Magnus Boström

Microscopic structures of Laves phases and structurally related compounds : a transmission electron microscopy study

Abstract We present microstructural investigations of Laves phases AB2 and structurally related compounds using transmission electron microscopy. Convergent-beam electron diffration in combination with selected-area diffraction has been used to determine uniquely the space group symmetry of the respective phases from very small illuminated regions. In addition stacking faults, domain boundaries, and intergrowth have been studied by HREM images. By electron beam irradiation intermetallic phases have been transformed in-situ into phases of different compositions. Polar intermetallic phases in the systems Ca—Al—Zn, Ba—Al and Ba—Al—Zn, as well as transition metal based Nb-Co phases have been chosen for this case study. In the Ca—Al—Zn system, the C15- and C36-type crystals did not show orderliness but a randomly mixed occupation of the B-net by Al and Zn atoms. Starting from C36, a C15 phase of constant Ca and lower Zn content as well as a new C36 phase with higher Ca content could be synthesized by means of electron beam irradiation. In the case of CaAlZn no ordering of Al and Zn were observed, i.e., Al and Zn randomly mixed occupy the Cu-site in the CeCu2 structure type. By electron beam irradiation of CaAlZn, a novel hexagonal phase with a hitherto unknown crystal structure is formed. The crystal structures of Ba21Al40 and Ba14Al22+xZn5–x are derived from Laves-type structures by omitting and modifying some of the triangular and Kagom, layers. In the case of Ba21Al40, intergrowth of motifs from the crystal structures of Ba3Al5 and Ba4Al5 were observed, whereas for Ba14Al22+xZn5–x the bulk phase displays a domain structure. Adjacent domains are misoriented by ∼120°, the specific angle resulting from the pseudo-trigonal symmetry of the Ba-net. Therefore, only the (Al,Zn)-net is disordered. No superstructure formation were detected for the three polytypes C36, C15 and C14 in the Nb—Co system. However, TEM images of C36-Nb1–xCo2+x reveal a high stacking fault density with intergrowth of stacks of C36 and C15 sequence. When the C15 phase is rich in Nb, stacking faults seem to be more important than for Co-rich C15 phases, whereas stacking faults have seldom been observed for the Co-rich C14 phase.

Re4Si7, First in a New MoSi2-Based Family of 14-Electron Phases

The compound Re4Si7 poses a long-standing structural mystery at the intersection of the quantum chemical and material properties areas of interest. Its atomic structure has gradually emerged over X ...

Re-determining the nowotny chimney-ladder structure VGe1.82 from powder diffraction data

This thesis is based on a study of five distinct intermetallic systems with the aim of expanding the general knowledge of aperiodically modulated crystal structures. Families of compounds that contain a variety of superstructures together with incommensurately modulated structures have been investigated mainly by means of single crystal X-ray diffraction and higher dimensional structure models.A uniform (3+1)-dimensional structure for Bi-Se phases was developed with the composition as a single variable. The structure description is based on a cubic NaCl type structure with homoatomic layer stackings. It is shown by computational modelling that the formation energies of bismuth selenides with more than 40 at. % Bi are close to zero, a result that supports the idea of a continuous series of stackings corresponding to an ordered solid solution of Bi in Bi2Se3.The Nowotny chimney-ladder structures are described with a (3+1)-dimensional composite structure, valid for all such compounds regardless of the included elements, the composition or the valence electron concentration. A new member is added to this family by the ZrBi1.62 compound. The modulation is believed to arise as a secondary effect of the criteria of a fixed electron count.A symmetry analysis is presented for the RE1+e(MB)4 (RE = rare earth elements, M = iron metal elements) family of compounds and a uniform (3+1)-dimensional composite structure description has been developed. The modulation may be due to the presence of unusually short contacts between the RE channel atoms, giving rise to a rotational modulation of the (MB)4 tetraederstern chains.A (3+1)-dimensional incommensurate structure has been determined for the novel δ1 – CoZn compound. The structure displays a unique assembly of fused icosahedra and the modulation is induced by geometric strain.The structure of the K(PtSi)4 compound was re-determined. Despite a close kinship with the RE1+e(MB)4 compounds, this structure is not modulated.