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Defects
Distortions of the crystal lattice often occur when impurities are added to a
solid. As a result, point defects often determine the properties of a material.
They can change the ease with which a material conducts electricity, its
mechanical strength, its ability to be shaped by hammering (malleability), or
to be drawn into wires (ductility). Dissolving small amounts of carbon in iron,
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for example, give the alloy known as steel, which is signicantly stronger
than iron. But higher percentages of carbon make steel so brittle that it can
shatter when dropped.
Point defects distort the lattice and provide a way for atoms to move about
the solid. Atoms can move from a lattice site into a vacancy, for example,
creating a new vacancy, as shown in the gure below.
Theoretical calculations of the ease with which one plane of atoms should slip
over another suggest that metals should be much more resistant to stress
than they are. In other words, metals are softer than one would expect.
Metallurgists have explained this by assuming that metals contain defects
that allow planes of atoms to slip past each other more readily than expected.
This hypothesis has been conrmed by microscopic analysis, which shows
dislocations that run through the crystal. There are two types of dislocations:
edge or screw dislocations. An edge dislocation is an extra half plane of
atoms that goes part way through a solid structure, as shown in the gure
below.
Imagine, for example, a single playing card inserted halfway into a deck of
cards. The line formed by the inserted card would be a dislocation line. The
presence of a dislocation defect allows one plane of atoms to slip more easily
over its neighboring plane of atoms, as shown in the gure below. Not all the
atoms in the two planes move past each other simultaneously; they move one
row at a time.
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Because they allow planes of atoms in a solid to move one row at a time,
dislocations can weaken a metal. Paradoxically, they can also strengthen a
metal when the dislocations intersect to product knots similar to the
intersecting wrinkles in the gure labeled "b" in the gure below. This
phenomenon is encountered with metals that have been work hardened.
Consider what happens, for example, when a piece of iron is heated,
hammered, cooled, reheated, and reworked to form wrought iron. In the
course of work hardening the metal, intersecting dislocations are generated
that hinder the movement of planes of atoms.
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Silver and copper metal are among the best conductors of electricity, with a
conductivity of only 106 ohm-cm. (This is why copper is the metal most often
used in electric wires.) The conductivity of semiconductors such as silicon
and germanium is 108 to 1010 times smaller. (When pure, these semimetals
have a conductivity of 10-2 to 10-4 ohm-cm.) Insulators include glass (10-10
ohm-cm), diamond (10-14 ohm-cm), and quartz (10-18 ohm-cm), which all have
an extremely small tendency to carry an electric current.
The 1024-fold range of conductivity is not the only dierence among metals,
semiconductors, and insulators. Metals become better conductors when they
are cooled to lower temperatures. Some metals are such good conductors at
very low temperatures that they no longer have a measurable resistance and
therefore become superconductors. Semiconductors show the opposite
behavior they become much better conductors as the temperature
increases. The dierence between the temperature dependence of metals and
semiconductors is so signicant it is often the best criterion for distinguishing
between these materials. The large range of conductivities of solids is shown
in the gure below.
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Now let's imagine what happens when enough lithium atoms come together
to form a piece of lithium metal. The valence electrons are no longer conned
to the region between pairs of lithium nuclei, as was the case for an isolated
Li2 molecule in the gas phase. In the metal, each lithium atom is perturbed by
its neighbors and the energy states of each atom are slightly altered. The 1s
orbitals on the various metal atoms interact to form a band of orbitals whose
energy falls within a range from slightly below the energy of the isolated 1s
orbital to slightly above this energy, as shown in the gure below. The same
thing happens to the 2s orbitals.
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Each of the orbitals in these bands can hold two electrons of opposite spin.
Because there were two electrons in each of the 1s orbitals that formed the
lower-energy band, the "1s" band is lled. But there was only one electron in
each of the 2s orbitals that formed the higher-energy band, which means that
the "2s" band is only half-lled. It takes little, if any energy, to excite one of
the electrons in the 2s band from one orbital to another in the band. (The
energy gap between orbitals in the 2s band in lithium is only about 10-45 kJ.)
By moving from orbital to orbital within the 2s band, electrons can move from
one end of the crystal to the other. This band of orbitals is therefore called a
conduction band because it enables lithium metal to conduct electricity.
Semiconductors also have a band structure that consists of lled and empty
bands. The gap between the highest energy lled band and the lowest energy
empty band is small enough, however, that electrons can be excited into the
empty band by the thermal energy the electrons carry at room temperature.
Semiconductors therefore fall between the extremes of metals and insulators
in their ability to conduct an electric current.
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If the amount of arsenic is kept very small, the distance between these atoms
is so large that they don't interact. As a result, the extra electrons from the
arsenic atoms occupy orbitals in a very narrow band of energies that lie
between the lled and empty bands of the semiconductor, as shown in the
gure below. This decreases the amount of energy required to excite an
electron into the lowest energy empty band in the semiconductor and
therefore increases the number of electrons that have enough energy to cross
this gap. As a result, this "doped" semiconductor becomes a very much better
conductor of electricity than the pure semiconductor. Because the electric
charge is carried by a ow of negative particles, these semiconductors are
called n-type.
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Thermal Conductivity
You may have noticed that metal ice-cube trays feel signicantly colder then
plastic ice-cube trays when you remove them from the freezer. Your senses
are obviously misleading you because the trays are at the same temperature
the temperature of the freezer. The metal trays feel colder because metals
are much better conductors of heat than plastic.
The ease with which metals conduct heat is related to their ability to conduct
an electric current. Most of the energy absorbed by a metal when it is heated
is used to increase the rate at which the atoms vibrate around their lattice
sites. But some of this energy is absorbed by electrons in the metal, which
move from orbital to orbital through the conduction band. The net result is a
transport of kinetic energy from one portion of the metal surface to another.
Metals feel cold to the touch because the electrons in the conduction band
carry heat away from our bodies and distribute this energy through the metal
object.
Plastics, on the other hand, are thermal insulators. They are poor conductors
of heat because orbitals in which electrons are held tend to be localized on an
individual atom or between pairs of atoms. The only way for electrons to
carry energy through a plastic is to use this energy to excite an electron from
a lled orbital to an empty orbital. But the dierence between the energies of
the lled and empty orbitals is so large that this rarely happens.
Thermal Thermal
Conductivity Conductivity
Material (J/scmK)a Material (J/scmK)a
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Thermal Expansion
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The same phenomenon, however, is used to form the thermostats that turn
electrical appliances on and o. When two metals with very dierent
coeicients of thermal expansion are joined to form a bimetallic strip, the
metal that expands the most when heated forces the adjoined metal strip to
bend toward the metal with the smallest thermal expansion. This bimetallic
strip can be used to make a device that will turn a heater on or o as contact
is made or broken with an electrical contact, as shown in the gure below.
Materials Science
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