The Nature of Materials

The chemist ordinarily considers the smallest functional portion of matter to be the
atom. The atom consists of a nucleus, made up of positively charged protons and
uncharged neutrons, surrounded by electrons. The electrons carry negative charges
and move in orbit at different levels. Each level of orbit can contain only a definite
number of electrons, and the number of levels or shells is determined by the atomic
number of the element. All the shells will usually be full except the outer one, which is
short of the maximum possible number of electrons for most materials. All of the
electrons are in constant motion, spinning about their own axes and traveling through
their orbits about the nucleus with speeds dependent on their energy level, which in turn
is strongly affected by the pressure and the temperature conditions. The physicist's
picture of an atom depicts it as a heavy nucleus containing most of the mass,
surrounded by a cloud of moving electrons.
METALLIC STRUCTURE
Definition of a Metal. Metals are usually defined as materials having some degree of
plasticity, relatively high hardness and strength, good electric and thermal conductivity,
crystallinity when solids, and opacity. A definition based on atomic structure is more
precise. A metallic solid is one that has free electrons available in the structure to carry
a current and that has a negative coefficient of conductivity with increasing temperature
States of Matter. The Diagram Below (States Of Matter) shows the relationship that
exists among the three states of matter for a crystalline material. At the intersection of
temperature T , and pressure P on the curve, notice that an increase of
temperature of a material for which this curve is valid would cause the material to
change directly from a solid to a gas. Similarly, a reduction of pressure (a shift toward
the left) would also cause the same change. Such a change of state from solid directly
to gas is known as sublimation. Arsenic is the only metallic material that sublimates at
atmospheric pressure. When the temperature is raised to T2 at pressure P2, the atoms
of the material will become sufficiently active that a change is made from a solid to a
liquid. A further increase in temperature at this same pressure to point T3 will cause a
second change from a liquid to a gas. The intersecting point of the curves at the
temperature Tx and pressure Px is known as the triple point and occurs at the
temperature and pressure conditions under which a material may exist as a solid, a
liquid, a gas, or partially all three at the same time. For most metals, this point occurs
below normal temperatures and well below atmospheric pressure; consequently, most
metals upon being heated go through the changes from solid to liquid to gas as the
temperature increases.

STATES OF MATTER
Space Lattices. As the energy of a liquid metal is reduced by taking away heat, the
attraction between atoms increases until they arrange themselves in definite three-
dimensional geometric patterns that are characteristic of the metal. These structures are
called space lattices and consist of network groupings of identical unit cells that are
aligned in parallel planes.
There are fourteen types of crystal lattices, but most of the common and commercially
important metals exist, in the solid state, in one of three structures. These are, as shown
below (Common Metallic Space Lattice Diagram), body-centered cubic, face-centered
cubic, and hexagonal closed-packed. In the illustrations of unit cells, the dots
representing atoms should be considered as centers of activity for the atoms and not as
graphic illustrations of the atoms themselves.
A single unit cell does not exist alone. To attain stability, it must grow past some critical
size by being joined with other cells that share the atoms on the outer adjacent surface.
For purposes of illustration, it has been assumed that a unit cell can exist by itself and
that all its atoms belong to it alone.

COMMON METALLIC SPACE LATTICE
Body-centered Cubic Lattice. The body-centered cubic cell is made up of nine atoms.
Eight are located the corners of the cube with the ninth positioned centrally between
them. The body-centered cubic is a strong structure, and in general, the metals that are
hard and strong are in this form at normal temperatures. These metals include
chromium, iron, molybdenum, tantalum, tungsten, and vanadium.
Face-centered Cubic Lattice. Face-centered cubic cells consist of fourteen atoms with
eight at the corners and the other six centered in the cube faces. This structure is
characteristic of ductile metals, which include aluminum, copper, gold, lead, nickel,
platinum, and silver. Iron, which is body-centered cubic at room temperature, is also of
the face-centered structure in the temperature range from about 910 C to 1,400 C.
This is a solid-state change that will be discussed more thoroughly in the following
chapter.
Hexagonal Close-packed Lattice. Seventeen atoms combine to make the hexagonal
close-packed unit cell. Seven atoms are located in each hexagonal face with one at
each comer and the seventh in the center. The three remaining atoms take up a
triangular position in the center of the cell equidistant from the two faces. The metals
with this structure are quite susceptible to work-hardening, which will be discussed in
the following chapter. Some of the more commonly used metals that crystallize with this
structure are cadmium, cobalt, magnesium, titanium, and zinc.
