the porous shell. It is shown that in the case of small temperature differences Ln the neighborhood of a slurry droplet at the second stage of drying (evaporation through a porous shell), the regime of slow evaporation and saturation (negligibly small drying rate) occurs. In the case of high temperature differences in the neighborhood of a slurry droplet at the second stage of drying, the pressure of the gas-vapor mixture within the porous shell significantly increases leading to the fragmentation of a porous shell. The comparison of the proposed model with the diffusion model, which neglects the Stefan's flux shows that the diffusion model incorrectly describes evaporation of a slurry droplet at the final stage of drying.
Phys. Rev. E, 2019
A simplified model is developed, which allows us to perform computer simulations of the particles transport in an evaporating droplet with a contact line pinned to a hydrophilic substrate. The model accounts for advection in the droplet, diffusion and particle attraction by capillary forces. On the basis of the simulations, we analyze the physical mechanisms of forming of individual chains of particles inside the annular sediment. The parameters chosen correspond to the experiments of Park and Moon [Langmuir 22, 3506 (2006)], where an annular deposition and snakelike chains of colloid particles have been identified. The annular sediment is formed by advection and diffusion transport. We find that the close packing of the particles in the sediment is possible if the evaporation time exceeds the characteristic time of diffusion-based ordering. We show that the chains are formed by the end of the evaporation process due to capillary attraction of particles in the region bounded by a fixing radius, where the local droplet height is comparable to the particle size. At the beginning of the evaporation, the annular deposition is shown to expand faster than the fixing radius moves. However, by the end of the process, the fixing radius rapidly outreaches the expanding inner front of the ring. The snakelike chains are formed at this final stage when the fixing radius moves toward the symmetry axis.
Aerosol Science and Technology, 2016
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 to 80 µm. Aqueous solutions of sodium nitrate were prepared in concentrations ranging from 5 mg/ml to 510-5 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.
Aerosol Science and Technology, 2016
The process of particle formation from evaporating droplets containing more than one solute was studied. Two-component microparticles were produced using a piezoceramic dispenser with an inner diameter of 30 µm. Initial droplets had a diameter in the range of 70 to 85 µm and contained sodium nitrate and potassium nitrate in different molar ratios of 30:70, 50:50, and 70:30, corresponding to weight ratios of 26.5:73.5, 45.7:54.3, and 66.2:33.8, in the form of aqueous solutions with initial concentrations of 1 or 10 mg/mL. The monodisperse droplets were dried in a dry laminar gas flow with temperatures of 50 or 100 °C. Different initial conditions affected the particle formation process and the particle morphology. The diameter of the final dried microparticles ranged from 4 to 10 µm. Their density varied from 1250 to 1950 mg/mL. The formulation and process conditions determined the distribution of chemical components in the dried microparticles, especially their surface composition as determined by energy-dispersive X-ray spectroscopy. The distribution of the chemical components was theoretically explained
Experiments in Fluids, 2016
Journal of colloid and interface science, 2015
We investigate the axisymmetric homogeneous growth of 10-100 nm water nanodroplets on a substrate surface. The main mechanism of droplet growth is attributed to the accumulation of laterally diffusing water monomers, formed by the absorption of water vapour in the environment onto the substrate. Under assumptions of quasi-steady thermodynamic equilibrium, the nanodroplet evolves according to the augmented Young-Laplace equation. Using continuum theory, we model the dynamics of nanodroplet growth including the coupled effects of disjoining pressure, contact angle and monomer diffusion. Our numerical results show that the initial droplet growth is dominated by monomer diffusion, and the steady late growth rate of droplet radius follows a power law of 1/3, which is unaffected by the substrate disjoining pressure. Instead, the disjoining pressure modifies the growth rate of the droplet height, which then follows a power law of 1/4. We demonstrate how spatial depletion of monomers could ...
Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2007
A method is proposed for preparing solid phases of desired morphologies from microscopic droplets on solid substrates with a GMS 417 Arrayer, which is commonly used for biochip production. The initial droplet of an aqueous solution is about 100 pl (about 100 m in diameter), and the evaporation time is about 0.5 s. Such small solution volumes are first considered from the viewpoint of the solute self-organization. Aqueous solutions of inorganic molecular and ionic substances, organic dyes, and latex colloid particles in the evaporating droplets are experimentally studied. Various substrates and solute concentrations are used. The morphology of the solid phase formed on the substrate after water evaporation is analyzed with the use of computer simulation of dynamics of the latex particles within the evaporating microdroplet. Elucidating the self-organization mechanisms will facilitate producing of the desired morphology of the solid phase, which can find an application in nanotechnology.
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