Fabrizio DErrico

_______________________________

Lecture Notes in Applied Metallurgy

for the course held at Politecnico di Milano for the Master
of Science (MS) Degree in Mechanical Engineering

This booklet is based on bibliography of the course. Several parts of this booklet, as well as pic-
tures and tables, have been freely taken from the original text books in the selected bibliography
of the course. This booklet is provided by the teacher for internal use only to the students at-
tending the course of Applied Metallurgy, course of the M.Sc. in Mech. Eng. at Politecnico di
Milano.
No other external uses and/or scopes that are out of preparation to final exam are therefore al-
lowed.
Any other different uses by the students shall be under their own responsibility.
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Table of Content
Chapter 1 - Resuming basic principles of metallurgy ........................................ 8

Introduction ........................................................................................................... 8

Atomic Structure and Interatomic Bonding ....................................................... 8

Atomic arrangements of metals ....................................................................... 12

Vacancies, interstitial spaces and grain boundaries as drive-force for

diffusion in metals ............................................................................................... 20

Elastic and plastic deformation in metal by micromechanical models ........... 31

Slip in polycrystalline crystal........................................................................... 41

Mechanisms of Strengthening in Metals ........................................................... 45

Strengthening by grain size reduction ............................................................. 45
Strain hardening .............................................................................................. 50
Phase boundaries as strengthening sources .................................................... 53

Grain Growth, Recovery and Recrystallization................................................ 57

Recovery .......................................................................................................... 58
Grain growth ................................................................................................... 59
Recrystallization .............................................................................................. 60

Mechanical behavior of metals by macroscopic approach .............................. 64

Tensile test ....................................................................................................... 64
Ductility ........................................................................................................... 67
Resilience ......................................................................................................... 67
Toughness ........................................................................................................ 68
Hardness .......................................................................................................... 70

Resuming the main contents, defining the main paradigm for mechanical
response of metals ................................................................................................ 72

Microstructural features of fracture in metallic materials .............................. 77

Ductile Fracture .............................................................................................. 78
Brittle Fracture ................................................................................................ 81

Chapter 2 - Damage mechanisms and root cause failure analysis basics ....... 85
The contributing factor: the stress concentration ........................................... 92
The energy criterion for fast fracture .............................................................. 94
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Micromechanisms of fast fracture ................................................................... 97

Mechanisms of crack propagation by ductile tearing ...................................... 97
Mechanisms of crack propagation, 2: cleavage ............................................ 100
The three stages of fatigue failure ................................................................. 111
Theories on failure mechanisms involved in fatigue contact: the Hertzian
theory of contact between elastic bodies ....................................................... 121
Traction and elasto-hydrodynamic lubrication (EHL) condition .................. 128
Subsurface crack initiated fatigue contact failure ......................................... 131

Friction and wear damage ................................................................................ 138

Actual surface contact between solids ........................................................... 138
Data for coefficients of friction ...................................................................... 141
Lubrication .................................................................................................... 143
Wear of materials .......................................................................................... 144
Adhesive wear ................................................................................................ 144
Abrasive wear ................................................................................................ 145

Corrosion ........................................................................................................... 147

Wet corrosion and electrochemical corrosion ............................................... 147
The corrosion morphology ............................................................................ 155
Uniform or generalized corrosion ................................................................. 155
Galvanic corrosion ........................................................................................ 156
Pitting corrosion ............................................................................................ 159
Crevice corrosion .......................................................................................... 161

Creep .................................................................................................................. 163

The Creep Curve ............................................................................................ 163
Creep Deformation Mechanisms ................................................................... 167
Creep Life Prediction .................................................................................... 169
Design Against Creep .................................................................................... 170

Chapter 3 Special Steels ................................................................................. 172

Introduction ................................................................................................. 172
Designation of steels ...................................................................................... 172
Classification of steels ................................................................................... 175
Designation of steels ...................................................................................... 176
Classification of steels ................................................................................... 178
Microstructures and heat treatment in steels................................................. 179
Strengthening of ferritic-perlitic structure..................................................... 184
Quenching and tempering of steels. ............................................................... 191
Tempering martensite .................................................................................... 193
Prediction of hardenability ......................................................................... 195
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Review of phase transformations and mechanical properties for iron-

carbon alloys................................................................................................. 200
Industrial quenching problems: distortions and quenching cracks ........ 202
Quenching and tempering steels ................................................................. 205
Basics of criteria selection ............................................................................. 215
The manufacturing cycle of quenching and tempering steels .................. 215
Reduction of microstructure and chemical composition inhomogeneity ....... 216
Control of quenching distortion ..................................................................... 220
Criteria for selection ...................................................................................... 226
Spring Steels ................................................................................................. 227
Heat treatments for steels and manufacturing cycle of springs ..................... 229
Patenting ........................................................................................................ 231
Pickling .......................................................................................................... 232
Shot peening................................................................................................... 232
Criteria selection ........................................................................................... 235
Surface hardening of mechanical components .......................................... 235
Surface Hardening by Localized Heat Treatment .......................................... 236
Manufacturing cycle for surface hardened product....................................... 238
Criteria for steel selection for surface hardening .......................................... 239
Carburizing steels ........................................................................................ 240
Carburizing cycle description ........................................................................ 243
Design aspects of carburizing........................................................................ 244
Nitriding steels ............................................................................................. 246
Design features of nitriding parts .................................................................. 249
Manufacturing cycle for nitriding parts......................................................... 250

Chapter 4 Tool Steels ..................................................................................... 253

Classification of tool steels ............................................................................ 253
The AISI classification ................................................................................... 253
Important properties required for various applications ................................ 254
Secondary hardening of tool steels ................................................................ 255
Manufacturing cycle of tool steels ................................................................. 257
Criteria for selection of tool steels for specific applications ......................... 257

Steels for Special Applications Specialty Alloyed Steels ............................. 260

High-Fracture-Toughness Steels ................................................................ 260
Mar-Aging Steels ......................................................................................... 262
High-Strength Low-Alloy Steels ................................................................. 264
Dual-Phase Steels ......................................................................................... 267
TRIP Steels ................................................................................................... 269

Chapter 5 Stainless Steels .............................................................................. 270

Introduction.................................................................................................. 270
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Classification of stainless steels ................................................................... 271

Ferritic Stainless Steels................................................................................ 273
Austenitic stainless steels ............................................................................. 279
Martensitic stainless steels .......................................................................... 284
Austenitic-Ferritic (Duplex) Stainless Steels ............................................. 288
Precipitation Hardening Stainless Steels ................................................... 290

Chapter 6 High-Temperature Resistant Alloys: Steels for High

Temperatures, Ni-Base Alloys and Ni-Superalloys ........................................ 292
Introduction ................................................................................................. 292
Chromium-molybdenum and chromium-molybdenum-vanadium steels294
Stainless steels for high temperatures ........................................................ 296

Chapter 7 Non-Ferrous Structural Alloys: Magnesium Alloys ................... 303

Introduction: the search for lightweighting in automotive ...................... 303
Magnesium Alloys for Structural Applications......................................... 311
The ASTM designation of Mg alloys and most used Mg alloys ..................... 314
Casting Alloys ................................................................................................ 315
Wrought Magnesium Alloys ........................................................................... 317

Chapter 8Titanium Alloys .............................................................................. 321

Titanium Metallurgy ................................................................................... 322
Titanium Alloys............................................................................................ 324
Commercially Pure Titanium......................................................................... 325
Alpha and Near-Alpha Alloys ........................................................................ 325
Beta Alloys ..................................................................................................... 327
Basics of fabrication of titanium alloys ...................................................... 328

Chapter 9 Steelmaking process: basics of primary fabrication and

secondary operations......................................................................................... 329
Introduction ................................................................................................. 329
Blast Furnace ................................................................................................ 332
Basic Oxygen Furnace................................................................................... 334
Electric Arc Furnace ..................................................................................... 336
Ladle Furnace................................................................................................ 337
From Ladle Furnace to Casting Process .................................................... 338
Ingot Casting ................................................................................................. 338
Continuous Casting ....................................................................................... 339
The cast product microstructure .................................................................... 341
Primary metalworking hot processes: the bulk deformation processes .. 345
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Chapter 1 - Resuming basic principles of metallurgy

Introduction
Some of the important properties of solid materials depend on geometrical
atomic arrangements, and also the interactions that exist among constituent
atoms or molecules. Several fundamental and important concepts name-
ly, atomic structure, electron configurations in atoms are here reviewed
briefly (for more details you may refer to: William D. Callister, Materials
Science and engineering: an introduction - 7. ed. - New York: John Wiley
& sons, 2007; F.C. Campbell, Metallurgy and Engineering Alloys, ASM
International, 2008).