Tin is an exception to the other commonly used metals in that the atomic configuration
is body-centered tetragonal, which is similar to the body-centered cubic but has wider
atomic spacing and an elongated axis between two of the opposite faces.
SOLIDIFICATION
Growth of a Crystal. As the temperature of the liquid metal is reduced and the atoms
become less active, they are attracted to each other and take definite positions to form
unit cells. Because cooling cannot be exactly the same for every atom, certain ones will
assume their positions ahead of others and become a nucleus for crystal formation. In
the process of assuming their positions, these first atoms will give up kinetic energy in
the form of heat, which retards the slowing down of other atoms; but as heat removal is
continued, other atoms will take their places along the sides of the already solidified unit
cell, forming new cells that share atoms with the first and with others to come later.
Orderly growth continues in all directions until the crystal, or as usually referred to for
metals, the grain, runs into interference from other grains that are forming
simultaneously about other nuclei.
Although with some metals and with special treatments it is possible to grow single
crystals several inches in diameter, with most metals and at the usual cooling rates,
great numbers of crystals are nucleated and growing at one time with different
orientations. If two grains that have the same orientation meet, they will join to form a
larger grain, but if they are forming about different axes, the last atoms to solidify
between the growing grains will be attracted to each and must assume compromise
positions in an attempt to satisfy a double desire to join with each. These misplaced
atoms are in layers about the grains and are known as grain boundaries. They are
interruptions in the orderly arrangement of the space lattices and offer resistance to
deformation of the metal. A fine-grained metal with large numbers of interruptions,
therefore, will be harder and stronger than a coarse-grained metal of the same
composition and condition.
Grain size, grain orientation, and the composition of grain boundaries are factors that
can influence some nondestructive tests. In radiography, at certain x-ray energies,
diffraction effects can produce images that resemble flaws and, at best, make
interpretation difficult. Ultrasonic testing of large grained castings and welds also may
be radically influenced by excessive noise and attenuation, which may produce false
indications or mark the presence of dangerous flaws.
GRAIN SIZE
The grain (crystal) sizes produced during solidification are dependent both upon the rate
of nucleation and upon the rate of growth of grains. For most materials the rate of
growth is relatively slow, and the primary influence on grain size is the rate of
nucleation. Grain size can be used as an indication, or measure, of properties. For this
reason, visual standards have been set up to aid accurate comparisons. While not in
routine usage, ultrasonic methods have been applied to grain size determination. If the
grains are randomly oriented, at high ultrasonic frequencies, reflection from grain
boundaries that would usually be considered noise can be related to grain size.
Importance of Grain Size. Grain size exerts an important influence on the mechanical
properties of materials and, fortunately, can be controlled by methods much more
precise than manipulation of the factors that influence growth during solidification. In
some processes though, particularly casting, the solidification grain size is important,
because with some materials and some shapes, grain size cannot be readily changed
after the first formation. In those cases in which changes can be effected, additional
processing costs will be added. The methods, other than solidification, that can be used
for grain-size control involve solid-state changes.
As has already been indicated, coarse grains in the harder materials have lower
strength than fine grains. Coarse-grained materials machine more easily, requiring less
power, although the quality of surface produced will not be as good as with a finer-
grained material. Coarse-grained ferrous material is easier to harden by heat treatment
than fine-grained material of the same composition but has increased susceptibility to
cracking under the thermal loads. Coarse-grained material will caseharden on the
surface more readily than fine-grained. It is evident, then, that coarse grains may
sometimes be desirable during processing, but fine grains are usually necessary in the
final product to provide the best mechanical properties. Some deformation processes of
shaping materials can be used so as to cause grain-size reduction automatically during
the shaping process with little or no additional cost involved.
HEAT TREATMENT OF STEEL
Steel has been treated by heating and cooling methods to vary its properties ever since
its discovery, but even today the exact mechanism by which these variations take place
cannot be completely explained by fully accepted theories. Most of the treatments have
been developed empirically. Various theoretical explanations have been used to
describe the mechanism, but it has been only in recent years that the theory has
advanced to the point that it is a prime source of new development of commercial heat-
treating methods.
