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Related Concept Videos

Metallic Solids02:37

Metallic Solids

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.
All metallic solids exhibit high thermal and electrical conductivity, metallic luster, and malleability. Many...

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Microcrystalline hexagonal tungsten bronze. 2. Dehydration dynamics.

Vittorio Luca1, Christopher S Griffith, John V Hanna

  • 1Australian Nuclear Science and Technology Organisation, ANSTO Minerals, New Illawarra Road, Lucas Heights, NSW 2234, Australia. vluca@cnea.gov.ar

Inorganic Chemistry
|June 13, 2009
PubMed
Summary
This summary is machine-generated.

Thermal treatment of hexagonal tungsten bronze (HTB) phases with sodium (Na+) or cesium (Cs+) cations causes structural changes. Water removal and cation locking in HTB tunnels influence ion extractability, particularly for Cs+ under acidic conditions.

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Area of Science:

  • Materials Science
  • Solid-State Chemistry
  • Inorganic Chemistry

Background:

  • Hexagonal tungsten bronze (HTB) phases, A(x)WO(3+x/2).zH(2)O, feature exchangeable cations (A = Na+, Cs+) in hexagonal tunnels.
  • Understanding thermal transformations is crucial for applications involving ion exchange and material stability.

Purpose of the Study:

  • To investigate the low-temperature thermal transformations of hydrothermally prepared HTB phases containing Na+ and Cs+.
  • To correlate structural changes with cation behavior and extractability.

Main Methods:

  • X-ray diffraction (XRD) in air and synchrotron XRD/neutron diffraction in vacuum.
  • Thermogravimetric analysis (TGA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT).
  • (23)Na and (133)Cs magic angle spinning (MAS) Nuclear Magnetic Resonance (NMR) spectroscopy.

Main Results:

  • Cesium-exchanged HTB showed cell volume contraction (25-350°C) due to water removal, followed by lattice expansion (350-600°C).
  • Net thermal contraction in Cs-HTB led to Cs+ locking in tunnels, reducing extractability in acidic media.
  • (133)Cs MAS NMR revealed a shift from multiple to a single Cs+ environment upon dehydration.
  • Sodium-exchanged HTB exhibited similar contraction, but Na+ was more easily extracted due to its smaller ionic radius.
  • (23)Na MAS NMR indicated complex Na+ speciation and dynamic interchange upon thermal treatment.

Conclusions:

  • Thermal treatment significantly alters HTB structure, impacting cation mobility and extractability.
  • The observed structural changes and cation locking in Cs-HTB explain reduced Cs+ extractability under acidic conditions.
  • Differences in Na+ and Cs+ behavior are attributed to their respective ionic radii and interactions within the HTB framework.