Amorphous solid

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An amorphous solid is a solid in which there is no long-range order of the positions of the atoms. (Solids in which there is long-range atomic order are called crystalline solids or morphous). Most classes of solid materials can be found or prepared in an amorphous form. For instance, common window glass is an amorphous ceramic, many polymers (such as polystyrene) are amorphous, and even foods such as cotton candy are amorphous solids.

In principle, given a sufficiently high cooling rate, any liquid can be made into an amorphous solid. Cooling reduces molecular mobility. If the cooling rate is faster than the rate at which molecules can organize into into a more thermodynamically favorable crystalline state, then an amorphous solid will be formed. Because of entropy considerations, many polymers can be made amorphous solids by cooling even at slow rates. In contrast, if molecules have sufficient time to organize into a structure with two- or three-dimensional order, then a crystalline (or semi-crystalline) solid will be formed. Water is one example. Because of its small molecular size and ability to quickly rearrange, it cannot be made amorphous without resorting to specialized hyperquenching techniques.

Amorphous materials can also be produced by additives which interfere with the ability of the primary constituent to crystallize. For example, addition of soda to silicon dioxide results in window glass, and the addition of glycols to water results in a vitrified solid.

Some materials, such as metals, are difficult to prepare in an amorphous state. Unless a material has a high melting temperature (as ceramics do) or a low crystallization energy (as polymers tend to), cooling must be done extremely rapidly. As the cooling is performed, the material changes from a supercooled liquid, with properties one would expect from a liquid state material, to a solid. The temperature at which this transition occurs is called the glass transition temperature or Tg.

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Amorphous solids produced by other routes, such as ion implantation and thin-film deposition are, technically speaking, not glasses.

One way to produce a material without an ordered structure is to take a crystalline material and remove the order by damaging it. A practical, controllable way to do this is by firing ions into the material at high speed, so that collisions inside the material knock all atoms from their original positions. This technique is known as ion implantation, and only forms amorphous solids if the material is too cold for atoms to diffuse back to their original positions as the process continues.

Techniques such as sputter deposition and chemical vapour deposition can be used to deposit a thin film of material onto a surface. If the surface is kept cold, the atoms being deposited will not, on average, gain enough energy to diffuse along the surface until they find a place in an ordered crystal. For every deposition technique, there is a substrate temperature below which the deposited film will be amorphous. However, surface diffusion requires much less energy than diffusion through the bulk, so that these temperatures are often lower than those required to make amorphous films by ion implantation.

It is difficult to make a distinction between truly amorphous solids and crystalline solids in which the size of the crystals is very small (less than two nanometres). Even amorphous materials have some short-range order among the atomic positions (over length scales of less than five nanometres). Furthermore, in very small crystals a large fraction of the atoms are located at or near the surface of the crystal; relaxation of the surface and interfacial effects distort the atomic positions, decreasing the structural order. Even the most advanced structural characterization techniques, such as x-ray diffraction and transmission electron microscopy, have difficulty in distinguishing between amorphous and crystalline structures on these length scales.

The transition from the liquid state to the glass, at a temperature below the equilibrium melting point of the material, is called the glass transition. From a practical point of view, the glass transition temperature is defined empirically as the temperature at which the viscosity of the liquid exceeds a certain value (commonly 1013 pascal-seconds). The transition temperature depends on cooling rate, with the glass transition occurring at higher temperatures for faster cooling rates. The precise nature of the glass transition is the subject of ongoing research. While it is clear that the glass transition is not a first-order thermodynamic transition (such as melting), there is debate as to whether it is a higher-order transition, or merely a kinetic effect.

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