NDT and Other Control Methods. Change of properties of steel can be accomplished by
cold working, by precipitation hardening, and by allotropic changes. Cold working
changes are important in most of the cold deformation processes and, in some cases,
may be the only treatment received by the metal. Precipitation hardening is seldom
used intentionally, except for stainless steels, although it may be an accidental
occurrence with some of the processing treatments. Causing allotropic changes by
heat-treating procedures is the most effective and most easily accomplished method of
varying mechanical properties of steel and therefore is the most frequently used way of
obtaining the desired properties.
Heat-treating is often defined as intentional heating and cooling for control of properties.
Such a definition is perfectly good, but it must be remembered that the effects of
temperature changes are no less important when they are caused by unintentional heat
transfer during a process such as fusion welding or during a service use in high
environmental temperatures such as in a furnace or gas turbine.
APPROXIMATE EQUILIBRIUM HEAT TREATMENT PROCESSES
Several heat-treating processes place the mate either a complete or an approximate
equilibrium energy condition. These processes include austenitzing, annealing,
normalizing, and spheroidizing. Except for the first, all are finalized at room temperature
but since austenitizing consists of diffusion of car into face-centered cubic iron that
exists at a minimum temperature of 727 C (eutectoid composition only, all others
higher), stability, or equilibrium this state can be maintained only at the higher
temperatures. Austenitization is therefore not a final process but only a step in one of
several heat-treat procedures. For these approximate equilibrium processes, it is
possible to predict the material behavior from the equilibrium phase diagrams.
AUSTENITIZATION
When steel is heated to or above its critical temperature (transformation temperature
range), the value of which is dependent upon the alloy percentages and held at
temperature for some period of time carbon unites in solid solution with iron in gamma
or face-centered cubic lattice form. In phase, as much as 2% carbon can dissolve at
eutectic temperature of 1,148 C at which the widest range of gamma composition
exists.
ANNEALING
Objectives of Annealing. The word anneal has been used before to describe heat-
treating processes for softening and regaining ductility in connection with cold working
of material. It has a similar meaning when used in connection with the heat-treating of
allotropic materials. The purpose of full annealing is to decrease hardness, increase
ductility, and sometimes improve machinability of high carbon steels that might
otherwise be difficult to cut. The treatment is also used to relieve stresses, refine grain
size, and promote uniformity of structure throughout the material.
NORMALIZING
The purpose of normalizing is somewhat similar to that of annealing with the exceptions
that the steel is not reduced to its softest condition and the pearlite is left rather fine
instead of coarse. Pearlite is a crystalline structure with layers of soft, ductile ferrite (iron
containing small amounts of dissolved carbon) and hard, brittle cementite (iron carbide
which is a mechanical mixture of iron with greater amounts of carbon). Refinement of
grain size, relief of internal stresses, and improvement of structural uniformity together
with recovery of some ductility provide high toughness qualities in normalized steel. The
process is frequently used for improvement of machinability and for stress relief to
reduce distortion that might occur with partial machining or aging. An attempt is made
during normalizing to dissolve all the cementite to eliminate, as far as possible, the
settling of hard, brittle iron carbide in the grain boundaries. The desired decomposition
products are small-grained, fine pearlite with a minimum of free ferrite and free
cementite.
SPHEROIDIZING
Minimum hardness and maximum ductility of steel can be produced by a process called
spheroidizing, which causes the iron carbide to form in small spheres or nodules in a
ferrite matrix. In order to start with small grains that spheroidize more readily, the
process is usually performed on normalized steel. Several variations of processing are
used, but all require the holding of the steel near the A, temperature (usually slightly
below) for a number of hours to allow the on carbide to form in its more stable and lower
energy state of small, rounded globules.
The main need for the process is to improve the machinability quality of high carbon
steel and to pre-treat hardened steel to help produce greater structural uniformity after
quenching. Because of the lengthy treatment time and therefore rather high cost,
spheroidizing is not performed nearly as much as annealing or normalizing.
HARDENING OF STEEL
Austenitization First Step. Most of the heat treatment hardening processes for steel
are based on the production of high percentages of martensite. The first step, therefore,
is that used for most of the other heat-treating processes - treatment to produce
austenite.
Fast Cooling - Second Step. The second step involves cooling rapidly in an attempt to
avoid pearlite transformation. The cooling rate is determined by the temperature and the
ability of the quenching media to carry heat away from the surface of the material being
quenched and by the conduction of heat through the material itself. The Table (Heat-
Treating Quenching) shows some of the commonly used media and the method of
application to remove heat, arranged in order of decreasing cooling ability.
