Ranko M. Vrcelj

The crystal growth and perfection of 2,4,6-trinitrotoluene

Abstract Large crystals of TNT were grown from ethyl acetate solution by both temperature lowering and solvent evaporation. The perfection of crystals grown from seeds under carefully controlled conditions was generally higher than those prepared by uncontrolled solvent evaporation. Examination by X-ray topography revealed the crystals to have a characteristic growth induced defect structure comprising growth sectors and boundaries, growth banding, solvent inclusions and dislocations. Twins and stacking faults (SF) were also observed. Many of the defects noted in the topographs can be attributed to impurities. The influence of the highly anisotropic crystal structure on the nature of growth defects is discussed. A structural model proposed to explain twinning and SF formation is partially supported by topographic evidence.

Cephalexin: a channel hydrate

The antibiotic cephalexin [systematic name: D-7-(2-amino-2-phenylacetamido)-3-methyl-8-oxo-5-thia-1-azabicyclo[4.2.0]oct-2-ene-2-carboxylic acid] forms a range of isomorphic solvates, with the maximum hydration state of two water molecules formed only at high relative humidities. The water content of the structure reported here (C(16)H(17)N(3)O(4)S.1.9H(2)O) falls just short of this configuration, having three independent cephalexin molecules, one of which is disordered, and 5.72 observed water molecules in the asymmetric unit. The facile nature of the cephalexin solvation/desolvation process is found to be facilitated by a complex channel structure, which allows free movement of solvent in the crystallographic a and b directions.

Two New Structures of 5-Nitrouracil

The structure of monoclinic anhydrous 5-nitrouracil, C4H3N3O4, and of the solvate 5-nitrouracil dimethyl sulfoxide, C4H3N3O4.C2H6OS, are presented and compared with the previously known structures of the orthorhombic anhydrous form and the monohydrate.

Growth and dislocation studies of β-HMX

BackgroundThe defect structure of organic materials is important as it plays a major role in their crystal growth properties. It also can play a subcritical role in “hot-spot” detonation processes of energetics and one such energetic is cyclotetramethylene-tetranitramine, in the commonly used beta form (β-HMX).ResultsThe as-grown crystals grown by evaporation from acetone show prismatic, tabular and columnar habits, all with {011}, {110}, (010) and (101) faces. Etching on (010) surfaces revealed three different types of etch pits, two of which could be identified with either pure screw or pure edge dislocations, the third is shown to be an artifact of the twinning process that this material undergoes. Examination of the {011} and {110} surfaces show only one type of etch pit on each surface; however their natural asymmetry precludes the easy identification of their Burgers vector or dislocation type. Etching of cleaved {011} surfaces demonstrates that the etch pits can be associated with line dislocations. All dislocations appear randomly on the crystal surfaces and do not form alignments characteristic of mechanical deformation by dislocation slip.ConclusionsCrystals of β-HMX grown from acetone show good morphological agreement with that predicted by modelling, with three distinct crystal habits observed depending upon the supersaturation of the growth solution. Prismatic habit was favoured at low supersaturation, while tabular and columnar crystals were predominant at higher super saturations. The twin plane in β-HMX was identified as a (101) reflection plane. The low plasticity of β-HMX is shown by the lack of etch pit alignments corresponding to mechanically induced dislocation arrays. On untwinned {010} faces, two types of dislocations exist, pure edge dislocations with b = [010] and pure screw dislocations with b = [010]. On twinned (010) faces, a third dislocation type exists and it is proposed that these pits are associated with pure screw dislocations with b = [010].Graphical abstractEtch pits on the twinned (010) face of β-HMX.

Hydration studies of a simple molecular solid

This paper presents novel information on the thermal dehydration and rehydration of the molecular solid, Oxalic Acid Dihydrate. Although the procedure of the overall decomposition process is well-defined, the structural basis and mechanism of the dehydration process has been poorly studied. We show that the dehydration occurs in a planar manner, with a resultant semi-topotactic relationship between hydrated and dehydrated structures, reflected in the molecular packing. During rehydration, the reconstruction of the phase can be seen to occur at a 3-dimensional phase boundary reaction front, i.e. a recrystallisation of the dihydrate on the surface of the reactant product, with the topotactic relationship leading to texturing and possibly epitaxial relationships between partially dehydrated and rehydrated structures. The proposed mechanism is shown to be consistent with the measured kinetics of the process.

Dehydration mechanism of a small molecular solid: 5-nitrouracil hydrate

Previous studies of the dehydration of 5-nitrouracil (5NU) have resulted in it being classified as a “channel hydrate” in which dehydration proceeds principally by the exit of the water molecules along channels in the structure. We have re-examined this proposal and found that in fact there are no continuous channels in the 5NU structure that would contribute to such a mechanism. Product water molecules would be immediately trapped in unlinked voids in the crystal structure and would require some additional mechanism to break loose from the crystal. Through a detailed structural analysis of the macro and micro structure of the 5NU as it dehydrates, we have developed a model for the dehydration process based on the observed development of structural defects in the 5NU crystal and the basic crystallography of the material. The model was tested against standard kinetic measurements and found to present a satisfactory account of kinetic observations, thus defining the mechanism. Overall, the study shows the necessity of complementing standard kinetic studies with a parallel macro and micro examination of the dehydrating material when evaluating the mechanisms of dehydration and decomposition processes.

Nonlinear ptychographic coherent diffractive imaging

Ptychographic Coherent diffractive imaging (PCDI) is a significant advance in imaging allowing the measurement of the full electric field at a sample without use of any imaging optics. So far it has been confined solely to imaging of linear optical responses. In this paper we show that because of the coherence-preserving nature of nonlinear optical interactions, PCDI can be generalised to nonlinear optical imaging. We demonstrate second harmonic generation PCDI, directly revealing phase information about the nonlinear coefficients, and showing the general applicability of PCDI to nonlinear interactions.