Atomic Structure and Interatomic Bonding

Bohr atomic model, in which electrons are assumed to revolve around the
atomic nucleus in discrete orbitals, and the position of any particular elec-
tron is more or less well defined in terms of its orbital. This model of the
atom is represented in Figure 1.1a.

(a) (b)

Figure 1.1 (a) A schematic representation of the Bohr atom; (b) covalent bond-
ing requires that electrons be shared between atoms in such a way that each atom
has its outer sp orbital filled. In silicon, with a valence of four, four covalent
bonds must be formed.

The electron configuration or structure of an atom represents the manner in

which electron statesvalues of energy that are permitted for electrons
 9

states are occupied. Valence electrons are those ones that occupy the
outermost shell: these electrons are extremely important for establishing
the bonding between atoms. And bonding between atoms are necessary to
form atomic and molecular aggregates.
This implies many of the physical and chemical properties of solids are
based on these valence electrons.
The basics of atomic bonding are best illustrated by considering how two
isolated atoms interact as they are brought close together from an infinite
separation (Fig. 1.2). At large distances, attraction forces exerted between
positive nucleus of one atom and the negative electrons of the other atom
are negligible (mutual attraction): this depend on the fact the two atoms are
too far apart to have an influence on each other. At small separation dis-
tances, each atom can actually exerts forces on the other, but when dis-
tance decrease too much, namely nuclei get close, repulsive forces be-
tween positive nuclei surpass attraction force. These counteracting forces,
attractive FA and repulsive FR, and the magnitude of each depends on the
separation or interatomic distance r (refer to Figure 1.2). The entity of at-
tractive force FA obviously shall depend on the particular type of bonding
that exists between the two atoms, as discussed in brief above. In Fig. 1.2b
the potential energy is shown (as integral of bonding force Fdr ).
Despite the above scheme deals with an ideal situation involving only two
atoms, a similar yet more complex condition exists for solid materials. The
magnitude of this bonding energy and the shape of the energyversus in-
teratomic separation curve (Fig.1.2b) that can vary from material to mate-
rial influence physical properties of materials. For example, large bonding
energies typically also have high melting temperatures; at room tempera-
ture, solid substances are formed for large bonding energies, whereas for
small energies the gaseous state is favored; liquids prevail when the ener-
gies are of intermediate magnitude. How much a material expands upon
heating or contracts upon cooling (that is, its linear coefficient of thermal
expansion) is related to the shape of its E vs r curve (a deep and narrow
trough, which typically occurs for materials having large bonding ener-
gies, normally correlates with a low coefficient of thermal expansion and
relatively small dimensional alterations for changes in temperature).
10

Figure 1.2 - (a) The dependence of repulsive, attractive, and net forces on intera-
tomic separation for two isolated atoms. (b) The dependence of repulsive, attrac-
tive, and net potential energies on interatomic separation for two isolated atoms.
 11

Physical principles of elastic modulus

Among various physical properties affected by energy or interatomic force
versus relative distance r (see again Fig.1.2a) curve shape diagram, we fo-
cus on the tangent to F versus r curve at its stable equilibrium (i.e. in r0 in
the Fig.1.2). Look at the Fig.1.3 that shows the F-r curve around the equi-
librium, r0 (equilibrium will vary at different temperature: increase if T in-
creases, decrease while T decreases).

Figure 1.3 - The force-distance curve for two materials, showing the relationship
between atomic bonding and the modulus of elasticity, a steep dF/da slope gives a
high modulus.

If we refer to general results obtained by a stress-strain curve (i.e.

curve, Fig. 1.4a), we observe most metals that are stressed in tension and at
relatively low levels result in a proportional stress and strain correlation to
each other, obeying to the relationship = E, also known as Hookes Law.
We define deformation in which stress and strain are proportional as elas-
tic deformation (a nonpermanent deformation) since each loading cycle
performed in this stress-strain curve region is fully reversible (by un-
loading, the piece returns to its original shape).
12

(a) (b)

Figure 1.4 (a) Typical engineering stressstrain behavior to fracture,

point F; (b) a detail of the stress-strain curve in the proportionality regime.

On an atomic scale, thus referring again to Fig.1.3, macroscopic elastic

strain is manifested as small changes in the interatomic spacing and the
stretching of interatomic bonds. As a consequence, the magnitude of the
modulus of elasticity is a measure of the resistance to separation of adja-
cent atoms, that is, the interatomic bonding forces. This modulus is propor-
tional to the slope of the interatomic forceseparation curve (Figure 1.3) at
the equilibrium, and it is a physical properties of material class: it does
mostly depend on atomic bonding force of crystal lattice of metals, over a
very low influence of varying chemical analysis (steels exhibits atomic
bonding force higher than aluminum, so its Young Modulus is higher;
Young Modulus of any steels slightly varies in the range 200.000
220.000 MPa).

Atomic arrangements of metals

During cooling, and thus solidifying phase, the vibrational energy 1 of at-
oms tends to decrease. By opposite reasoning we can say that increasing
vibration energy causes progressively equilibrium distance r0 to increase.

Atoms vibrates around their equilibrium r0 position at any temperature; at -

1

273 K vibration ceases.

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The material, if it is solid, remains in this state till the equilibrium distance
that is increased by increasing temperature (consider that heating up pro-
vides energy for increase atom vibration) is lower than low-bonding ener-
gy regime (see again Fig.1.2b: as interatomic atom distance increases, at-
tractive force, i.e. bonding energy decreases). If atoms reaches high intera-
interatomic distance, their mutual attractive force decreases and atoms
separate each other. While this phenomenon happens in metal, it is observe
a change in status of aggregation: it passes from solid to liquid state.
Now, proceed again in back track: cool down temperature of metal that is
provided in molten state. The vibration energy of atoms progressively de-
creases, till some atoms can attract each others. These early movements
make some atoms to link each others, and some nuclei of solidified materi-
als appears in the melting phase (see Fig.1.5a)
What distinguishes metals, some polymers and many ceramics is that when
solid state is reached, atoms occupies regular ordering of atoms that ex-
tends through the material (Fig.1.5b and c). Particularly here we refer to
metals.

Figure 1.5 - Schematic diagrams of the various stages in the solidification of a

polycrystalline material; the square grids depict unit cells. (a) Small crystallite nu-
clei. (b) Growth of the crystallites; the obstruction of some grains that are adjacent
to one another is also shown. (c) Upon completion of solidification, grains having
irregular shapes have formed. (d) The grain structure as it would appear under the
microscope; dark lines are the grain boundaries.
14

For a metal, crystalline solid is built up during cooling down and solidifi-
cation by way of a periodic and repeated arrangement of atoms that ex-
tends throughout the entirety of the specimen. The basic cell that repeat in
the space at is called the unit cell and its geometry varies for metals. In
Fig. 1.6 are show various possibility of arrangement in metals and the
highlighted ones are those we deal with in this course.

Figure 1.6 - The fourteen types of Bravais lattices grouped in seven crystal sys-
tems. The highlighted structures are those of our interest.
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The representation in Fig.1.6 is just schematic; in reality, the lattice struc-

ture is made up by atoms that get close each other, compacting and pack-
ing in the unit cell above illustrated. In Fig.1.7 is shown the more real
structure of a face centered cubic, or FCC, unit cell (Fig.1.7a) compared
with the schematic representation (Fig.1.7b) of unit cell, and how the unit
cells combine in the space to form solid material (namely, each single
grain of Fig.1.5).

Fig.1.7 - For the face centered cubic crystal structure, (a) a hard sphere unit cell
representation, (b) a reduced-sphere unit cell, and (c) an aggregate of many atoms.

Now, imagine to start from the scheme in Fig.1.7b made of ping pong balls
at the corner and in center of 6 faces of the cube, and pack as you can, try-
ing to realize by outer uniform compression a compact cube. What hap-
pens is that some spaces will remain in your compacted cube. These spaces
we call interstitial spaces, or sites. In Fig.1.8, for example, are shown the
16

interstitial spaces present in three type of unit cells. In Fig.1.9 the octahe-
dral site inside the face centered cubic cell.

Figure 1.8 - The location of the interstitial sites in cubic unit cells. Only repre-
sentative sites are shown. The name of the site (e.g. octahedral, tetrahedral, etc.)
depends on its location in the

Figure 1.9 - The location of the octahedral site in a face centered cubic unit cell.

