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"
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pllos puB slBuoleru
lo ornleN oql

32

Materials and Processes for NDT Technology

not tied closely together. In this liquid state, the

materials have fixed volume but assume the shape of
the container in which they are placed.
As the energy level is further decreased, the mobility of the atoms decreases. There are at least four
different mechanisms by which the atoms can assume
positions well fixed enough that for practical purposes the material could be called so/id. Of the
materials of interest to manufacturing, all the metals
occur as crystalline solids.
and

METALI,IC 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 coefficieni of conductivity with increasing temperature.
States of Matter. Figure 4-1 shows the relationship that exists among the three states of matter for a
crystalline material. At the intersection of temperature ?t and pressure P1 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 73 will cause a second change

from a liquid to a gas. The intersecting point of the

curves at the temperature Ty and. pressure Ps 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.
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 nctwork groupings of
identical ttnit cells that are aligned in parallel planes.
There ere fourteen types of crystal latl,ices, but
rnost of the common and commercially important
metals exist, in the solid state, in one of three structures. These are, as shown in Figure 4-2, body-centered cubic, face-centered cubic, and hexagonal closedpacked. In the illustrations ofunit cells, the dots representing atoms should be considered as centers of activ.
ity for the atoms and not as graphic illsutrations of the
atoms themselves.

/l

/\

FACE - CENTERED OUBIC

EOOY-CENTERED CUBIC LATTICE

---l-r---'a
/

LATTICE

\r-A
iJ,t..,'i!
i,r,l

l,

,i

,,

\t-;.;--)..',

I
I

lrj

E
:f

k(E

lrj
o-

l=
d
F

HEXAGONAL CLOSE.PACKED LATTICE

!
f,

Pl

Px

PRESSURE

------f
Figure 4-1
States of matter

Figure 4-2
Common metallic space lattice

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Aq
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luel-ilpe ralno
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'uor

a'

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34

Materials and Processes for NDT Technology

costs

will be added. The methods. other than solidification, that can be used for grain-size control involve

WORK HARDENING

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 Iess 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 suscepti-

to a solid material in

bility to cracking under the thermal loads.

grained material

will

Coarse-

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 tnaterials
can be used so as to cause grain-size reduction automatically durir,g the shaping process with little or no
additional cost involved.

Effects of Deformation. The application of loads

processing or in service can
cause two kinds of deformation. If the load does not
stress the material past its elastic limit, the deformation is "elastic," and the material returns to its
original position upon removal of the load' If, however. the elastic limit is exceeded, the material does
not return completely to its original position when
the load is removed and is permanently deformed by
plastic flow within its crystalline structure. When the
elastic limit is passed, elastic properbies are not lost,
but instead are enhanced, providing the deformation
is produced by cold work. The strength of metal is
increased by plastic flow and the elastic Iimit is
raised. Some of the deformation processes produce
improved properties at the same time the shaping is
being performed.

PLASTIC DEFORMATION
Permanent deformation of metallic crystals occurs
in three ways: slip, twinning, and rotational deformation. The degtee of each is dependent largely on the
characteristics of the particular metal.

SOLID STATE CHANGES IN METALS

In the previous section the process of metal solidification was briefly described. The properties of a material are derived from the crystalline structure, including the atomic arrangement and the crystal sizes, and
are affected by the boundary layers that join the grains
together. The atomic arrangement is primarily a function of the material composition, which may consist of
a single material or a combination of materials that are
completely soluble, partially soluble, or totally insoluble in each other in the solid state. The structure and
grain size also may be influenced by the operating temperature changes and by mechanical loads that stress
the material sufficiently to cause plastic flow in combination with time and heat effects.
Some materials, particularly those that are cast to
shape, may be used with the structure in which they
solidify, but some of the cast materials and nearly all
metals processed by other methods are treated in
some way in the solid state to obtain improved
mechanical properties.
These treatments include work hardening, recrystalization, age hardening, and heat treating of allotropic materials to cause crystal transformations. In
many cases, treatment may be inherent in the
process. This may be beneficial, as in many cases of
deformation shaping with associated work hardening,
or may be detrimental, as in other cases in which cold
working develops directional properties in a material
to make some kinds of further cold work difficult or
impossible.

