Two centuries of morphology of crystals: Integration of principles of mathematical crystallography, statistical mechanics of surface models and chemistry

Progress in Materials Science

Kim

et al. 2016

With the highly competitive development of chemical and pharmaceutical industries, mastering crystal growth is becoming increasingly necessary. Modern industrial manufacturers place high importance on the ability to grow crystals with a specific habit using tailored operating conditions. A detailed understanding of crystal growth is, therefore, vital for researchers in crystallography and crystallization to respond and realize this objective. Various models to predict crystal shape in the literature are reviewed here. The most commonly adopted are usually non-mechanistic and limited in their predictive power and utility, especially for products of industrial interest. Mechanistic models offer far more potential for rational crystal design, but

Section: Pbc Algorithmmentioning

confidence: 99%

A design aid for crystal growth engineering

Progress in Materials Science

Kim

et al. 2016

“…Within this analysis, PBCs − are assumed to represent the energetics entirely (they are the strong, directional, repeating interactions within the crystal). An energy cutoff of 0.5 kT is used that allows the PBCs to encompass at least 90% of the lattice energy; furthermore, this should be appropriate since 1 kT serves as a boundary estimate for step roughening. − …”

Section: Mechanistic Modelingmentioning

confidence: 99%

Predicting the Effect of Solvent on the Crystal Habit of Small Organic Molecules

Crystal Growth & Design

Green

Marshall

et al. 2016

In order to develop a practical engineering tool for predicting the relative growth rates and morphology of solution-grown faceted crystals, a method for quickly determining solvent-modified crystal surface energies is required. The bulk interface approximation and model by van Oss, Chaudhury, and Good provides the most practical option available for small organic molecules. Applying these techniques to the mechanistic growth modeling of four centrosymmetric crystal systems provides evidence of the utility of this treatment, since both sublimation and solution growth shape predictions correspond to experimental shapes. The fact that the approach correctly predicts the changes between sublimation and solution growth shapes supports the ability of this technique to accurately account for the solvent effect.

Modeling layered crystal growth at increasing supersaturation by connecting growth regimes

Doherty

2017

AIChE Journal

Mechanistic modeling facilitates rational crystallization engineering and design space screening. For an accurate model, the dominant growth mechanism operating on each face must be determined, which is highly dependent on supersaturation. Considering the case of centrosymmetric growth units, we developed and connected existing mechanistic expressions for spiral and two‐dimensional‐nucleation growth regimes, through application of stationary nucleation rate theory. Our approach enables calculation of crossover supersaturations and forms a framework to model the specific mechanism operating on each face under given crystallization conditions. Increasing supersaturation can change the crystal morphology; as face families switch growth mechanisms, they may grow out of the steady‐state shape, or influence its aspect ratio. Application of the model to naphthalene, biphenyl, pentaerythritol and β‐HMX shows the ability to capture experimentally observed examples of such supersaturation‐dependent crystal habits. This methodology broadens the applicability of mechanistic crystal growth modeling to include higher‐supersaturation industrial processes. © 2017 American Institute of Chemical Engineers AIChE J, 63: 1338–1352, 2017