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SOLID MATERIALS 32.6
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32.2.4 Molecular or van der Waals Bonds In addition to the three strong primary bonds discussed above, there are also several much weaker (and therefore called secondary) bonds which provide the interatomic attractive forces that hold some types of atoms together in a solid material. These forces are referred to as either secondary bonds, molecular bonds, or van der Waals bonds. These bonds are due to residual electrostatic fields between neutral molecules whose charge distribution is not uniform. Covalently bonded atoms frequently form molecules that behave as electric or magnetic dipoles. Although the molecule itself is electrically neutral, there is an electrical imbalance within the molecule. That is, the center of the positive charge and the center of the negative charge do not coincide, and it is this dipole that creates molecular bonding.
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32.3 ATOMIC STRUCTURES
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Whereas the electrical properties of a material depend on the internal structure of the atoms, the mechanical properties depend on the types of structures that groups of atoms form. In this context, atomic structures refer to the structures that are built by particular arrangements of atoms, not to the internal structure of individual atoms. All solid materials can be classified on the basis of atomic structure into three groups: amorphous, molecular, or crystalline (in order of increasing importance to mechanical properties). Knowledge of the atomic structure of solids makes it possible to understand why a given material has its unique properties and thus to be able to specify the type of material and the condition it should be in to achieve optimum mechanical properties.
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32.3.1 Amorphous Solids Amorphous materials are those whose structure has no repetitive arrangement of the atoms of which it is comprised. In a sense, they have no structure. Although gases and liquids are amorphous materials, the only important amorphous solids are the glasses, and they are frequently considered simply as supercooled liquids. Glass behaves as a typical liquid at high temperatures. The atoms are very mobile and do not vibrate in a fixed location in space. A given mass of hot glass, like any liquid, takes the shape of the container in which it is placed. As a hot glass cools, its atoms vibrate at lower amplitudes and come closer together, resulting in an overall thermal contraction or decrease in specific volume. This decrease in specific volume of a liquid as temperature decreases is approximately linear and occurs with all liquids, including liquid metals. This is illustrated in Fig. 32.1. When any unalloyed liquid metal (a pure metallic element) or chemical compound is cooled to its freezing (or melting) temperature Tm , the atoms come much closer together and become relatively immobile with respect to one another. They form a crystalline structure with very efficient packing, and thus there is a very marked decrease in specific volume at this temperature, as shown in Fig. 32.1. When an alloyed liquid metal freezes to form a solid solution, the transition from liquid to solid takes place in the range of temperatures between the liquidus and the solidus. Further cooling of both solid metals results in a further decrease in specific volume, also linear but of lower slope than in the liquid state.
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Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
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SOLID MATERIALS 32.7
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FIGURE 32.1 Specific volume versus temperature. (A) Glass with a transition temperature Tg ; (B) a crystal that melts at a fixed temperature Tm , such as a pure element or a compound; (C) a crystal that melts over a range of temperature, such as a solid-solution alloy with TL the liquidus temperature and Ts the solidus temperature.
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When hot liquid glass is cooled to some temperature Tg , called the glass transition temperature, there is an abrupt change in the slope of the specific volume versus temperature curve. Unlike crystalline solids, the glass shows no marked decrease in specific volume at this temperature. Below Tg , glass behaves as a typical solid.
32.3.2 Molecular Solids A molecule is a group of atoms that are held together by strong ionic or covalent bonds. A molecular solid is a structure made up of molecules that are attracted to each other by weak van der Waals forces. The two most common types of molecular solids are silicates and polymers. The silicates have ionic intramolecular bonds, and the polymers have covalent ones. Since it is the latter materials that are more important in terms of mechanical properties, they will be discussed in more detail. Polymers are organic compounds of carbon, hydrogen, and oxygen to which other elements such as chlorine or fluorine may be added. They cover a wide range of structural arrangements, with resulting variations in properties. Large molecules are constructed from a repeating pattern of small structural units. The hydrocarbons have repeating structural units of carbon and hydrogen atoms. Figure 32.2 shows some of the more common monomers or unsaturated molecules that are used in the building of macromolecules. The simplest monomer is ethylene (C2H4); it is shown in Fig. 32.2a. It is the base of the group of hydrocarbons called olefins. The olefins have the chemical formula CnH2n. The benzene molecule, shown in Fig. 32.2d, is another important building unit. Because of the shape of the molecule, it is described as a ring molecule or compound. The benzene group is also called the aromatic hydrocarbons. Figure 32.3 illustrates the addition polymerization of the ethylene monomer. The double bonds of ethylene are broken in the presence of a catalyst such as boron tri-
Downloaded from Digital Engineering Library @ McGraw-Hill (www.digitalengineeringlibrary.com) Copyright 2004 The McGraw-Hill Companies. All rights reserved. Any use is subject to the Terms of Use as given at the website.
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