Imperfections in the Atomic and Ionic Arrangements

Thus far it has been tacitly assumed that perfect order exists throughout
crystalline materials on an atomic scale. However, such an idealized solid
does not exist. Meanwhile cooled down, a metal solidifies by solid nuclei
formation (see again Fig.5) and grain growth. It is worth of noticing that
the simplified scheme of solidification in Fig.5 actually it is to be consid-
ered as a low magnification representation; if you imagine to observe by
an atomic microscope (we imagine we holds such a marvelous equip-
 17

ment) nuclei that are forming inside liquid phase as illustrated in Fig.5, ac-
tually we have to consider they are building up meanwhile atoms by atoms
occupy fixed position inside the specific unit cell. Each metal, we know,
has its own specific atomic arrangement it is just like the DNA code for
organisms - that mainly depends on the base element, e.g. body cubic cen-
tered, BCC, for Fe (at ambient temperature), face cubic centered, FCC, for
aluminum, highly compact hexagonal for Mg, etc. Thus, when metal cools
down and rapidly solidifies, it is impossible all atoms perfectly arrange to
build up a perfect crystal lattice into perfect grain: in reality many atoms
will occupy wrong positions.

Point defects
We call these wrong positions imperfections of crystal lattice, or more
simply defects. Basic defects of a real crystal lattice consists in a punctual
(single) wrong position occupied by an atom that is missing, thus we call it
a vacancy, or it is inserted in an insufficient space, thus we can define a
self-interstitial atom (see Fig. 1.10). We call this type of imperfections
point defects, because of their effect onto lattice irregularity: they can be
several, but they are punctual imperfections distributed in crystal planes.

Figure 1.10 - Two-dimensional representations of a vacancy and a self-interstitial.

If you consider the most generalized case of non-pure metals, namely the
solid solutions of two or more elements, we call metal alloys, like Fe-C al-
loys, aluminum silicon added alloys, etc. exhibit same type of defects as
vacancies, but additionally to the self-interstitial atoms, crystalline defects
can refer also to irregular occupancy of an alloying element atom that
would have a smaller or wider radius than base element. In Fig.1.11 it is
18

shown a summary of possible point defect situations we can observe in

metal alloys. Whichever is origin of point defect, all of these defects dis-
rupt the perfect arrangement of the surrounding atoms.

Figure 1.11 - Point defects: (a) vacancy, (b) interstitial atom, (c) small substitu-
tional atom, (d) large substitutional atom,

Interfacial defects: grain boundary

Grain boundary is represented schematically from an atomic perspective in

Figure 1.14. Within the boundary region, which is probably just several at-
om distances wide, there is some atomic mismatch in a transition from the
crystalline orientation of one grain to that of an adjacent one. Various de-
grees of crystallographic misalignment between adjacent grains are possi-
ble (Figure 1.15).When this orientation mismatch is slight, on the order of
a few degrees, then the term small- (or low-) angle grain boundary is used.
These boundaries can be described in terms of dislocation arrays. One
simple small-angle grain boundary is formed when edge dislocations are
aligned in the manner of Figure 4.8. This type is called a tilt boundary; the
angle of misorientation, , is also indicated in the figure. When the angle
of misorientation is parallel to the boundary, a twist boundary results,
which can be described by an array of screw dislocations.
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Figure 1.14 Schematic diagram showing small and high-angle grain boundaries
and the adjacent atom positions.

Figure 1.15 A tilt boundary having an angle of misorientation , results from an

alignment of edge dislocations.
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As special type of grain boundary twin boundary is worth of noticing: it

exhibits a specific mirror lattice symmetry (it depends on crystal lattice).
Thus atoms on one side of the boundary are located in mirror-image posi-
tions of the atoms on the other side (Figure 1.16).

Figure 1.16 Schematic diagram showing a twin plane or boundary and the
adjacent atom positions (colored circles).

Vacancies, interstitial spaces and grain boundaries as

drive-force for diffusion in metals
Firstly we address the diffusion by the phenomenological point of view.
Let us see the scheme in Fig. 1.16. The phenomenon of diffusion may be
demonstrated with the use of a diffusion couple, which is formed by join-
ing bars of two different metals together so that there is intimate contact
between the two faces; this is illustrated for copper and nickel. which in-
cludes schematic representations of atom positions and composition across
the interface. This couple is heated for an extended period at an elevated
temperature (but below the melting temperature of both metals) and cooled
to room temperature. Chemical analysis will reveal a condition similar to
that represented in Figure 1.15 namely, pure copper and nickel at the
two extremities of the couple, separated by an alloyed region. Concentra-
tion of both metals vary with position as shown in Figure 1.15f. This result
indicates that copper atoms have migrated or diffused into the nickel, and
that nickel has diffused into copper. This process, whereby atoms of one
metal diffuse into another, is termed inter-diffusion, or impurity diffusion.
There is a net drift or transport of atoms from high- to low-concentration
regions.
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Diffusion also occurs for pure metals, but all atoms exchanging positions
are of the same type; this is termed self-diffusion. Of course, self-diffusion
is not normally subject to observation by noting compositional changes.
This was the experiment, to allow us to observe results of diffusion: but
which are mechanisms that causes diffusion into metals?

(a) (d)

(b) (e)

(c) (f)

Figure 1.16 Start experiment time: (a) a coppernickel diffusion couple before a
high-temperature heat treatment; (b) schematic representations of Cu (red circles)
and Ni (blue circles) atom locations within the diffusion couple; (c) concentrations
of copper and nickel as a function of position across the couple; (d) the copper
nickel diffusion couple after a high-temperature heat treatment, showing the al-
loyed diffusion zone; (e) schematic representations of Cu (red circles) and Ni
(blue circles) atom locations within the couple; (f) Concentrations of copper and
nickel as a function of position across the couple.

Mechanisms of diffusion into metal

From an atomic perspective, diffusion is just the stepwise migration of at-
oms from lattice site to lattice site. In fact, the atoms in solid materials are
in constant motion, rapidly changing positions. For an atom to make such a
move, two conditions must be met: (1) there must be an empty adjacent
site, and (2) the atom must have sufficient energy to break bonds with its
22

neighbor atoms and then cause some lattice distortion during the displace-
ment. As stated, this energy is vibrational in nature until cooling down
metals to -273 K. At a specific temperature some small fraction of the total
number of atoms is capable of diffusive motion, by virtue of the magni-
tudes of their vibrational energies. This fraction increases with rising tem-
perature.
Several different models for this atomic motion have been proposed; of
these possibilities, two dominate for metallic diffusion.

Vacancy Diffusion: involves the interchange of an atom from a

normal lattice position to an adjacent vacant lattice site or vacancy,
as represented schematically in Fig.1.17a. This process of course
necessitates the presence of vacancies, and the extent to which va-
cancy diffusion can occur is a function of the number of these de-
fects that are present.

Interstitial Diffusion: The second type of diffusion involves atoms

that migrate from an interstitial position to a neighboring one that is
empty; this mechanism is found for interdiffusion of impurities and
very small-radius atoms (such as hydrogen, carbon, nitrogen, and
oxygen) that are small enough to fit into the interstitial positions and
move (Fig.1.17b). In most metal alloys, interstitial diffusion occurs
much more rapidly than diffusion by the vacancy mode, because the
interstitial atoms are smaller and thus more mobile. Furthermore,
there are more empty interstitial positions than vacancies; hence, the
probability of interstitial atomic movement is greater than for va-
cancy diffusion.
 23

Figure 1.17 Schematic representations of (a) vacancy diffusion and (b) intersti-
tial diffusion.

Box - Modeling of diffusion into metals

Diffusion is a time-dependent processthat is, in a macroscopic sense, the

quantity of an element that is transported within another is a function of
time. Often it is necessary to know how fast diffusion occurs, or the rate of
mass transfer. This rate is frequently expressed as a diffusion flux (J), de-
fined as the mass (or, equivalently, the number of atoms) M diffusing
through and perpendicular to a unit cross-sectional area of solid per unit of
time. In mathematical form, this may be represented as:

(. 1.1) =

where A denotes the area across which diffusion is occurring and t is the
elapsed diffusion time. In differential form, this expression becomes:

1
(. 1.2) =

The units for J are kilograms or atoms per meter squared per second
(kg/m2. s or atoms/m2. s). If the diffusion flux does not change with time, a
steady-state condition exists.
24

Steady-state diffusion and Ficks first law

One common example of steady-state diffusion is the diffusion of atoms of

a gas through a plate of metal for which the concentrations (or pressures)
of the diffusing species on both surfaces of the plate are held constant.
This is represented schematically in Figure 1.17a.

Figure 1.17 (a) Steady-state diffusion across a thin plate. (b) A linear concentra-
tion profile for the diffusion situation in (a).