Heat-Treating Quenching
MEDI A METHOD
1. Brine
2. Water
3. Light Oil
1. Blast
2. Violent agitation
3. Slow agitation
4. Heavy Oil
5. Air
4. Still
Care Necessary in Heating and Cooling. High temperature gradients contribute to high
stresses that cause distortion and cracking, so the quench should be only as extreme
as is necessary to produce the desired structure. Care must be exercised in quenching
that heat is removed uniformly to minimize thermal stresses. For example, a long
slender bar should be end-quenched, that is, inserted into the quenching medium
vertically so that the entire section is subjected to temperature change at one time. If a
shape of this kind were to be quenched in a way that caused one side to drop in
temperature before the other, change of dimensions would likely cause high stresses
producing plastic flow and permanent distortion. Cracks created by either heating or
quenching can be detected by various NDT surface examinations including eddy
current, magnetic particle, and the penetrant methods. For parts subject to fatigue
failure, such cracks can be serious.
Distortion and Cracking Minimized by Martempering. Several special types of quench
are conducted to minimize quenching stresses and decrease the tendency for distortion
and cracking. One of these, is called martempering and consists of quenching an
austenitized steel in a salt bath at a temperature about that needed for the start of
martensite formation. The steel being quenched is held in this bath until it is of uniform
temperature but is removed before there is time for the formation of bainite to start.
Completion of the cooling in air then causes the same hard martensite that would have
formed with quenching from the high temperature, but the high thermal or "quench"
stresses that are the primary source of cracks and warping will have been eliminated.
Austempering - a Terminal Step. A similar process performed at a slightly higher
temperature is called austempering. In this case the steel is held at the bath
temperature for a longer period, and the result of the isothermal treatment is the
formation of bainite. The bainite -structure is not as hard as the martensite that could be
formed from the same composition, but in addition to reducing the thermal shock to
which the steel would be subjected under normal hardening procedures, it is
unnecessary to perform any further treatment to develop good impact resistance in the
high hardness range.
TEMPERING
A third step usually required to condition a hardened steel for service is tempering, or as
it is sometimes referred to, drawing. With the exception of austempered steel, which is
frequently used in the as hardened condition, most steels are not serviceable "as
quenched". The drastic cooling to produce martensite causes the steel to be very hard
and to contain both macroscopic and microscopic internal stresses with the result that
the material has little ductility and extreme brittleness. Reduction of these faults is
accomplished by reheating the steel to some point below the lower transformation
temperature.
The structural changes caused by tempering of hardened steel are functions of both
time and temperature, with temperature being the most important. It should be
emphasized that tempering is not a hardening process, but is, instead, the reverse. A
tempered steel is one that has been hardened by heat treatment and then stress
relieved, softened, and provided with increased ductility by reheating in the tempering or
drawing procedure.
CORROSION
Corrosion Definition. In general, corrosion is the deteriotian corrosion is the
deterioration of metals by the chemical action of some surrounding or contracting
medium which may be liquid, gas, or some combination of the two. To some degree
corrosion can influence all metals, but its effect varies widely depending upon the
combination of metal and corrosive agent.
The term "corrosion" is used to describe action that is normally considered to be
detrimental, but the principle is actually used for benefit in some cases. For example,
acids and alkalies are used to corrode metal away in the manufacturing process of
chemical milling. Also, aluminum alloys are frequently anodized to produce an oxide
coating that resists further oxidation and, in addition, may serve as an improved surface
for paint adhesion.
Corrosion attacks metals by direct chemical action, by electrolysis (electrochemical
action), or commonly by a combination of the two. The subject is complex and many
persons have devoted their lives to its study. This discussion will summarize some of
the known facts concerning the subject in order to develop some, understanding of
corrosion, its detection, and prevention.
DIRECT CHEMICAL ACTION
Theoretically, all corrosion phenomena are electromechanical because a transfer of
electrons takes place but the term direct chemical action is used to describe those
reactions where coupled anodes and cathodes existing in an electrolyte are not
identifiable. The chemical milling mentioned above is direct chemical action.
Another example is pickling of steel, a process in which heated dilute sulpheric acid
baths are used to dissolve surface scale without leaving a residue and producing only
minor chemical attack on the steel proper. This figure below illustrates another example
of direct chemical action.

DIRECT CHEMICAL ATTACK OF NITRIC ACID IN WHICH A MAGNESIUM ALLOY PRODUCT IS IMMERSED.
