Engineering Nanoparticles for Biomedical Applications: From Theory to Experiments and Modeling, wiley, ss.1-21, 2026
This chapter explores the crystallization-driven synthesis of nanoparticles, emphasizing the critical roles of thermodynamics and kinetics in determining crystal size, size distribution, and morphology. Crystallization is a bottom-up approach widely employed in nanomaterial fabrication and proceeds via crystal nucleation and subsequent growth. The chapter begins by outlining Classical Nucleation Theory (CNT), highlighting the influence of supersaturation, temperature, and interfacial energy on the activation energy barrier and nucleation rate. The discussion extends to phase stability and transformations, underscoring the prevalence of metastable phases and the implications of Ostwald's rule of stages. Growth mechanisms, categorized into diffusion- and surface reaction-controlled, are described with reference to models like LaMer's and further examined in the context of Ostwald ripening and particle-based assembly. A central theme of the chapter is the control of particle characteristics through modulation of crystallization parameters. The chapter details strategies for tuning nucleation and growth, such as burst nucleation, seeding, and the use of additives or spatial confinement to regulate size and uniformity. Morphology control is discussed through the lens of internal crystal structure and external growth conditions, including the influence of supersaturation, pH, and selective facet binding. Finally, practical examples of spherical and anisotropic nanoparticles, including iron oxide, gold, and polymeric systems, demonstrate how synthesis techniques and reaction parameters can be tailored to produce nanomaterials with desired structural features. By integrating theoretical insights with experimental case studies, this chapter offers a comprehensive framework for understanding and engineering nanoparticle formation via crystallization.