Materials Amorphous

In such materials, there are four different states, illustrated on the graphs in Fig. 7.13. 

Below Tg, the material is solid and glassy, and has high modulus (several [GPa ). 

For molecular weights below a value Me, which depends on the compound, and at temperatures above Tg, the material is a liquid with viscosity proportional to M. 

As chains are not chemically bonded together, they behave like a very viscous liquid at higher temperatures. The viscosity rj now varies as M . This is the behaviour of very hot spaghetti, as opposed to merely warm spaghetti. 

Note that above Tg, the behaviour described here as a function of temperature could just as well have been presented as a function of time scale. For rapid excitations, the response is rubbery for longer times, the response is that of a viscous fluid. Once again, the spaghetti analogy is perfect raising the fork too slowly, it all slides off. 

The modeling of amorphous solids is a more dilhcult problem. This is because there is no rigorous way to determine the structure of an amorphous compound or even dehne when it has been found. There are algorithms for building up a structure that has various hybridizations and size rings according to some statistical distribution. Such calculations cannot be made more efficient by the use of symmetry. 

Overall, solid-state modeling requires more time on the part of the researcher and often more CPU-intensive calculations. Researchers are advised to plan on 

Theoretical Aspects and Computer Modelling of the Molecular Solid State A. Gavezotti, Ed., John Wiley Sons, New York (1997). 

Pisani, Quantum-Mechanical Ah Initio Calculation of the Properties of Crystalline Materials Springer-Verlag, New York (1996). 

Hoffmann, Solids and Surfaces A Chemist s View of bonding in Extended Structures VCH, New York (1988). 

With materials of this type FIM finds its limitations. Several attempts have been made to use field ion microscopy to study amorphous materials such as metallic glasses and amorphous silicon or hydrogenated amorphous silicon thin films deposited on metal tip surfaces.96 98 100-102 Since there is no well defined crystal lattice, the structure of an amorphous material is usually described by the pair distribution function of the 

In Fe8oB2o, Jacobaeus et al,96 claim to be able to derive a triplet correlation of atomic positions from field ion images. Specifically, they find that the distribution of bond angles between neighbor atoms exhibits a fairly distinctive peak at 60°, a broad peak between 90 and 125°, and a 

The vapour deposition method is widely used to obtain amorphous solids. In this technique, atoms, molecules or ions of the substance (in dilute vapour phase) are deposited on to a substrate maintained at a low temperature. Most vapour-deposited amorphous materials crystallize on heating, but some of them exhibit an intervening second-order transition (akin to the glass transition). Amorphous solid water and methanol show such transitions. The structural features of vapour-deposited amorphous solids are comparable to those of glasses of the same materials prepared by melt-quenching. 

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Amorphous materials exliibit speeial quantum properties with respeet to their eleetronie states. The loss of periodieify renders Bloeh s theorem invalid k is no longer a good quantum number. In erystals, stnietural features in the refleetivify ean be assoeiated with eritieal points in the joint density of states. Sinee amorphous materials eaimot be deseribed by k-states, seleetion niles assoeiated with k are no longer appropriate. Refleetivify speetra and assoeiated speetra are often featureless, or they may eonespond to highly smoothed versions of the erystalline speetra. 

Density, mechanical, and thermal properties are significantly affected by the degree of crystallinity. These properties can be used to experimentally estimate the percent crystallinity, although no measure is completely adequate (48). The crystalline density of PET can be calculated theoretically from the crystalline stmcture to be 1.455 g/cm. The density of amorphous PET is estimated to be 1.33 g/cm as determined experimentally using rapidly quenched polymer. Assuming the fiber is composed of only perfect crystals or amorphous material, the percent crystallinity can be estimated and correlated to other properties. 

In an amorphous material, the aUoy, when heated to a constant isothermal temperature and maintained there, shows a dsc trace as in Figure 10 (74). This trace is not a characteristic of microcrystalline growth, but rather can be well described by an isothermal nucleation and growth process based on the Johnson-Mehl-Avrami (JMA) transformation theory (75). The transformed volume fraction at time /can be written as... 

Iron(III) hydroxide [1309-33-7], FeH02, is a red-brown amorphous material that forms when a strong base is added to a solution of an iron(III) salt. It is also known as hydrated iron(III) oxide. The fully hydrated Fe(OH)3 has not been isolated. The density of the material varies between 3.4-3.9 g/cm, depending on its extent of hydration. It is insoluble in water and alcohol, but redissolves in acid. Iron(III) hydroxide loses water to form Fe203. Iron(III) hydroxide is used as an absorbent in chemical processes, as a pigment, and in abrasives. Salt-free iron(III) hydroxide can be obtained by hydrolysis of iron(III) alkoxides. 

Pyrolusite is a black, opaque mineral with a metallic luster and is frequendy soft enough to soil the fingers. Most varieties contain several percent water. Pyrolusite is usually a secondary mineral formed by the oxidation of other manganese minerals. Romanechite, a newer name for what was once known as psilomelane [12322-95-1] (now a group name) (7), is an oxide of variable composition, usually containing several percent water. It is a hard, black amorphous material with a dull luster and commonly found ia the massive form. When free of other oxide minerals, romanechite can be identified readily by its superior hardness and lack of crystallinity. 

Condensed phosphates are derived by dehydration of acid orthophosphates. The resulting polymeric stmctures are based on a backbone of P—O—P linkages where PO tetrahedra are joined by shared oxygen atoms. The range of materials within this classification is extremely broad, extending from the simple diphosphate, also known as pyrophosphate, to indefinitely long-chain polyphosphates and ultraphosphates (see Table 1). Both weU-defined crystalline and amorphous materials occur among the condensed phosphates. 

Fig. 4. Specific volume vs temperature for a crystallizahle polymer. The dashed line represents amorphous material (6). Numbers refer to individual states.

Over 50 acidic, basic, and neutral aluminum sulfate hydrates have been reported. Only a few of these are well characterized because the exact compositions depend on conditions of precipitation from solution. Variables such as supersaturation, nucleation and crystal growth rates, occlusion, nonequilihrium conditions, and hydrolysis can each play a role ia the final composition. Commercial dry alum is likely not a single crystalline hydrate, but rather it contains significant amounts of amorphous material. 

E — E is defined as the fl-gap which leads to the existence of semiconducting behavior in amorphous materials. 

Percent Crystallinity. For samples that consist of a mixture of crystalline and amorphous material, it is possible to determine the percent of crystallinity by measuring the integrated intensity of sharp Bragg reflections and the integrated intensity of the very broad regions due to the amorphous scattering. 

The properties of elastomeric materials are also greatly iafluenced by the presence of strong interchain, ie, iatermolecular, forces which can result ia the formation of crystalline domains. Thus the elastomeric properties are those of an amorphous material having weak interchain iateractions and hence no crystallisation. At the other extreme of polymer properties are fiber-forming polymers, such as nylon, which when properly oriented lead to the formation of permanent, crystalline fibers. In between these two extremes is a whole range of polymers, from purely amorphous elastomers to partially crystalline plastics, such as polyethylene, polypropylene, polycarbonates, etc. 

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