When concentration C is plotted versus position (or distance) within the

solid x, the resulting curve is termed the concentration profile; the slope at
a particular point on this curve is the concentration gradient:

(. 1.3) =

In the present experiment, the concentration profile is assumed to be line-

ar, as depicted in Figure 1.17b, and:

(. 1.4) = =

The mathematics of steady-state diffusion in a single (x) direction is rela-

tively simple, in that the flux is proportional to the concentration gradient
through the expression:
 25

(. 1.5) =

The constant of proportionality D is called the diffusion coefficient, which

is expressed in square meters per second. The negative sign in this expres-
sion indicates that the direction of diffusion is down the concentration gra-
dient, from a high to a low concentration. Equation 1.5 is sometimes called
Ficks first law. When diffusion is according to Equation 5.3, the concen-
tration gradient is the driving force.

Non-steady state diffusion and Ficks second law

The diffusion flux and the concentration gradient at some particular point
in a solid vary with time, with a net accumulation or depletion of the dif-
fusing species resulting. This is illustrated in Figure 1.18, which shows
concentration profiles at three different diffusion times. In this case, in-
stead the Ficks first law, a partial differential equation is used to more
precisely model the phenomenon:

(. 1.6) = ( )

The above equation is known as Ficks second law. If the diffusion coeffi-
cient is independent of composition (which should be verified for each
particular diffusion situation), Equation 1.6 simplifies to:

2
(. 1.7) =

Solutions to this expression (concentration in terms of both position and

time) are possible when physically meaningful boundary conditions are
specified.
26

Figure 1.18 - Concentration profiles for nonsteady-state diffusion taken at three

different times, t1, t2, and t3.

The use of Erf Function in modeling diffusion

Frequently, the source of the diffusing species is a gas phase, the partial
pressure of which is maintained at a constant value. Furthermore, the fol-
lowing assumptions are made:
1. Before diffusion, any of the diffusing solute atoms in the solid are uni-
formly
2. distributed with concentration of C0.
3. The value of x at the surface is zero and increases with distance into the
solid.
4. The time is taken to be zero the instant before the diffusion process be-
gins.
These boundary conditions are simply stated as
For t =0, C= C0 at 0 x
For t > 0, C = Cs (the constant surface concentration) at x = 0
C= C0 at x =

Application of these boundary conditions to Equation 1.7 yields the solu-

tion:

(. 1.8) =
0 2

Where:
 27

o Cs is the surface concentration of gas diffusing into the surface,

o Co is the initial concentration of the element in the solid, x is the
distance from the surface,
o D is the diffusivity of the solute element in the solvent matrix,
and t is time;
o erf (error function) is a mathematical function that can be found
in standard mathematical tables, also included in excel function;

Case study - Carburization process modeling

Assume gas carburizing process conducted on 1020 steel, at 930
C;
Assume that the steel has a nominal carbon content of 0.20%, and
the carbon content at the surface is 0.90%.
The diffusion coefficient under these conditions is D930C =1.28
10-11 m2/s
The time necessary to increase the carbon content to 0.40% at
0.50mm below the surface can be calculated in the following
manner:

Figure 1.19 Carbon concentration during carburizing.

28

Internal factors that affect diffusion

In the following are listed two main inner factors among various which af-
fect diffusion kinetics.

Diffusing species: The magnitude of the diffusion coefficient D is indica-

tive of the rate at which atoms diffuse. The diffusing species as well as the
host material influence the diffusion coefficient. For example, there is a
significant difference in magnitude between self-diffusion and carbon in-
terdiffusion in iron at 500C, the D value being greater for the carbon in-
terdiffusion (3.0 x 10-21 vs. 2.4 x 10-12 m2/s). This comparison also provides
a contrast between rates of diffusion via vacancy and interstitial modes as
discussed earlier. Self-diffusion occurs by a vacancy mechanism, whereas
carbon diffusion in iron is interstitial.

Temperature: Temperature has a most profound influence on the coeffi-

cients and diffusion rates. For example, for the self-diffusion of Fe in -
Fe, the diffusion coefficient increases approximately six orders of magni-
tude in rising temperature from 500C to 900C. The temperature depend-
ence of the diffusion coefficients is:

(eq.1.9) = 0 exp

Where:
D0 is a temperature-independent pre-exponential (m2/s)
Qd is the activation energy for diffusion (J/mol)
R is the gas constant, 8.31 J/molK
T is the absolute temperature (K)

The activation energy may be thought of as that energy required to pro-

duce the diffusive motion of one mole of atoms. A large activation energy
results in a relatively small diffusion coefficient.
 29

Box - Determining D0 and Qd

Taking natural logarithms of Equation 1.9 yields:

Q 1
(. 1.10) = 0
2.3

Because D0, Qd, and R are all constants, Equation 1.10 takes on the form of
an equation of a straight line: y = b+ mx. where y and x are analogous, respec-
tively, to the variables log D and 1/T. Thus, if log D is plotted versus the re-
ciprocal of the absolute temperature, a straight line should result, having
slope and intercept of -Qd/2.3R and log D0, respectively. This is the manner
in which the values of Qd and D0 are determined experimentally. From such
a plot for several alloy systems (Figure 1.20), it may be noted that linear rela-
tionships exist for all cases shown.

Figure 1.20 - Plot of the logarithm of the diffusion coefficient versus the re-
ciprocal of absolute temperature for several metals.
30

Line defects: dislocations in metals

Punctual defects are not the only type of wrong arrangement of atoms in-
side crystal lattice. Several atoms can occupy wrong positions, at the same
time. We therefore talk about the line or plane defect. Let us see what it
does mean. Assume to consider a perfect ordered crystal lattice, as it is
schematically represented by perfect cubes link together in a perfect spatial
order, as the scheme in Fig.1.21a depicts.

Figure 1. 21 Constructions of a line defect (dislocation): (a) a perfect crystal; (b)

an extra half-plane of atoms is inserted; (c) the bottom edge of the extra plane is
an edge dislocation.

Now consider a half-plane is inserted in the perfect crystal, by operation on

Fig.1.21b. The results is a locally deformed lattice (see Fig. 1.21c), be-
cause of the presence of the added semi plane. We call this defect disloca-
tion and it is a linear or one-dimensional defect around which some of the
atoms are misaligned: the half-plane edge terminates within the crystal.
This is termed also as edge dislocation and the final row of atoms that
held to the dislocation plane is called the dislocation line, which, for the
edge dislocation in Fig.1.21c is perpendicular to the plane of the page. A
more detailed representation of an edge dislocation is provided in Fig.1.22.
 31

Figure 1.22 - The atom positions around an edge dislocation; extra half-plane of
atoms shown in perspective.

As the point defects above discussed disrupt the perfect arrangement of the
surrounding atoms, irregularities induced by dislocations works in similar
way: within the region around the dislocation line there is some localized
lattice distortion. The atoms above the dislocation line in Figure 1.13 are
squeezed together, and those below are pulled apart; this is reflected in the
slight curvature for the vertical planes of atoms as they bend around this
extra half-plane.

Elastic and plastic deformation in metal by microme-

chanical models
Let us consider the scheme in Figure 1.23, representing by micromechan-
ics approach a perfect crystal lattice of metal: spheres represent atoms of
same specie (thus we deal in this moment with pure metal), no defects, nei-
ther vacancies, or dislocations are present. The link (electric bonding we
discussed in previous paragraph) between atoms is represented by a spring
that exhibits, if loaded in tension, an attractive force (this is in analogy
with electric attraction between nuclei and opposite atoms electrons). Fi-
nally, we assume, for the sake of simplicity, that the box-shaped atoms
grid that represents the 2D-dimension crystal lattice of our metal is actual-
ly a single grain. This means that square perimeter of the grid in Fig.1.23a
actually corresponds to the grain boundary. Now let us apply on this grid a
tensile load, as it is illustrated by the arrows in Fig.1.23b. What does it
happen to our grid in term of deformation?
32

(a) (b) (c)

Figure 1.23 (a) Tensile external load applied to perfect crystal lattice; (b) tensile
stress leads to elastic deformation, and eventually to (c) a brittle rupture consisting
in simultaneous breaking of atom bonds.

Let us proceed reasoning about the assumptions we stated.