DIRECT CHEMICAL REACTION IS USUALLY EVIDENT FROM BUBBLES FORMED BY GAS EVOLUTION.
Galvanic Series. This table below shows a list of metals arranged in order of their
decreasing chemical activity in sea water. This is a special arrangement of the
electromechanical and the electromotive force series. It should be noted that most of
the list is made up of pure metals and indicates their relative resistance to sea water
corrosion. If the metals are alloyed or if the corroding medium is different, the
arrangement of such a list might change somewhat. In general, a metal high in the
series will displace from solution a metal lower in the series.
GALVANIC SERIES OF SOME METALS IN SEA WATER
Anodic (Most Corrodible)
Magnesium
Aluminum
Aluminum Cu Alloy
Zinc
Iron
Steel
Tin
Lead
Nickel
Brass CuZn
Bronze CuSn
Copper
Stainless Steel
Silver
Gold
Platinum
Cathodic (Least Corrodible)
ELECTROLYTIC (ELECTROCHEMICAL)
The electrochemical type corrosion also involves chemical change but involves the flow
of an electric current between two electrodes, an anode (positive, where electrons leave
and negative ions are discharged) and a cathode (negative, where electrons enter and
negative ions are formed). An electrical contact must exist in addition to electron flow
through the electrolyte to complete the circuit. The system is analogous to a plating
system in which the anode supplies the metal to be deposited. The anode eventually is
depleted thereby.
Sacrificial Metals. Although there are other factors that influence corrodibility, at least
theoretically the metals high in a galvanic series, which are anodic to any metal below
them, when connected electrically both by contact and through an electrolyte will
dissolve while the cathode is protected. This is the basic use of zinc coatings on steel.
The zinc is attacked and sacrificed in order to protect the steel. Protection will continue
as long as exposed areas of steel do not grow large enough to develop their own
galvanic cells to cause corrosion. The larger the anode area, the better is the protection.
The same principle is used when magnesium rods are hung in hot water heaters to
lower corrosion of the tank. Large anodes of magnesium, aluminum, or zinc may be
attached to the steel hull of a ship to provide protection below the waterline, as shown in
the figure below:

A SHIPS STEEL HULL MAY BE PROTECTED BY ATTACHMENT OF SACRIFICIALANODIC PLATES
TO THE SIDES UNDER THE WATER LINE. BURIED STEEL PIPE ALSO MAY
BE PROTECTED BY ATTACHING ANODES AS SHOWN BELOW:

PREFERENTIAL CORROSION RESULTING IN PROTECTION FOR BURIED STEEL PIPE BY ELECTRICAL ATTACHMENT OF ANODIC
MATERIAL TO THE STEEL.
CORROSION RATE DEPENDENT ON SEVERAL FACTORS
METAL OR METALS OF A CORROS I ON S YS TEM
1. Position in the electrochemical series-The higher, the greater tendency for corrosion. In multi-metal
systems-the farther apart, the greater the electrochemical action
2. The presence of residual stresses such as shown in the figure below.
ELECTROLYTE PRESENT
1. Concentration-High concentration usually increases corrosion.
2. Oxygen content-Oxygen particularly harmful in corrosion of iron.
3. Acidity-In general, the higher the acid content, the higher the corrosion rate.
4. Motion-Velocity of a flowing electrolyte may move corrosion products exposing new metal to attack.
Movement of electrolyte also may prevent formation of concentration cells, thus reducing corrosion.
5. Temperature-Increase usually accelerates corrosion.
6. Stray electrical currents-Localized currents from leaks, grounds, or eddy currents usually accelerate
corrosion.

MATERIAL: Deformed Carbon Steel
EXPOSURE: Humid Atmosphere

TYPES OF CORROSION
General Corrosion. The most common type corrosion is that appearing relatively
uniformly over the entire surface of the exposed metal. The bluish green color of a
copper roof or the dulling of polished aluminum and brass are examples of general
corrosion. Some of this type corrosion is self-limiting because the products of early
corrosion inhibit further corrosion.
CORROSION PROTECTION
There is no simple answer to preventing serious problems from the attack of corrosion.
There is no cure-all because of the variety of metals, possible environments, and
corrosive media. The general combat methods include: selection of the most suitable
metals, treatment of or controlling the presence of the corroding media, coating the
metal with a protective layer, and occasionally stress relieving parts containing high
stress areas.