UNSTRAINEO GRAIII
ft

SLIP DEFORIIED

GRAIN

Figure 4-3
Slip

Slip Deforrnation. Slip deformation is illustrated

in Figure 4-3 and occurs by translation or sliding between the atomic platres within a grain. If the deformation causes more than a very minor shift, a large
number of atomic planes in each grain will slide over
adjacent planes to occupy new locations with new
neighbors. The planes through the crystal that are
usually most subject to slip are those of the greatest
atomic population and gteatest distance between
planes. The orientation of the planes along which slip
takes place most easily will, of course, be different
for different types of crystal lattices. Because of the
usual random orientation of the crystals, the slip
planes of many will not be in line with the direction
of loading. When the best slip planes are completely

tit

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36

Materials and Processes for NDT Technology

by treatment for recovery, most of the distorted

crystalline lattice remains as it was produced by cold

work. The elastic limit for the material has been
raised close io the ultimate strength, and further
deformation will cause fracture failure. Recovery of
ductility to permit further change of shape by deformation can be obtained only by elimination of the
deformed grains, and this can be accomplished by
recrystallization. By this heat-treating process' new'
smaller, unstrained glains with fully recovered capacity for plastic flow can be formed by solid-state
change in the metal. It is important to note that in
the absence of allotropic changes, which will be discussed later, no grain-size changes by heating metal to
any temperature below the melting point can be
accomplished unless the strained condition of coldworked metal is present. Recrystallization is the
nucleation and growth of new, strain-free crystals
from the strained crystals of a cold-worked material.
Recrystallization Temperatures. The phenomenon
occurs over a wide temperature range with the length
of time required for complete recrystallization in'
versely related to the temperature and to the degtee
of strain present. For practical purposes, recrystallization temperatures, such as shown in Table 4-I, ate
temperatures which will permit complete recrystallization in a time period of approximately t hour
for metals that have been fully hardened by previous
cold work.
TABLE 4-1

Recrystallization Temperatures for Some Common

M"t"lt
Material

Aluminum (pure)
Aluminum alloys
Copper (pure)

All"ys

""d
"c

80

316

120

316

Copper alloys
lron (pure)

Lowcarbonsteel,.....

400
540

Magnesium (purel
Magnesium alloys

65
232

......
......

10

Zinc

Tin

oF

175
600
250
600
750
1000
150

450
50
25
25

-4
-4
The table shows that zinc, tin, and lead recrystallize at temperatures below room temperature.
Lead

This means that these metals in the pure state cannot,

at ordinary temperatures, maintain a work-hardened
condition. The normal use of deformation processes
on these materials would be hot working rather than
cold working since it would be performed above their
recrystallization temperatures. Examination of the
table also reveals that contamination of a pure metal
with other elements makes it more difficult for recrystallization to occur, and the temperatures must
be increased for completion to occur in a reasonable
length of time.

Theory of Recrystallization. It is belierud

recrystallization takes place by the nucleation d
grains mainly about the high energy points of
cation in a work-hardened grain. They then
grow until they fill the old grain space and elimuqH
the existing strain by realignment of the atoms into e
new crystal lattice. Recrystallization can thus be a
grain-refining process as well as a method for recovery
of ductility, if it is discontinued as soon as complete
recrystallization has taken place.
The new gSains formed during recrystallization are
likely to take positions with preferred orientations'
Directional properties caused by preferred orientation
are objectionable for most manufacturing operations.
This tendency can be reduced and more random

orientation obtained by the addition of small

of an alloying element or by recrystallizing
before maximum work hardening has been per-

amounts

5
;,

formed.

Recrystallization Seldom Terminal. In a few

recrystallization may be used as an end process
to leave a product in its most ductile condition or
with its best electrical and chemical properbies, but
more often it is an in-process treatment for ductility
improvement or for grain refinement. In many cold
deformation processes, such as deep drawing, the
ductility of the material may be reduced by cold
working to the point where fracture failure is imminent. Ductility may be retumed to the material any
number of times by repeated recrystallization between steps of the forming operation. In most cases
tire last forming operation will not be followed by
recrystallization, in order that the higher hardness
and strength of the cold-worked material may be retained in the product.
Although heating for recovery is a stress-relieving
process, recrystallization at a higher temperature is
cases,

sometimes also called stress relieving. The same process may be referred to as process annealing, particular-

ly

when performed in conjunction with deformation

processes.