Each spring in the micromechanical model that represents the atom bond
obeys to a well-known mechanical relation F=Kx; this means, each spring
has same behavior and same maximum strength. Applying tensile stress,
the grid will extend as shown in Fig.1.23b. But, when the load is so high
and springs extend too much that they exceed their own maximum re-
sistance, springs finally break 2. Moreover, if one single spring breaks, all
the springs distributed in the row perpendicular to the force direction break
at the same time (remember that they have same maximum strength, as
they are similar). The result in this case is that all the atoms of the grid,
from the left side to the right side, detach as Fig.1.23c shows. In other
words, the grain (remember the square grid for us represent a single grain)
rapidly fracture into two pieces. This is the failure scheme which is usual
in brittle materials, like ceramics. Think to throw a ceramic piece onto
floor: it breaks into two or more separate pieces, with no deformation. We
know by experience that metals, usually, when they break exhibit also
large deformed surface. The scheme in Fig.1.23 cannot therefore explain
the plastic deformation in metals; on the other hand, it can well explain the
elastic deformation, as in the next we can understand. Look again at

2
You can read this statement as follows: when atoms are separated by a distance that
determine attractive force drastically reduces, see Fig. 1.2.
 33

Fig.1.4. We stated initial stage of the stress-strain curve in metal concerns

on reversible, or elastic, deformation. Once the load is removed, the spec-
imen recovers original dimension. This is well explained by the microme-
chanical model shown in Fig.1.23a, since until tensile load we apply is suf-
ficiently low (i.e. onto macro-mechanical model, this means keeping
stress below the Yield Strength, YS), the springs in the atomic grid elas-
tically extends. As soon as we remove the load, the grid recovers its origi-
nal shape.
Thus, which way should we modify the micromechanical model to well
explain what we macroscopically observe when specimen surpasses the
YS and enters in plastic deformation regime? We know in metals, as stress
arises above the YS, the elastic regime stage is abandoned, thus metal
starts to permanently deform. We now want to seek a micromechanical
model that allows us to explain such a plastic regime. Let us consider the
same atomic grid of Fig.1.13 but now we want to check what happens if
we apply a shear stress scheme, instead of the tensile stress, accordingly
with the scheme in Fig.1.24.

Slip plane internal

(a) (b)
Figure 1.24 (a) Shear stress applied to perfect crystal lattice; (b) on certain plane
shear stresses can develop and induce atoms in two facing rows to slip. The final
shape of the perimeter of the grid irreversibly changes, thus depicting plastic de-
formation has occurred.

By such a stress field, shear stresses develop onto the intermediate plane,
as shown in the scheme of Fig.1.14b. Let us for the next that shear stress is
higher enough (well better comment how much high it should be), it is
capable to make one crystal lattice plane to slip over the opposite one; the
result of this movement is clearly shown in Fig.1.24b. The atoms of the
upper part of the grid have moved of one step ahead, of the order of an in-
teratomic space. If you imagine to remove the external load, the perimeter
34

of the grid cannot be restored at its original shape. The irreversible defor-
mation has occurred, without implying brittle rupture of atomic bonds.
Thus, the plastic deformation in metal can be effectively explained by this
micromechanical scheme.
But, there is still a but. If we refer to perfect crystal lattice shown in
Fig.1.24, during the slip movement of one step order, 6 atomic bonds have
been broken and 5 have been restored. It appears the net balance of energy
concerns on 1 atomic bonds, but we need to consider the start of the
movement has required in any case external load is sufficient to develop
shear stresses capable to break out 6 atom bonds. You should take into ac-
count that were enormously reducing the scale of a grain to a 36 atoms!
But if we consider a grain in reality, the number of atoms from one border
to the opposite border is of the order of millions! This means that to realize
a very insignificant variation of perimeter of grain, shear stress along the
grain should be capable to break millions of atomic bonds, simultaneously,
thus recovering this huge quantity of energy as the atoms onto slip plane
advance one step (see again the scheme in Fg.1. 24b). This cannot be ex-
plainable in reality, since too much high would be the minimum shear
stress to activate the slip that no machines on Earth would be adequate to
plastically deform metals. From our knowledge of the metallic bond, it is
possible to derive a theoretical value for the stress required to produce slip
by the simultaneous movement of atoms along a plane in a metallic crystal.
However, the strength actually obtained experimentally on single crystals
is only about one-thousandth (1/1000) of the theoretical value, assuming
simultaneous slip by all atoms on the plane. Obviously, slip does not occur
by the simple simultaneous block movement of one layer of atoms sliding
over another. The modern concept is that slip occurs by the step-by-step
movement of dislocations through the crystal. But, how does it contribute
in plastic deformation of metals?

Dislocation and plastic deformation in metal

Fortunately in metals there are millions of dislocations distributed into
crystal lattice, as that one shown in the scheme of Fig.1.22. To compre-
hend how dislocation positively works for plastic deformation, let us con-
sider the scheme in Fig.1.25.
When force is applied such that it shears the upper portion of the crystal to
the right the plane of atoms above the dislocation can easily establish
bonds with the lower plane of atoms to its right, with the result that the dis-
location moves one lattice spacing at a time. Note that only single bonds
are being broken at any one time, rather than the whole row. The atomic
distribution is again similar to the initial configuration, and so, the slipping
 35

of atom planes can be repeated. The movement is much like that of ad-
vancing a carpet along a floor by using a wrinkle that is easily propagated
down its length.
This stress required to cause plastic deformation is orders of magnitude
less when dislocations are present than in dislocation-free, perfect crystal-
line structures.

Figure 1.25 - Line dislocation movement.

If a large number of dislocations move in succession along the same slip

plane, the accumulated deformation becomes visible, resulting in macro-
scopic plastic deformation. This effect is represented by a simplified
scheme in Fig.1.26 representing the macroscopic effect of grain boundary
modification into polycrystalline metal. If a large number of dislocations
move in succession along the same slip plane, the accumulated defor-
mation becomes visible, resulting in macroscopic plastic deformation.
Fig.1.26 also introduces further important key-point: dislocations do not
move with the same degree of ease on all crystallographic planes nor in all
crystallographic directions. Ordinarily, there are preferred planes, and in
these planes, there are specific directions along which dislocation motion
can occur. These planes are called slip planes, and the direction of move-
ment is known as the slip direction. The combination of a slip plane and a
slip direction forms a slip system
36

45

No force applied, dislocation Force applied, maximum shear

inside grain do not move stress induces dislocations on 45
slip planes to move to grain
boundary

Figure 1.26 Permanent deformation occurring at grain boundaries in polycrystal-

line metals that reveal macroscopic deformation onto surface of specimen under
tensile loading.

Slip planes in metals

For a particular crystal structure, the slip plane is that plane having the
most dense atomic packing; that is, it has the greatest planar density. The
slip direction corresponds to the direction, in this plane, that is most close-
ly packed with atoms, that is, has the highest linear density.
Consider, for example, the FCC crystal structure, a unit cell of which is
shown in Figure 1.27a. There is a set of planes, the {111} family, all of
which are closely packed. A (111)-type plane is indicated in the unit cell;
in Figure 1.27b, this plane is positioned within the plane of the page, in
which atoms are now represented as touching nearest neighbors.
 37

Figure 1.27 (a) A {111} slip system shown within an FCC unit cell. (b) The
(111) plane from (a) and three slip directions (as indicated by arrows) within that
plane constitute possible slip systems.

Slip occurs along -type directions within the {111} planes, as indicated by
arrows in Figure 1.27. Hence, represents the slip plane and direction com-
bination, or the slip system for FCC. Figure 1.27b demonstrates that a giv-
en slip plane may contain more than a single slip direction. Thus, several
slip systems may exist for a particular crystal structure; the number of in-
dependent slip systems represents the different possible combinations of
slip planes and directions. For example, for face-centered cubic, there are
12 slip systems: four unique {111} planes and, within each plane, three in-
dependent directions.
The possible slip systems for BCC and HCP crystal structures are listed in
Table 1.1. For each of these structures, slip is possible on more than one
family of planes (e.g., {110}, {211}, and {321} for BCC). For metals hav-
ing these two crystal structures, some slip systems are often operable only
at elevated temperatures.

Table 1.1. - Slip Systems for Face-Centered Cubic, Body-Centered Cubic, and
Hexagonal Close-Packed Metals.
38

Face-centered cubic (fcc) metals have a large number of slip systems (12)
and are therefore capable of moderate-to-extensive plastic deformation.
Although body-centered cubic (bcc) systems often have up to 12 slip sys-
tems, some of them, like steel, exhibit a ductile-to-brittle transition as the
temperature is lowered due to the strong temperature sensitivity of their
yield strength, which causes them to fracture prior to reaching their full po-
tential of plastic deformation. In general, the number of slip systems avail-
able for hexagonal close-packed (hcp) metals is less than that for either the
fcc or bcc metals, and their plastic deformation is much more restricted.
The hcp structure normally has only three to six slip systems, only one-
fourth to one-half the available slip systems in fcc.
Since plastic deformation takes place by slip, or sliding, on the close-
packed planes, the greater the number of slip systems available, the greater
the capacity for plastic deformation.

