page_title: Structure of liquids and glasses
section_title: Network glasses
hierarchical_section_title: Structure of liquids and glasses / Network glasses
context_page_description: The structure of liquids, glasses and other non-crystalline solids is characterized by the absence of long-range order which defines crystalline materials. Liquids and amorphous solids do, however, possess a rich and varied array of short to medium range order, which originates from chemical bonding and related interactions. Metallic glasses, for example, are typically well described by the dense random packing of hard spheres, whereas covalent systems, such as silicate glasses, have sparsely packed, strongly bound, tetrahedral network structures. These very different structures result in materials with very different physical properties and applications.
  The study of liquid and glass structure aims to gain insight into their behavior and physical properties, so that they can be understood, predicted and tailored for specific applications. Since the structure and resulting behavior of liquids and glasses is a complex many body problem, historically it has been too computationally intensive to solve using quantum mechanics directly. Instead, a variety of diffraction, NMR, Molecular dynamics, and Monte Carlo simulation techniques are most commonly used.
context_section_description: Early theories relating to the structure of glass included the crystallite theory whereby glass is an aggregate of crystallites (extremely small crystals). However, structural determinations of vitreous SiO₂ and GeO₂ made by Warren and co-workers in the 1930s using x-ray diffraction showed the structure of glass to be typical of an amorphous solid
  In 1932 Zachariasen introduced the random network theory of glass in which the nature of bonding in the glass is the same as in the crystal but where the basic structural units in a glass are connected in a random manner in contrast to the periodic arrangement in a crystalline material.
  
  Despite the lack of long range order, the structure of glass does exhibit a high degree of ordering on short length scales due to the chemical bonding constraints in local atomic polyhedra. For example, the SiO₄ tetrahedra that form the fundamental structural units in silica glass represent a high degree of order, i.e. every silicon atom is coordinated by 4 oxygen atoms and the nearest neighbour Si-O bond length exhibits only a narrow distribution throughout the structure. The tetrahedra in silica also form a network of ring structures which leads to ordering on more intermediate length scales of up to approximately 10 Angstroms.
  Alternative views of the structure of liquids and glasses include the interstitialcy
  model 
  and the model of string-like correlated motion. 
  Molecular dynamics computer simulations indicate these two models are closely connected
  Oxide glass components can be classified as network formers, intermediates, or network modifiers. Traditional network formers (e.g. silicon, boron, germanium) form a highly cross-linked network of chemical bonds. Intermediates (e.g. titanium, aluminium, zirconium, beryllium, magnesium, zinc) can behave both as a network former or a network modifier, depending on the glass composition. The modifiers (calcium, lead, lithium, sodium, potassium) alter the network structure; they are usually present as ions, compensated by nearby non-bridging oxygen atoms, bound by one covalent bond to the glass network and holding one negative charge to compensate for the positive ion nearby. Some elements can play multiple roles; e.g. lead can act both as a network former (Pb⁴⁺ replacing Si⁴⁺), or as a modifier. The presence of non-bridging oxygens lowers the relative number of strong bonds in the material and disrupts the network, decreasing the viscosity of the melt and lowering the melting temperature.
  The alkali metal ions are small and mobile; their presence in a glass allows a degree of electrical conductivity. Their mobility decreases the chemical resistance of the glass, allowing leaching by water and facilitating corrosion. Alkaline earth ions, with their two positive charges and requirement for two non-bridging oxygen ions to compensate for their charge, are much less mobile themselves and hinder diffusion of other ions, especially the alkali's. The most common commercial glass types contain both alkali and alkaline earth ions (usually sodium and calcium), for easier processing and satisfying corrosion resistance. Corrosion resistance of glass can be increased by dealkalization, removal of the alkali ions from the glass surface by reaction with sulphur or fluorine compounds. Presence of alkaline metal ions has also detrimental effect to the loss tangent of the glass, and to its electrical resistance; glass manufactured for electronics (sealing, vacuum tubes, lamps ...) have to take this in account.
caption: The random network structure of glassy SiO2 in two-dimensions. Note that, as in the crystal, each Silicon atom is bonded to 4 oxygen atoms, where the fourth oxygen atom is obscured from view in this plane.