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Ionic crystals consist of two or more different kinds of ions that usually have different sizes. The packing of these ions into a crystal structure is more complex than the packing of metal atoms that are the same size.
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Solids in which the atoms, ions, or molecules are arranged in a definite repeating pattern are known as crystalline solids. Metals and ionic compounds typically form ordered, crystalline solids. A crystalline solid has a precise melting temperature because each atom or molecule of the same type is held in place with the same forces or energy. Amorphous solids or non-crystalline solids (or, sometimes, glasses) which lack an ordered internal structure and are randomly arranged. Substances that...
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Metallic solids such as crystals of copper, aluminum, and iron are formed by metal atoms. The structure of metallic crystals is often described as a uniform distribution of atomic nuclei within a “sea” of delocalized electrons. The atoms within such a metallic solid are held together by a unique force known as metallic bonding that gives rise to many useful and varied bulk properties.
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The structure of a crystalline solid, whether a metal or not, is best described by considering its simplest repeating unit, which is referred to as its unit cell. The unit cell consists of lattice points that represent the locations of atoms or ions. The entire structure then consists of this unit cell repeating in three dimensions. The three different types of unit cells present in the cubic lattice are illustrated in Figure 1.
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The modulated average structure of mullite.

Johannes Birkenstock1, Václav Petříček2, Bjoern Pedersen3

  • 1FB5 - Geowissenschaften/Kristallographie, Universität Bremen, Klagenfurter Str., 28359 Bremen, Germany.

Acta Crystallographica Section B, Structural Science, Crystal Engineering and Materials
|June 1, 2015
PubMed
Summary

Single crystals of mullite were studied using X-ray and neutron diffraction, revealing inherent structural disorder and incommensurate modulations. The refined modulated structure represents the true average structure of mullite, clarifying its complex atomic arrangements.

Keywords:
2:1 mulliteceramicsdiffuse scatteringdisordered modulated structureneutron diffraction

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Area of Science:

  • Solid State Chemistry
  • Crystallography
  • Materials Science

Background:

  • Mullite (Al(4.8)Si(1.2)O(9.6)) is a critical ceramic material with a complex crystal structure.
  • Previous studies indicated inherent disorder and diffuse scattering in mullite, but a definitive average structure remained elusive.

Purpose of the Study:

  • To investigate the structural characteristics of homogeneous, inclusion-free 2:1 mullite single crystals.
  • To confirm and further elucidate the nature of diffuse scattering and satellite reflections in mullite.
  • To refine the incommensurately modulated crystal structure of mullite using the superspace approach.

Main Methods:

  • Growth of 2:1 mullite single crystals using the Czochralski technique.
  • X-ray and neutron diffraction analysis to study crystal structure and diffuse scattering.
  • Microprobe analysis for precise chemical composition determination.
  • Superspace refinement of the one-dimensional incommensurately modulated structure.

Main Results:

  • Confirmation of inherent diffuse scattering and satellite reflections as features of the mullite structure.
  • Precise chemical composition (Al(4.82(3))Si(1.18(1))O(9.59(5))) and significant silicon occupancy (8-20%) at the T* site.
  • Determination of three incommensurate modulation vectors (q1, q2, q3) and refinement of the q1-modulated structure.
  • Identification of harmonic occupational modulations in tetrahedral units as the primary driver of the modulated structure.

Conclusions:

  • The refined modulated structure, characterized by small-amplitude harmonic modulations, represents the true average structure of mullite.
  • Mullite exhibits local ordering but a long-range average structure that is not completely disordered.
  • The study clarifies the complex interplay of vacancies and tetrahedral units, providing a deeper understanding of mullite's structural behavior.