Nucleation | EPFL Graph Search

In thermodynamics, nucleation is the first step in the formation of either a new thermodynamic phase or structure via self-assembly or self-organization within a substance or mixture. Nucleation is typically defined to be the process that determines how long an observer has to wait before the new phase or self-organized structure appears. For example, if a volume of water is cooled (at atmospheric pressure) below 0 °C, it will tend to freeze into ice, but volumes of water cooled only a few degrees below 0 °C often stay completely free of ice for long periods (supercooling). At these conditions, nucleation of ice is either slow or does not occur at all. However, at lower temperatures nucleation is fast, and ice crystals appear after little or no delay. Nucleation is a common mechanism which generates first-order phase transitions, and it is the start of the process of forming a new thermodynamic phase. In contrast, new phas

Precipitation, Characterization, Kinetic, and Thermodynamic Modelling of Synthetic C-S-H Systems (C-S-H, CASH, CSH+$)

Maya Nicole Harris

This thesis investigates the effects of aluminates, sulfates, and heterogeneous substrates on the nucleation and growth of synthetic calcium-silicate-hydrates (C-S-H) produced by dropwise precipitation. The use of synthetic C-S-H, separate from other cementitious phases, allows formation mechanisms and kinetics effects to be investigated in a simplified system. The addition of other ions and substrates then allows an approach to the more complicated, multi-phase system of cement and concrete. The first goal of this thesis was to reproducibly synthesize single-phase C-S-H with Ca:Si from 1 to 2. Guidelines were described for collection, drying, and handling of the precipitates to prevent the formation of Ca(OH)2 during synthesis and minimize carbonation. Interlayer spacing in precipitates was studied by transmission XRD to compare the effects of Ca:Si, relative humidity, and time, using the 14Å tobermorite structure as a baseline for synthetic C-S-H. The growth and nucleation kinetics of C-S-H were then investigated with the combined thermodynamic and population balance equation model (PBEM). The surface characteristics of C-S-H, C-A-S-H, and C-S-H +

were investigated by acoustophoresis to compare the effects of Ca:Si, washing, and dispersion media on zeta potential measurements. Results showed the necessity of full characterization of both solutions and precipitates in order to understand and compare acoustophoresis results. In the final section of the thesis C-S-H, C-A-S-H, and C-S-H +

were grown on the surface of heterogeneous substrates, quartz and calcite, to approach C-S-H growth in real systems. Overall, the results from this thesis provided helpful information on synthetic C-S-H, C-A-S-H, and C-S-H + $ at the full range of Ca:Si molar ratios, particularly ratios above 1.5, as observed in Portland cement. As we get closer to understanding and controlling C-S-H in real systems, this work will help provide insight as to how heterogenous substrates and aluminates introduced by SCMs, in addition to sulfates, commonly added to cement via gypsum, affect the early age strength and kinetics of C-S-H formation.

EPFL2022

Temperature-Dependent Nucleation and Electrochemical Performance of Zn Metal Anodes

Di Yang, Kangning Zhao

A fundamental understanding of the nucleation and growth behaviors of Zn metal anodes over a wide range of temperatures is of great value for suppressing Zn dendrite growth. However, work focused on the early nucleation and growth behavior of Zn metal at various temperatures is still absent. Here, we study the effect of cycling temperature on Zn nuclei size and areal density and find that low temperature induces a smaller and dense nucleus, which prevents the formation of dendrites. Based on this finding, a cooling-treatment-based self-healing strategy is developed to in situ eliminate dendrites, which effectively prolongs the lifespan of the Zn anode by 520%. This novel self-healing strategy could be employed as a reliable strategy for restoring batteries in situ to reach a longer lifespan.

AMER CHEMICAL SOC2022

Spatial and Morphological Control of Cyanine Dye Thin Films

Nicolas Alexandre Serge Leclaire

Cyanine dyes are organic semiconductor compounds with light absorption and emission properties useful for emerging technologies such as solar cells and light-emitting devices. The characteristics of these materials in the solid state depend on their organization of the constituting building blocks. This thesis focuses on controlling the morphology of cyanine dye thin films at different length scales and clarifying the resulting properties. When microstructures present features whose size matches visible light wavelengths, new properties may arise from light-matter interactions. Here the properties resulting from the light-matter interactions of cyanine droplet films cast from solution are studied. Based on experimental evidence, it is shown that dye droplet ensembles scatter light with different efficiencies and wavelength ranges depending on their dimensions. FDTD simulations are used to show that this effect results fromscattering enhancement at the absorption edge of the dye where the refractive index varies considerably. Simulations also provide a better understanding of individual dropletsâ interaction with light. While earlier work had hypothesized that the observed scattering phenomenon were due to crystalline clusters within the droplets, this work highlights the contribution of the dye filmmorphology. Cyanines also form single crystals whose fabrication induces molecular-scale order in the material. Previous work demonstrated that thin single crystals could be grown by solvent vapor annealing of dye droplets. Here it is shown that in uncontrolled conditions, cyanine single crystals destabilize to formdendritic crystals. In-situ microscopy observations highlight the solute reservoir role of the droplet distribution surrounding a growing crystal; when the distance between droplets and the crystal front is large, the solute supply is diffusion-limited. Moreover variations in local pressure equilibrium between the droplets and crystal front lead to advection fluxes which perturb the crystal growth. These observations help design configurations to either prevent crystal destabilization or take advantage of the dendritic growth in a controlled manner. In addition, the patterning of crystals on a substrate is relevant for their application in devices. A practical challenge is to induce single crystal growth at specific locations. Here, surfaces patterned with SAMs of hydrophilic and hydrophobic thiols are used to create dye droplet arrays from which crystals can be grown. This method is shown to yield local crystallization of the dye and to prevent crystal destabilization through better control of the droplet distribution. By varying the dye solution concentration, partial control over crystal density is achieved, however it proved difficult to control the number of nuclei per droplet. A more controlled evaporation and solvent vapor annealing system might be necessary to master the nucleation process. Finally the structure and optical properties of cyanine single crystals are addressed. The crystal structure was determined by X-ray diffraction. Structural aspects are shown to lead to excitonic couplings, which are evidenced by orientation-dependent spectroscopic measurements of single crystals. Although further investigation of the absorption band structure is necessary, the results are promising for photovoltaic devices as they might improve exciton transport compared to amorphous layers.

EPFL2018