This work deals with the study of the drying-mediated assembly of colloidal gold nanoparticles (Au NPs) in mesoscale aggregation patterns and their manipulation by atomic force microscopy (AFM) on model surfaces. The assembly of NPs in mesoscale and complex aggregation patterns assisted by the wetting and the drying of complex fluids (suspensions of NPs, NPs/biopolymers mixed solutions) on homogeneous and heterogeneous molecular surfaces was studied. This issue is important, both for understanding fundamental processes of self-organization, and for generating new functional mesostructures. The drying of complex fluids often leads to the emergence of highly complex aggregation structures as shown and discussed in this work. The richness and the aesthetics of these complex structures generated by these interfacial phenomena reflect not only the bulk properties of fluids (different sizes and lengths- scales, kinetic changes in state), but more importantly, the coupling between the fluid properties and those of the substrate surface (wetting interactions, confinement, hydrodynamics). In the case of two important heterogeneous fluids which are Au NPs and polysaccharide solutions, these drying-mediated structure formation lead to the genesis of unusually large and highly ramified dendrites aggregation patterns. The growth mechanism and the critical parameters that control the morphogenesis of these complexes structures are addressed in this work. In addition, the aging mechanisms and kinetics of these structures that are metastable and evolve either through direct dislocation via clusters NPs mobility on the surface, or through undulation-induced roughning of the dendrite branches. To better understanding this NPs mobility and thus the dislocation mechanism of the aging, a detailed study based on the manipulation of NPs by atomic force microscopy in tapping mode (AFM) was developed. The threshold dissipated energy to manipulate (move) the NPs can be quantified according to the intrinsic parameters of the particle (size, shape, and chemical nature), the chemical nature and topography of the substrate, and finally the operating and environment conditions. This work enabled us to understand the mechanisms and characterize the critical parameters that may intervene in the dislocation (aging) of NPs-based functional structures, depending on the nature of the environment liquid and the substrate. Finally, this work proposes an approch of evaluation and of monitoring the stability and the aging of these aggregation structures, in particular, those formed from the drying of films and drops of nano-particles solutions (metal nanoparticles, blood: proteins, viruses ...).

Élaborer ou structurer des matériaux à l’échelle nanométrique permet d’aborder une physique nouvelle mais également de réaliser des dispositifs fonctionnant sur des principes originaux utilisées dans divers domaines (médecine, énergie, électronique, optique, catalyse..). Ce travail porte sur l’étude de l’assemblage des nanoparticules d’or colloïdales (NPs) en structures d’agrégation mésoscopiques, assisté par le séchage des fluides complexes et de leur manipulation par Microscope à Force Atomique (AFM) sur des surfaces modèles. Une première partie présente la synthèse des NPs d’or et des surfaces moléculaires auto-assemblées sur des substrats rigides. Ensuite, l’étude de la formation des structures d’agrégation assistée par le mouillage et le séchage des fluides complexes ( NPs et polysaccharide) sur des surfaces moléculaires a permis de mettre en évidence le rôle crucial du couplage entre les propriétés de volume singulières de ces fluides, et celles de surface du substrat dans la formation de structures d’agrégation complexes (fractales, et dendrites en particulier). Dans un troisième temps, les travaux abordent à l’étude et la compréhension du vieillissement (dégénérescence et reconstruction) des structures mésoscopiques élaborées. Entre autres résultats, ces travaux ont mis en évidence la nature ‘diffusionnelle’ de la dislocation des structures, laquelle se traduit par la mobilité d’agrégats nanoparticulaires en surface. Afin de mieux appréhender cette problématique de mobilité individuelle et/ou collective (cluster) des NPs, une étude détaillée basée sur la manipulation des NPs par AFM en mode Tapping a été réalisée. L’ensemble des résultats obtenus au cours de ce travail de thèse a permis d’une part, i) de proposer de nouvelles approches d’assemblage de macromolécules et de particules, assisté par les phénomènes de mouillage, ii) de comprendre les mécanismes à l’origine de la formation de ces structures d’agrégation complexes (fractales compactes et fibrillaires) sur des substrats homogènes et hétérogènes, et d’autre part, iii) de contrôler la stabilité et le vieillissement de ces structures d’agrégation complexes en vue d’une validation de la fiabilité éventuelle de nanomatériaux issus d’assemblages à base de NPs. / This work deals with the study of the drying-mediated assembly of colloidal gold nanoparticles (Au NPs) in mesoscale aggregation patterns and their manipulation by atomic force microscopy (AFM) on model surfaces. The assembly of NPs in mesoscale and complex aggregation patterns assisted by the wetting and the drying of complex fluids (suspensions of NPs, NPs/biopolymers mixed solutions) on homogeneous and heterogeneous molecular surfaces was studied. This issue is important, both for understanding fundamental processes of self-organization, and for generating new functional mesostructures. The drying of complex fluids often leads to the emergence of highly complex aggregation structures as shown and discussed in this work. The richness and the aesthetics of these complex structures generated by these interfacial phenomena reflect not only the bulk properties of fluids (different sizes and lengths- scales, kinetic changes in state), but more importantly, the coupling between the fluid properties and those of the substrate surface (wetting interactions, confinement, hydrodynamics). In the case of two important heterogeneous fluids which are Au NPs and polysaccharide solutions, these drying-mediated structure formation lead to the genesis of unusually large and highly ramified dendrites aggregation patterns. The growth mechanism and the critical parameters that control the morphogenesis of these complexes structures are addressed in this work. In addition, the aging mechanisms and kinetics of these structures that are metastable and evolve either through direct dislocation via clusters NPs mobility on the surface, or through undulation-induced roughning of the dendrite branches. To better understanding this NPs mobility and thus the dislocation mechanism of the aging, a detailed study based on the manipulation of NPs by atomic force microscopy in tapping mode (AFM) was developed. The threshold dissipated energy to manipulate (move) the NPs can be quantified according to the intrinsic parameters of the particle (size, shape, and chemical nature), the chemical nature and topography of the substrate, and finally the operating and environment conditions. This work enabled us to understand the mechanisms and characterize the critical parameters that may intervene in the dislocation (aging) of NPs-based functional structures, depending on the nature of the environment liquid and the substrate. Finally, this work proposes an approch of evaluation and of monitoring the stability and the aging of these aggregation structures, in particular, those formed from the drying of films and drops of nano-particles solutions (metal nanoparticles, blood: proteins, viruses ...).