Slip in single crystal: the Schmids law

A further explanation of slip is simplified by treating the process in single
crystals, then making the appropriate extension to polycrystalline materi-
als. By mechanics in solid we know that, though an applied stress may be
pure tensile (or compressive), shear components exist. Existence of shear
stress is necessary to activate slip planes, so to move dislocation onto this
plane along its slip direction. However the shear stress acting along this di-
rection shall be sufficiently higher to promote dislocation movement. We
need therefore to calculate the projected shear stress along the slip direc-
tion of the external tensile force F applied (see again Fig.1.28a), thus com-
pare the value of this shear stress to the minimum shear stress necessary
for dislocation movement, or critical shear stress, c. The former shear
stress is called the resolved shear stress, r and its magnitude depends not
only on the applied stress, but also on the orientation of both the slip plane
and direction within that plane. To best understand last statement, look at
the scheme in Fig.1.28a. Assume the normal, n, of the slip plane lies at an
angle, , to the tensile axis. The area A of the slip plane considered for all
the specimen will be A0/cos . Similarly, if the slip plane lies at an angle,
, to the tensile axis, the component of the axial force, F, acting on the slip
direction will be Fcos . The resolved shear stress, r, is then given by:
cos
(. 1.20) = = cos cos
cos
Where is the applied stress. If we consider the theoretical case of a single
crystal (grain) specimen where the slip direction is orthogonal to tensile
 39

stress we applied on specimen (see Fig.1.29), the shear stress r for the
Schmid law is 0: this means that also for high applied tensile stress, re-
solved shear stress does not develop and any dislocations cannot move. Ul-
timately, slip of planes cannot occur and plastic deformation cannot occur.

(a) (b)

Figure 1.28 (a) Tensile test of single crystal and the Schmids Law components.
(b) If dislocation is present perpendicular onto slip plane, it can be activated, and
planes slip.

Figure 1.29 - If a slip plane is perpendicular to applied stress , the shear stress r
= 0. Also for high applied stress, no resolved shear stress develop and no disloca-
tion can move. Slip cannot occur, deformation cannot occur.

In general, + 0 because it need not be the case that the tensile axis,
the slip plane normal, and the slip direction all lie in the same plane. A
metal single crystal has a number of different slip systems that are capable
of operating. The resolved shear stress normally differs for each one be-
40

cause the orientation of each relative to the stress axis ( and angles) also
differs. However, one slip system is generally oriented most favorably
that is, has the largest resolved shear stress, r (max):

(. 1.21) = (cos cos )

In response to an applied tensile or compressive stress, slip in a single

crystal commences on the most favorably oriented slip system when the
resolved shear stress reaches a critical value, termed the critical resolved
shear stress crss; it represents the minimum shear stress required to initi-
ate slip and is a property of the material that determines when yielding oc-
curs. The single crystal plastically deforms or yields when r (max) = crss,
and the magnitude of the applied stress required to initiate yielding (i.e.,
the yield strength y) is:

(. 1.22) =
(cos cos )

The minimum stress necessary to introduce yielding occurs when a single

crystal is oriented such that = = 45; under these conditions:

(. 1.23) = 2

For example, if a single-crystal specimen is stressed in tension (see

Fig.1.30), and their slip planes are favorably 45 oriented with tensile
stress direction, slip occurs at minimum tensile stress value, accordingly
with the Schmids law solved in eq.1.22 and calculated in eq.1.23.
 41

(a) (b)

Fig.1.30 Theoretical deformation occurring in a single crystal specimen. (a) A

favorable slip direction in crystal lattice are favorable 45 around oriented; (b) in
this particular case the tensile stress necessary for activating slip of planes is the
minimum value, accordingly with the eq.1.22 and solve eq.1.23.

Slip in polycrystalline crystal

However, instead this very simplified and most theoretical case, most met-
als used in industry are not single crystal. Under an applied axial load, the
Schmids factor will be different for each grain 3. Let us consider a 2D
simplified scheme that can take into account existence of various slip sys-
tem inside specimen loaded in tension. In the example, two grains are
marked with bold arrows: the arrows represent the slip direction for each
random oriented crystal lattices of various grains. These two grains have
their slip directions 45 around oriented with the tensile stress direction.
Thus, these two grains will result in the maximum Schmids factor, thus
they will result in the minimum value in the eq.1.22, namely the mini-
mum tensile stress for activating the movement of dislocations onto slip
plane (necessary condition for grain plastic deformation).

3 For randomly oriented grains, the average value of the Schmid factor is ~1/3, which is

referred to as the Taylor factor. It then follows that the yield strength should have a value of
approximately 3c.
42

max
+45 45

max

Fig.1.31 Scheme of polycrystalline plastic deformation initiation: in crystal lat-

tice there are several grains with several slip systems. Because grains have random
orientation, their slip planes have, too. Some grains therefore could result most fa-
vorable oriented for activating dislocation movements if slip directions (represent-
ed by arrows in the grains) are favorably 45 angles oriented with the load axis.
The 45 orientations represents orientation of such planes where the shear stress
produced by external tensile load reaches its maximum value.

Dislocations start to move in these grains, thus plastic deformation initiates

in these grains. However, with continued extension of specimen, in-
creases and this causes other dislocation systems in other grains not 45
oriented will be activated (i.e. the Schmids factor is lower in other grains
but the stress rises to values for satisfying the eq.1.22).
Finally, you might consider that in real crystal lattice, 3D oriented, there
are several slip systems, as Table 1.1 has shown. For FCC and BCC met-
als, slip may eventually begin along a second slip systemthe system that
is next most favorably oriented with the tensile axis (see the Fig.1.32 and
Fig.1.33).
 43

Figure 1.32 - Slip lines on the surface of a polycrystalline specimen of copper that
was polished and subsequently deformed.

Figure 1.33 - Alteration of the grain structure of a polycrystalline metal as a result

of plastic deformation. (a) Before deformation the grains are equiaxed. (b) The de-
formation has produced elongated grains.
44

Box - DEFORMATION BY TWINNING

In addition to slip, plastic deformation in some metallic materials can occur by

the formation of mechanical twins, or twinning. The concept of a twin concerns
with a shear force that in some crystal lattices can produce atomic displace-
ments such that on one side of a plane (the twin boundary), atoms are located in
mirror-image positions of atoms on the other side. The manner in which this is
accomplished is demonstrated in Figure 1.34. Here, open circles represent at-
oms that did not move, and dashed and solid circles represent original and final
positions, respectively, of atoms within the twinned region. As may be noted in
this figure, the displacement magnitude within the twin region (indicated by ar-
rows) is proportional to the distance from the twin plane.

Figure 1.34 - Schematic diagram showing how twinning results from an applied shear
stress . In (b), open circles represent atoms that did not change position; dashed and sol-
id circles represent original and final atom positions, respectively.

Slip and twinning deformations are compared in Figure 8.13 for a single crystal
that is subjected to a shear stress .

Figure 1.35 - For a single crystal subjected to a shear stress , (a) deformation by slip, (b) defor-
mation by twinning.

Mechanical twinning occurs in metals that have BCC and HCP crystal struc-
tures, at low temperatures, and at high rates of loading (shock loading), condi-
tions under which the slip process is restricted; that is, there are few operable
slip systems.
 45

Mechanisms of Strengthening in Metals

Metallurgical and materials engineers are often called on to design alloys
having high strengths yet some ductility and toughness; typically, ductility
is sacrificed when an alloy is strengthened. Several hardening techniques
are at the disposal of an engineer, and frequently alloy selection depends
on the capacity of a material to be tailored with the mechanical characteris-
tics required for a particular application. Important to the understanding of
strengthening mechanisms is the relation between dislocation motion and
mechanical behavior of metals. Because macroscopic plastic deformation
corresponds to the motion of large numbers of dislocations, the ability of a
metal to deform plastically depends on the ability of dislocations to move.
Because hardness and strength (both yield and tensile) are related to the
ease with which plastic deformation can be made to occur, by reducing the
mobility of dislocations, the mechanical strength may be enhanced; that is,
greater mechanical forces will be required to initiate plastic deformation.
In contrast, the more unconstrained the dislocation motion, the greater is
the facility with which a metal may deform, and the softer and weaker it
becomes. Virtually all strengthening techniques rely on this simple princi-
ple: Restricting or hindering dislocation motion renders a material harder
and stronger. The present discussion is confined to strengthening mecha-
nisms for single-phase metals by grain size reduction, solid-solution alloy-
ing, and strain hardening. Deformation and strengthening of multiphase al-
loys are more complicated, involving concepts beyond the scope of the
present discussion; later chapters treat techniques that are used to strength-
en multiphase alloys.