GRAIN GROWTH
If a metal is kept heated at or above its recrystallization temperature after the new, unstrained
grcins have formed, the tendency is for some of the
new grains to absorb others and grow to larger size.
Large grains are more stable than small grains because
of the higher grain-to-boundary-area ratio, which is a
lower energy state. If fine grain structure is desired
after the recrystallization process, it is necessary to
reduce the temperature quickly to prevent subsequent grain growth. This is usually performed by
some kind of quench.
Grain-Size Control During processing, small grain
size is not always wanted because large grains usually
exhibit gteater ductility, better machinability, and
require less pressure to be deformed. The final

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38

Materials and Processes for NDT Technology

from a body-centered cubic (BCC) lattice to a facecentered cubic (FCC) lattice. A second phase change
occurs with further heating to 1,394o C (2541' F),
where the lattice structure retums to the bodycentered cubic form. The reverse transformation
occurs on cooling through the same temperatures.
Iron in the temperature range up to 912" C is called
alpha iron; from 912' C to 1,394" C, gamma iron;
and above 1,394' C to 1,538o c (2,800' F), the melting point, delta iron. Little attention is given to delta
iron because the changes that occur in this range have
little or no effect in commercial practice of treatment
for properties. The changes that take place between
alpha and gamma iron at 912" C, however, are extremely important. The most effective change is the
difference of carbon solubility in the two phases,
which serves as the basis for all heat-treat hardening
and most grain-size control for steel.
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
occutrence 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 fumace or gas turbine.
Assessment of thermal treatment, whether inten'
tional or not, is often amenable to nondestructive test'
ing techniques that are capable of measuring subtle

changes in electrical conductivity. The heat treatment

in this chapter produce various

physical property changes including electrical conductivity. Both eddy current and thermo'electric methods are capable of indicating changes in electrical conductivity and to some extent can provide absolute
measures of electrical conductivity. However, both
methods only probe relatively small volumes of the
test material essentially at an exposed surface. During
heat treatment, exposed surfaces tend to heat and cool
at a different rate from the interior. Thus, measurements of surface characteristics do not necessarily
characterize the condition of the interior, but in many
practical cases can provide adequate information for
process control purposes.

processes described

APPROXIMATE EQUILIBRIUM HEAT TREATMENT PROCESSES

Several heat-treating processes place the material in
either a complete or an approximate equilibrium
energy condition. These processes include austenitizing, annealing, normalizing, and spheroidizing. Except
for the first, all are finalized at room temperature,
but since austenitizing consists of diffusion of carbon
into face-centered cubic iron that exists at a minimum temperature of 727" C (eutectoid composition
only, all others higher), stability, or equilibrium, in
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-treating
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 the
gamma or face-centered cubic lattice form. In this
phase, as much as 27" carbon can dissolve at the
eutectic temperature of 1,1-48" C at which the widest
range of gamma composition exists.
Grain-Size Control. It is important that the
austenitization temperatures not be exceeded more
than necessary to accomplish the work in a reasonable length of time because grain growth can occur
rapidly as the temperature is increased. One of the
important features of austenitization is grain refinement that occurs with the formation of the new facecentered cubic lattice. These new small grains are
nucleated with the raising of the metal temperature
through the austenite range and will remain small if
the temperature is not raised too high or maintained
too long. With lowering temperature and decompo-

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40

Materials and Processes for NDT Technology

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, ln 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 intemal 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, conosion 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 de-

its effect
varies widely depending upon the combination of
gree, corrosion can influence all metals, but

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 withut leaving a residue and producing only minor chemical attack on the steel proper.
Figure 4-5 illustrates another example of direct chemical action.

f
a

:
:i

Figure 4-5
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'

:j

Galvanic Series. Table 4-3 shows a list of metals arranged in order of their decreasing chemical activity in
sea water. This is a special arrangement of the electro-

mechanical and the electromotive force series.

It

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42

Materials and Processes for NDT Technology

4_.."#

Figure 4-9
Corrosion likely when dissimilar metals are in

MATERIAL: Deformed Carbon Steel

EXPOSURE: Humid Atmosohere

intimate contact
Galvanic Cells. The system described above causes
the flow of electrical current that in turn causes and accelerates corrosion. A type of battery called a galvanic
cell can be made of electrodes of two different metals
immersed in an electrolyte. A similar result (current
flow) is produced when two similar metals are joined,
or even a single metal, when contact is made with an
electrolyte that is not chemically uniform. This type of
cell is known as a concentration cell and is particularly
detrimental when the chemical variation of the electrolyte is in its oxygen concentration. Figure 4-10 illustrates the results from this type reaction.