Droplet evaporation is ubiquitous to multitude of applications such as microfluidics, surface patterning and ink-jet printing. In many of the process like food processing tiny concentrations of suspended particles may alter the behavior of an evaporating droplet remarkably, leading to partially viscous and partially elastic dynamical characteristics. This, in turn, may lead to some striking mechanical instabilities, such as buckling and rupture. In this thesis, we provide a comprehensive physical description of the vaporization, self-assembly, agglomeration and buckling kinetics of sessile nanofluid droplet pinned on a hydrophobic substrate in various configurations. We have deciphered five distinct regimes of droplet lifecycle. Regime I-III consists of evaporation induced preferential agglomeration that leads to the formation of unique dome shaped inhomogeneous shell with stratified varying density liquid core. Regime IV involves capillary pressure initiated shell buckling and stress induced shell rupture. Regime V marks rupture induced cavity inception and growth. We provide a regime map explaining the droplet morphology and buckling characteristics for droplets evaporating on various substrates. Specifically, we find that final droplet volume and radius of curvature at buckling onset are universal functions of particle concentration. Furthermore, flow characteristics inside the heated and unheated droplets are investigated and found to be driven by the buoyancy effects. Velocity magnitudes are observed to increase by an order at higher temperatures with self-similar flow profiles. With an increase in the surface temperature, droplets exhibit buckling from multiple sites over a larger sector in the top half of the droplet. In addition, irrespective of the initial nanoparticle concentration and substrate temperature, hydrophobicity and roughness, growth of daughter cavity (subsequent to buckling) inside the droplet is found to be controlled by the solvent evaporation rate from the droplet periphery. The results are of great significance to a plethora of applications like DNA deposition and nanofabrication. In the next part of the thesis, we deploy the droplet in a rectangular channel. The rich physics governing the universality in the underlying dynamics remains grossly elusive. Here, we bring out hitherto unexplored universal features of the evaporation dynamics of a sessile droplet entrapped in a 3D confined fluidic environment. Increment in channel length delays the completion of the evaporation process and leads to unique spatio-temporal evaporation flux and internal flow. We show, through extensive set of experiments and theoretical formulations, that the evaporationtimescale for such a droplet can be represented by a unique function of the initial conditions. Moreover, using same theoretical considerations, we are able to trace and universally merge the volume evolution history of the droplets along with evaporation lifetimes, irrespective of the extent of confinement. These results are explained in the light of increase in vapor concentration inside the channel due to greater accumulation of water vapor on account of increased channel length. We have formulated a theoretical framework which introduces two key parameters namely an enhanced concentration of the vapor field in the vicinity of the confined droplet and a corresponding accumulation lengthscale over which the accumulated vapor relaxes to the ambient concentration. Lastly, we report the effect of confinement on particle agglomeration and buckling dynamics. Compared to unconfined scenario, we report non-intuitive suppression of rupturing beyond a critical confinement. We attribute this to confinement-induced dramatic alteration in the evaporating flux, leading to distinctive spatio-temporal characteristics of the internal flow leading to preferential particle transport and subsequent morphological transitions. We present a regime map quantifying buckling & non-buckling pathways. These results may turn out to be of profound importance towards achieving desired morphological features of a colloidal droplet, by aptly tuning the confinement space, initial particle concentration, as well as the initial droplet volume. These findings may have implications in designing functionalized droplet evaporation devices for emerging engineering and biomedical applications.