Strengthening by grain size reduction

The size of the grains, or average grain diameter, in a polycrystalline metal
influences the mechanical properties. Adjacent grains normally have dif-
ferent crystallographic orientations and, of course, a common grain bound-
ary, as indicated in Fig. 1.36. During plastic deformation, slip or disloca-
tion motion must take place across this common boundary say, from
grain A to grain B in Fig.1.36.The grain boundary acts as a barrier to dis-
location motion for two reasons:

1. Because the two grains are of different orientations, a dislocation

passing into grain B will have to change its direction of motion;
this becomes more difficult as the crystallographic misorientation
increases.
46

2. The atomic disorder within a grain boundary region will result in a

discontinuity of slip planes from one grain into the other.
It should be mentioned that, for high-angle grain boundaries, it may not be
the case that dislocations traverse grain boundaries during deformation; ra-
ther, dislocations tend to pile up (or back up) at grain boundaries. These
pileups introduce stress concentrations ahead of their slip planes, which
generate new dislocations in adjacent grains. A fine-grained material (one
that has small grains) is harder and stronger than one that is coarse grained
because the former has a greater total grain boundary area to impede dislo-
cation motion. For many materials, the yield strength y varies with grain
size according to:
1
(. 1.24) = 0 + 2

In this expression, termed the HallPetch equation, d is the average grain

diameter, and 0 and Ky are constants for a particular material. Note that
Equation 1.24 is not valid for both very large (i.e. coarse) grain and ex-
tremely fine grain polycrystalline materials. Fig.1.37 demonstrates the
yield strength dependence on grain size for a brass alloy 4.

Figure 1.36 - The motion of a dislocation as it encounters a grain boundary, illus-

trating how the boundary acts as a barrier to continued slip. Slip planes are discon-
tinuous and change directions across the boundary.

4
Grain size may be regulated by the rate of solidification from the liquid phase, and also
by hot plastic deformation, as discussed in Chapter 9.
 47

Figure 1.37 - The influence of grain size on the yield strength of a 70 Cu30 Zn
brass alloy. Note that the grain diameter increases from right to left and is not lin-
ear.

It should also be mentioned that grain size reduction improves not only the
strength, but also the toughness of many alloys; this fact can be explained
as follows. Considering the scheme in Fig.1.31, if you imagine to reduce
the grain size, many grains will appear in the same round window. This
fact implies several further slip systems will add, because they are perti-
nent to each single new grain you may consider. The result is the follow-
ing. On one hand increasing of number of grain boundaries, that leads to
increasing strength as above discussed; on the other hand, the increasing
number of slip systems can contemporarily lead material to be prone dislo-
cation movement inside the grain; this phenomenon results in higher ener-
gy absorption during dislocation movement inside the grain, toward the
grain boundaries where dislocation will pile up.
Small-angle grain boundaries are not effective in interfering with the slip
process because of the slight crystallographic misalignment across the
boundary. On the other hand, twin boundaries will effectively block slip
and increase the strength of the material. Boundaries between two different
phases are also impediments to movements of dislocations; this is im-
portant in the strengthening of more complex alloys.
48

Solid solution strengthening

Another technique to strengthen and harden metals is alloying with impuri-
ty atoms that go into either substitutional or interstitial solid solution. Ac-
cordingly, this is called solid solution strengthening. High-purity metals
are almost always softer and weaker than alloys composed of the same
base metal. Increasing the concentration of the impurity results in an at-
tendant increase in tensile and yield strengths, as indicated in Fig.1.38a
and 1.38b, respectively, for nickel in copper; the dependence of ductility
on nickel concentration is presented in Fig. 1.38c.

Figure 1.38 - Variation with nickel content of (a) tensile strength, (b) yield
strength, and (c) ductility (%EL) for coppernickel alloys, showing strengthening.

Alloys are stronger than pure metals because impurity atoms that go into
solid solution typically impose lattice strains on the surrounding host at-
oms. Lattice strain field interactions between dislocations and these impu-
rity atoms result, and, consequently, dislocation movement is restricted.
For example, an impurity atom that is smaller than a host atom for which it
substitutes exerts tensile strains on the surrounding crystal lattice, as illus-
trated in Figure 1.39a.
 49

Figure 1.39 - (a) Representation of tensile lattice strains imposed on host atoms by
a smaller substitutional impurity atom. (b) Possible locations of smaller impurity
atoms relative to an edge dislocation such that there is partial cancellation of im-
puritydislocation lattice strains.

Figure 1.40 - (a) Representation of compressive strains imposed on host atoms by

a larger substitutional impurity atom. (b) Possible locations of larger impurity at-
oms relative to an edge dislocation such that there is partial cancellation of impuri-
tydislocation lattice strains.

Conversely, a larger substitutional atom imposes compressive strains in its

vicinity (Figure 1.40a).These solute atoms tend to diffuse to and segregate
around dislocations in such a way as to reduce the overall strain energy
that is, to cancel some of the strain in the lattice surrounding a dislocation.
To accomplish this, a smaller impurity atom is located where its tensile
strain will partially nullify some of the dislocations compressive strain.
For the edge dislocation in Figure 1.39b, this would be adjacent to the dis-
location line and above the slip plane. A larger impurity atom would be
situated as in Figure 1.40b. The resistance to slip is greater when impurity
50

atoms are present because the overall lattice strain must increase if a dislo-
cation is torn away from them. Furthermore, the same lattice strain interac-
tions (Figures 1.39b and 1.40b) will exist between impurity atoms and dis-
locations that are in motion during plastic deformation. Thus, a greater
applied stress is necessary to first initiate and then continue plastic defor-
mation for solid-solution alloys, as opposed to pure metals; this is evi-
denced by the enhancement of strength and hardness.

Strain hardening
Strain hardening is the phenomenon by which a ductile metal becomes
harder and stronger as it is plastically deformed. Sometimes it is also
called work hardening or, because the temperature at which deformation
takes place is cold relative to the absolute melting temperature of the
metal, cold working. Most metals strain harden at room temperature. Fig.
1.41a and 1.41b demonstrate how steel, brass, and copper increase in yield
and tensile strength with increasing cold work. The price for this en-
hancement of hardness and strength is in a decrease in the ductility of the
metal. This is shown in Fig.1.41c, in which the ductility, in percent elonga-
tion, experiences a reduction with increasing percent cold work for the
same three alloys.

Figure 1.41 - For 1040 steel, brass, and copper, (a) the increase in yield strength,
(b) the increase in tensile strength, and (c) the decrease in ductility (%EL) with
percent cold work

The influence of cold work on the stressstrain behavior of a low-carbon

steel is shown in Figure 8.20; here stressstrain curves are plotted at
0%CW, 4%CW, and 24%CW.
 51

Figure 1.42 - The influence of cold work on the stressstrain behavior of a low-
carbon steel; curves are shown for 0% cold worked, 4% cold worked, and 24%
cold worked.

Strain hardening is demonstrated in a stressstrain diagram presented in

Fig.1.43. Initially, the metal with yield strength y0 is plastically deformed
to point D. The stress is released, then reapplied with a resultant new yield
strength, yi. The metal has thus become stronger during the process be-
cause is greater than y0.

Figure 1.43 Schematic tensile stressstrain diagram showing the phenomena of

elastic strain recovery and strain hardening.
52

The strain-hardening phenomenon is explained on the basis of dislocation

dislocation strain field interactions similar to those discussed for the solid
solution strengthening, but more effective. The dislocation density in a
metal increases with deformation or cold work because of dislocation mul-
tiplication or the formation of new dislocations, as noted previously. Con-
sequently, the average distance of separation between dislocations de-
creasesthe dislocations are positioned closer together. On the average,
dislocationdislocation strain interactions are repulsive. The net result is
that the motion of a dislocation is hindered by the presence of other dislo-
cations. As the dislocation density increases, this resistance to dislocation
motion by other dislocations becomes more pronounced.
As a metal is plastically deformed, new dislocations are thus created, so
that the dislocation density becomes higher and higher. In addition to mul-
tiplying, the dislocations become entangled and impede each others mo-
tion. Dislocations, in fact, are influenced by the presence of other disloca-
tions and interact with each other, as shown for a number of different
interactions in Fig. 1.44.

Figure 1.44 Examples of dislocation interactions.

