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Table of contents
Affidavit
List of Publications and Conferences
Abstract
Résumé
Résumé étendu
Chapter 1 Introduction
1.1 Motivation
1.2 Background and Objective
1.3 Structure of the Thesis
Chapter 2 Literature Review
2.1 Fundamentals of Crystallization
2.1.1 Mechanisms of Nucleation
2.1.2 Classical Nucleation Theory
2.1.3 Two-step Nucleation Theory (2-SNT)
2.2 Nucleation Kinetics: Approaches on Data Acquisition and Treatment
2.2.1 Deterministic Approach
2.2.2 Stochastic Approach
2.3 Droplet-based Microfluidics in Crystallization Studies
2.3.1 Principle of Droplet Generation in Microfluidics
2.3.2 Recent Advances in Microfluidics Crystallization
2.4 Principle of Microdroplet Evaporation
2.4.1 Contact Line Behavior (CCA, CCR, SS mode)
2.4.2 Evaporation Rate Models
Chapter 3 Materials and Methods
3.1 Model Compounds
3.1.1 Para-Aminobenzoic acid (PABA)
3.1.2 Glutamic acid (GA)
3.1.3 Sodium chloride (NaCl)
3.2 Polymers used in the microfluidic set-up
3.2.1 Polyetheretherketone (PEEK)
3.2.2 Fluorinated ethylene propylene (FEP)
3.2.3 Polydimethylsiloxane (PDMS)
3.2.4 Polymethylmethacrylate (PMMA)
3.3 Process Analytical Tools (PATs)
3.3.1 Optical Reflectance Measurement (ORM)
3.3.2 In situ Raman spectroscopy
3.4 Experimental Setups
3.4.1 Setup for Liter Scale Experiments
3.4.2 Setup for mL Scale Experiments
3.4.3 Setup for μL Scale Experiments
3.4.4 Setup for Sessile Microdroplet Experiment
Chapter 4 Measuring Primary Nucleation Rates in Agitated Systems using Particle Count Approach
4.1 Introduction
4.2 Materials and Methods
4.2.1 Chemicals and Equipment
4.2.2 Solubility Measurement
4.2.3 Calibration of in-situ Raman Spectroscopy
4.2.4 Calibration of In-situ 3D ORM
4.2.5 Crystallization Process Monitoring
4.3 Results and Discussion
4.3.1 Identification of Polymorphs
4.3.2 Solubility Data
4.3.3 Calibration Curves of ORM
4.3.4 Validation of ORM Measurement by Raman Spectroscopy
4.3.5 Total Nucleation Rates from in-situ ORM
4.3.6 Estimation of Primary Nucleation Rate
4.4 Conclusion
Chapter 5 Nucleation Kinetics in Agitated Systems: Particle Counts vs Induction Time Approach
5.1 Introduction
5.2 Materials and Methods
5.2.1 Chemicals and Equipment
5.2.2 Induction Time Measurement
5.2.3 Extraction of Nucleation Rate from Induction Time
5.3 Results and Discussion
5.3.1 Nucleation Rates from Induction Time Probability Distribution
5.3.2 Confidence Intervals of Estimated Parameters
5.3.3 Comparing Nucleation Kinetic Parameters
5.4 Conclusion
Chapter 6 Quantifying Nucleation Kinetics: A Multi-scale Comparison
6.1 Introduction
6.2 Material and Methods
6.2.1 Liter Scale
6.2.2 Milliliter Scale
6.2.3 Submicroliter Scale
6.3 Results and Discussion
6.4 Conclusion
Chapter 7 Probing Nucleation in Microdroplets via Image Analysis: Effect of Diffusive Interactions
7.1 Introduction
7.2 Materials and Methods
7.2.1 Details of Instrumentation
7.2.2 Microdroplet Generation
7.2.3 Humidity Regulation
7.2.4 Numerical Detection of Oscillations
7.3 Results and Discussion
7.3.1 Effect of Diffusive Interactions
7.3.2 Eliminating Diffusive Interactions
7.4 Conclusion
Chapter 8 Nucleation in Sessile Microdroplets: Measuring Induction Time via Deliquescence-Efflorescence Cycle
8.1 Introduction
8.2 Materials and Methods
8.3 Results and Discussion
8.3.1 Analysis of σ-curves
8.3.2 Assessment of Reproducibility
8.3.3 Statistical Analysis
8.3.4 Checking for Possible Influence of Impurities
8.3.5 Nucleation Kinetic Parameter Estimation
8.4 Conclusion
Chapter 9 Modeling the Evaporation Dynamics of Sessile Saline Microdroplets
9.1 Introduction
9.2 Modeling
9.2.1 Influence of oil thickness on the evaporation rate
9.2.2 Considering the presence of neighboring droplet
9.2.3 Considering the evolution of droplet density as water evaporate
9.2.4 Dependence of water activity on solute concentration
9.2.5 Models for Contact Line Behavior
9.3 Materials and Methods
9.4 Results and Discussion
9.4.1 Model Predictions for Pure Microdroplets
9.4.2 Model Predictions for Saline Microdroplets
9.4.3 Implications on Crystallization Studies
9.5 Conclusion
Chapter 10 Modeling the Nucleation Kinetics of Aqueous NaCl with Modified Poisson Distribution
10.1 Introduction
10.2 Theory and Modeling
10.2.1 Classical Nucleation Theory for Ionic Systems
10.2.2 Modified Poisson Distribution Function
10.3 Results and Discussion
10.3.1 Kinetic Parameter Estimation
10.3.2 Comparison with Literature
10.3.3 Observing Confinement Effects
10.4 Conclusion
Chapter 11 Concluding Remarks and Perspective
11.1 Notable Findings
11.2 Perspective
11.2.1 Influence of interfering variables in Agitated Crystallizers
11.2.1 Evaporative microdroplet experiments
References