VARIATION OF

MATERIAL: Butt Welded Carbon Steel

EXPOSURE: Humid Atmosphere

Figure

4-11

Some common examples of corrosion in materials

that have localized high stresses

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.

Figure 4-10
Electrochemical corrosion can occur with contacting
similar metals when the concentration of the
electrolyte varies. Most likely under
stagnant conditions.

CORROSION RATE DEPENDENT ON SEVERAL

FACTORS

Metal or Metals of a Corrosion System.

1. Position in the electrochemical series.-The
higher, the greater tendency for corrosion. In multimetal systems-the farther apart, the greater the electrochemieal action.

2. The presence of residual stresses suchas shownin

Figure 4-11.
Electrolyte Present.
1. Concentration-High concentration usually increases corrosion.

6. Stray electrical currents-Localized currents

from leaks, grounds, or eddy currents usually accelerate corrosion.
Atmospheric Corrosion. Moisture is usually
blamed for atmospheric corrosion and although moisture may be present, pure water has relatively small effect. The combination of moisture with impurities,
especially salts of chlorine and sulphur, accelerates
atmospheric corrosion greatly.
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 col-

or 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.

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Materials and Processes for NDT Technology

The first is basically a design problem. The second is

usually a manufacturing or service problem such as
treating coolant water used in a machine tool with a
chemical corrosion inhibiter or decerating boiler feed
water to remove oxygen. The third is the most common approach and includes: coating with anodic materials to promote preferential corrosion, developing a
coating to retard corrosion, and application of a coating to exclude the corrosion medium. The coatings
used are metals, chemical compounds, and organic ma-

terials and plastics.

Metal Coatings. Coating of metal with another
metal can be accomplished by electroplating, dipping
in molten metal, metal spraying, cladding by rolling
thin layers over the base metal and by heating the product in fine metallic powders.
Chemical Compounds. Most coatings that consist
of chemical compounds are made by treating the base
metal to change the chemistry of its surface. Anodizing of aluminum is the artificial formation of aluminum oxide to a controlled depth on the surface of an
aluminum alloy. Steel can be given a protective coating of iron phosphate by soaking the product in hot
solution of manganese phosphate.
Non-metallic Coatings. Paint, enamel, varnishes,
greases, plastics, and many other materials are used to
coat objects for corrosion protection. Most of these
materials are used to exclude the corrosive environment but some contain chemical inhibitors to exert
greater control. Some are for only temporary protection such as for a few days or weeks, but others may
have a useful life of several years.
In all cases of corrosion protection regardless of the
type, suitable preparation and cleaning of the original
metal surface is essential. Where control of coating
thickness is important, several methods of NDT are
available. Eddy current lift-off techniques are most
readily applied, but depending upon the type of coating and substrate, beta-backscatter, magnetic field
and radioisotopic tagging procedures have been used
effectively.

NDT for Corrosion Detection. As apparent from

the foregoing discussion of corrosion, its effects are

almost always detrimental to the serviceability of criti

cal components, assemblies, and structures. The NDT

specialist must understand the effects of the various

types of corrosion in order to properly select and direct
the nondestructive tests most effective in detecting
and assessing the extent of corrosion.
For corroded surfaces that are accessible, penetrant,
magnetic particle, and eddy current tests are particulary useful in detecting the effects of corrosion that result in small surface cracks or pits. Very small corrosion cracks have been detected and recorded by magnetic rubber techniques. For corrosion on the inside of
pipes, vessels, and assemblies, other tehcniques are applied. Ultrasonic techniques are particularly effective
in the detection and accurate measurement of overall
thinning that results from corrosion. Radiography is
commonly applied to detect corrosion and corrosion
thinning in interior and otherwise inaccessible regions
of assemblies, insulated components, and the like. Neutron radiography has been used to detect interior corrosion by virtue of the corrosion products having large
neutron cross-sections as well as actually imaging corrosion in exceptionally dense materials like lead and
uranium. Acousic emission monitoring has been used
to monitor the initiation and growth of stress corrosion
and hydrogen embrittlement cracks.
Visual means are also important in the detection of
corrosion. Both corrosion discontinuities and corrosion
products leave telltale signs by virtue of visible
changes in texture, coloration, topography, and geometry. Some corrosion products fluoresce when illuminated by ultraviolet light. Further study of corrosion sites and corrosion products by spectrographic
analyses can reveal otherwise elusive evidence as to
the cause of corrosion.