The complex multiscale physics of nanoparticle laden functional droplets in a reacting environment is of fundamental and applied significance for a wide variety of applications ranging from thermal sprays to pharmaceutics to modern day combustors using new brands of bio-fuels. Understanding the combustion characteristics of these novel fuels (laden with energetic nanoparticle NP) is pivotal for lowering ignition delay, reducing pollutant emissions and increasing the combustion efficiency in next generation combustors. On the way to understanding the complex dynamics of sprays is to first study the behaviour of an isolated droplet. A single droplet represents a sub-grid unit of spray. In vaporizing functional droplets under high heat flux conditions, the bubble formation inside the droplet represents an unstable system. This may be either through homogenous nucleation at the superheat limit or by dispersed nanoparticle acting as heterogeneous nucleation sites. First it is shown that such self-induced boiling in burning functional pendant droplets can induce severe volumetric shape oscillations in the droplet. Internal pressure build-up due to ebullition activity force ejects bubbles from the droplet domain causing undulations on the droplet surface and oscillations in bulk thereby leading to secondary break-up of the primary droplet. Through experiments, it is established that the degree of droplet deformation depends on the frequency and intensity of these bubble expulsion events. However, in a distinct regime of single isolated bubble growing inside the droplet, pre-ejection transient time is identified by Darrieus-Landau (DL) instability at the evaporative bubble-droplet interface. In this regime the bubble-droplet system behaves as a synchronized driver-driven system with bulk bubble-shape oscillations being imposed on the droplet. However, the agglomeration of suspended anaphase additives modulates the flow structures within the droplet and also influences the bubble inception and growth leading to distinct atomization characteristics. Secondly, the secondary atomization characteristics of burning bi-component (ethanol-water) droplets containing titania nanoparticle (NPs) at both dilute (0.5% and 1% by weight) and dense particle loading rates (PLR: 5% and 7.5 wt. %) are studied experimentally at atmospheric pressure under normal gravity. It is observed that both types of nanofuel droplets undergo distinct modes of secondary break-up that are primarily responsible for transporting particles from the droplet domain to the flame zone. For dilute nanosuspensions, disruptive response is characterized by low intensity atomization modes that cause small-scale localized flame distortion. In contrast, the disruption behavior at dense concentrations is governed by high intensity bubble ejections which result in severe disruption of the flame envelope. The atomization events occur locally at the droplet surface while their cumulative effect is observed globally at the droplet scale. Apart from this, a feedback coupling between two key interacting mechanisms, namely, atomization frequency and particle agglomeration also influence the droplet deformation characteristics by regulating the effective mass fraction of NPs within the droplet. Thus, third part of the study elucidates how the initial NP concentration modulates the relative dominance of these two mechanisms thereby leading to a master-slave configuration. Secondary atomization of novel nanofuels is a crucial process since it enables an effective transport of dispersed NPs to the flame (a pre-requisite condition for NPs to burn). Contrarily, NP agglomeration at the droplet surface leads to shell formation thereby retaining NPs inside the droplet. In particular, it is shown that at dense concentrations shell formation (master process) dominates over secondary atomization (slave) while at dilute particle loading it is the high frequency bubble ejections (master) that disrupt shell formation (slave) through its rupture and continuous out flux of NPs. These results in distinct combustion residues at dilute and dense concentrations, thus, providing a method of manufacturing flame synthesized microstructures with distinct morphologies. Next, it is shown that by using external stimuli (preferential acoustic excitation) the secondary atomization of the droplet can be suppressed i.e. the external flame-acoustic interaction with bubbles inside the droplet results in controlled droplet deformation. Particularly, by exciting the droplet flame in a critical, responsive frequency range i.e. 80 Hz ≤ fP ≤ 120 Hz, the droplet deformation cycle is altered through suppression of self-excited instabilities and intensity/frequency of bubble ejection events. The acoustic tuning also enables the control of bubble dynamics, bulk droplet-shape distortion and final precipitate morphology even in burning nanoparticle laden droplets. Droplets in a non-reacting environment (heated radioactively) are also subject to instabilities. One such instability observed in drying colloidal droplets is the buckling of thin viscoelastic shell formed through consolidation of NPs. In the final part of the thesis, buckling instability driven morphology transition (sphere to ring structure) in an acoustically levitated heated nanosilica dispersion droplet is elucidated using dynamic energy balance. Droplet deformation featuring formation of symmetric cavities is initiated by the capillary pressure that is two to three orders of magnitude greater than acoustic radiation pressure, thus indicating that the standing pressure field has no influence on the buckling front kinetics. With increase in heat flux, the growth rate of surface cavities and their post-buckled volume increases while the buckling time period reduces, thereby altering the buckling pathway and resulting in distinct precipitate structures. Thus, the cavity growth is primarily driven by evaporation. However, irrespective of the heating rate, volumetric droplet deformation exhibits linear time dependence and droplet vaporization is observed to deviate from the classical D2-law. Understanding such transients of buckling phenomenon in drying colloidal suspensions is pivotal for producing new functional microstructures with tenable morphology and is particularly critical for spray drying applications that produce powders through vaporization of colloidal droplets.