Growth modification of hematite by phosphonate additives

• Published in: Journal of crystal growth Vol. 310; no. 3; pp. 688 - 698
• Main Authors: Aschauer, U., Jones, F., Richmond, W.R., Bowen, P., Rohl, A.L., Parkinson, G.M., Hofmann, H.
• Format: Journal Article
• Language: English
• Published: Amsterdam Elsevier B.V 01.02.2008; Elsevier
• Subjects: A1. Adsorption; A1. Computer simulation; A1. Crystal morphology; A1. Surface structure; B1. Oxides; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Exact sciences and technology; Inorganic compounds; Materials science; Methods of crystal growth; physics of crystal growth; Physics; Solid surfaces and solid-solid interfaces; Structure of solids and liquids; crystallography; Structure of specific crystalline solids; Surfaces and interfaces; thin films and whiskers (structure and nonelectronic properties); Theory and models of crystal growth; physics of crystal growth, crystal morphology and orientation; 81.05.Je; 81.07.Wx; B1. Oxides; 31.15.Qg; A1. Surface structure; 81.10.Aj; A1. Adsorption; A1. Computer simulation; A1. Crystal morphology; Hematite; Al. Adsorption; Al. Computer simulation; Al. Crystal morphology; Al. Surface structure; Bl. Oxides; Iron oxide; Adsorption; Growth mechanism; Phosphonates; Computerized simulation; Electron microscopy; Crystal morphology; 31.15.Qg; 81.05.Je; 81.07.Wx; 81.10.Aj; Surface energy; Surface structure
• ISSN: 0022-0248; 1873-5002
• DOI: 10.1016/j.jcrysgro.2007.11.114

The hydroxylated surface structures of seven morphologically important crystallographic surfaces of hematite were calculated—allowing the determination of the surface energies and, consequently, the hematite equilibrium morphology. The docking of two organic phosphonate additives (methyl nitrilo-dimethylenephosphonic acid—MNDP, ethylenediamine tetraphosphonic acid—EDTP) was then simulated on these surfaces and the replacement energies calculated. With these energies, the effect of MNDP and EDTP on the hematite equilibrium morphology could be predicted. Results without the additive show a bipyramidal morphology of (1 0 2) faces capped with (2 2 2) faces at each end. The interaction with the EDTP additive predicts the stabilization of the (1 0 1¯) face to be far more pronounced than for the MNDP additive. This leads to the appearance of (1 0 1¯) faces in the morphology predicted in presence of EDTP. Experimental validation by means of electron microscopy shows morphologies close to those calculated, confirming that a computational approach can be used for the prediction of morphologies of crystals grown in the presence of additives.