Dislocations of the same sign will repel each other, while dislocations of
opposite signs will attract each other and, if they meet, annihilate each oth-
er. If the two dislocations of opposite signs are not on the same slip plane,
 53

they will merge to form a row of vacancies. These types of interactions oc-
cur because they reduce the internal energy of the system.
The result, in any case, is increasing resistance to plastic deformation with
increasing dislocation density. Work hardening thus results in a simultane-
ous increase in strength and a decrease in ductility. Since the work hard-
ened condition increases the stored energy in the metal and is thermody-
namically unstable, the deformed metal will try to return to a state of lower
energy. This generally cannot be accomplished at room temperature. Ele-
vated temperatures, in the range of 1/2 to 3/4 of the absolute melting point,
are necessary to allow mechanisms, such as diffusion, to restore the lower-
energy state. The process of heating a work-hardened metal to restore its
original strength and ductility is called annealing. Metals undergoing form-
ing operations often require intermediate anneals to restore enough ductili-
ty to continue the forming operation. Approximately 5% of the energy of
deformation is retained internally as dislocations when a metal is plastical-
ly deformed, while the rest is dissipated as heat.
The imposed stress necessary to deform a metal increases with increasing
cold work. In the mathematical expression relating true stress and strain
shown by equation 1.25:

(. 1.25) =

the parameter n is called the strain-hardening exponent, which is a meas-

ure of the ability of a metal to strain harden; the larger its magnitude, the
greater is the strain hardening for a given amount of plastic strain.

Phase boundaries as strengthening sources

While a grain boundary is an interface between grains of the same compo-
sition and same crystalline structure (/ interface) with different orienta-
tions, a phase boundary is one between two different phases (/ interface)
that can have different crystalline structures and/or different compositions.
In two-phase alloys, such as copper-zinc brass alloys containing more than
40% Zn, second phases, such as the one shown in Fig. 1.45, can form due
to the limited solid solubility of zinc in copper.
54

Figure 1.45 Phase boundary in copper-zinc system.

There are three different types of crystalline interfaces that can develop be-
tween two phases (Fig. 1.46): coherent, semicoherent, and incoherent. A
fully coherent phase boundary (Fig. 1.46a, b) occurs when there is perfect
atomic matching and the two lattices are continuous across the interface.
The interfacial plane will have the same atomic configuration in both
planes. Since there is perfect matching at the interface, the interfacial ener-
gy is low. When the distances between atoms at the interface are not iden-
tical (Fig. 1.46c), coherency strains start to develop. However, since there
is still perfect atomic matching, it is still a coherent phase boundary; only
the interfacial energy will be higher than one with no distortion. When the
mismatch becomes sufficiently large, dislocations form to accommodate
the growing disregistry. The result is called a semicoherent interface (Fig.
1.46d) that has an medium-high interfacial energy. Finally, an incoherent
interface (Fig. 1.46e, f) is an interphase boundary that results when the ma-
trix and precipitate have very different crystal structures, and little or no
atomic matching can occur across the interface. The interfacial energy is
even greater. An incoherent boundary is essentially equivalent to a high-
angle grain boundary.
 55

Figure 1.46 Phase boundaries systems.

In many instances, second phases have a tendency to form at the grain

boundaries. This occurs because they reduce their interfacial energy by oc-
cupying a grain boundary; that is, by occupying a grain boundary, part of
the interfacial energy is eliminated, and the total energy of the system is
reduced.
Depending on the type of their phase boundaries, such fine particles can
exhibit slight or very high obstruction to dislocation movement. These in
fact are in any case an irregularity for the matrix crystal lattice constituting
the grain where dislocation can move. These fine precipitate particles, in
other words, act as barriers to the motion of dislocations and provide re-
sistance to slip, thereby increasing the strength and hardness.
Particles are usually classified as deformable or non-deformable, meaning
that the dislocation is able to cut through it (deformable) or the particle is
so strong that the dislocation cannot cut through (non-deformable). When a
dislocation encounters a fine particle, it must either cut through the particle
or bow (loop) around it, as shown schematically in Fig. 1.47.
56

Figure 1.47 Particle strengthening.

For effective particle strengthening (Fig. 1.48), the matrix should be soft
and ductile, while the particles should be hard and discontinuous. A ductile
matrix is better in resisting catastrophic crack propagation. Smaller and
more numerous particles are more effective at interfering with dislocation
motion than larger and more widely spaced particles. Preferably, the parti-
cles should be spherical rather than needlelike to prevent stress-
concentration effects. Finally, larger amounts of particles increase
strengthening.
 57

Figure 1.48 Particle-hardening considerations.

In summary we have discussed mechanisms that may be used to strengthen

and harden single-phase metal alloys: strengthening by grain size reduc-
tion, solid-solution strengthening, strain hardening and second phase-
dispersed (or fine particles) hardening. Of course they may be used in con-
junction with one another; for example, a solid-solution-strengthened alloy
may also be strain hardened.

Grain Growth, Recovery and Recrystallization

Plastically deforming a polycrystalline metal specimen at temperatures that

are low relative to its absolute melting temperature produces microstruc-
tural and property changes that include (1) a change in grain shape, (2)
strain hardening, and (3) an increase in dislocation density. Some fraction
of the energy expended in deformation is stored in the metal as strain ener-
gy, which is associated with tensile, compressive, and shear zones around
the newly created dislocations.
These properties and structures may revert back to the precold-worked
states by appropriate heat treatment, sometimes termed an annealing
treatment. Such restoration results from two different processes that occur
at elevated temperatures: recovery and recrystallization, which may be fol-
lowed by grain growth.
58

Recovery
Recovery is the initial stage of the annealing cycle before recrystallization
occurs. During recovery, some of the stored internal strain energy is re-
lieved by virtue of dislocation motion (in the absence of an externally ap-
plied stress), as a result of enhanced atomic diffusion at the elevated tem-
perature. There is some reduction in the number of dislocations, and
dislocation configurations are produced having low strain energies.
During recovery, basic types of processes that occur are:
(1) the annihilation of excess point defects, particularly vacancies; the
vacancies that were generated during cold working are annealed
out by migrating to dislocations, grain boundaries, or surfaces;
(2) the rearrangement of dislocations into lower energy configura-
tions, which also annihilates many of them; At slightly higher
temperatures, the rearrangement of dislocations occurs, and, in the
process, the annihilation of dislocations of opposite signs takes
place. The rearrangement of dislocations is assisted by thermal en-
ergy, which aids in both climb and slip mechanisms.
(3) the formation of subgrains that grow and interlock into sub-
boundaries (Fig.1.49).

Figure 1.49 - the coalescence mechanism of two grains by mutual accommodation

(rotation) and coalescence.
 59

Grain growth
It should also be noted that the strengthening effects due to grain size re-
duction and strain hardening can be eliminated or at least reduced by an el-
evated-temperature heat treatment. Regarding with the enlarging of grain
size, heating up metals produces diffusivity to increase. The higher is the
diffusivity (refer to eq. 1.9), the higher is the diffusion of species in matrix.
This is true also for the self-diffusion of element. When atoms move from
one position to another obeying to diffusion mechanisms (refer to par.
Vacancies, interstitial spaces and grain boundaries as drive-force for dif-
fusion in metals), they also can move from one grain boundary to anoth-
er: what could happen is schematically shown in Fig.1.50a. Basing on the
grain boundary migration, in the Fig. 1.50b is shown the mechanisms
that provokes grain growth by small grains disappearing. Ultimately, grain
growth occurs because of metal with its original microstructure is heated
up to certain temperature (Fig.1.51).

(a)

(b)

Figure 1.50 (a) Schematic representation of grain growth via atomic diffusion;
(b) disappearing of small grains.
60

Empirically, it has been shown that grain growth occurs according to:

(. 1.26) =

Where:
D is the average grain diameter,
t is time,
n is a constant,

= 0 2

The constant n increases with temperature and approaches a theoretical

value of 0.5. It should also be noted that the activation energy, Q, also var-
ies with temperature.

Figure 1.51 Schematic representation of grain size versus treatment temperature

relationship.

Recrystallization
Even after recovery is complete, the grains are still in a relatively high
strain energy state. Recrystallization is the formation of a new set of strain-
free and equiaxed grains (i.e., having approximately equal dimensions in
all directions) that have low dislocation densities and are characteristic of
the precold-worked condition. The driving force to produce this new
grain structure is the difference in internal energy between the strained and
unstrained material. The new grains form as very small nuclei and grow
until they completely consume the parent material, processes that involve
short range diffusion. Two stages in the recrystallization process are repre-
sented in Fig.1.52a, 1.52b and 1.52c. In these photomicrographs, the small,
speckled grains are those that have recrystallized.
 61

Recrystallization of cold-worked metals may be used to refine the grain

structure. Also, during recrystallization, the mechanical properties that
were changed as a result of cold working are restored to their precold-
worked values; that is, the metal becomes softer and weaker, yet more duc-
tile (the extent of recrystallization depends on both time and temperature),
as shown in Fig.1.53.
The influence of temperature is demonstrated in Figure 1.54, which plots
tensile strength and ductility (at room temperature) of a brass alloy as a
function of the temperature and for a constant heat treatment time of 1 h.
The grain structures found at the various stages of the process are also pre-
sented schematically.
Recrystallization is considered complete when the mechanical properties
of the recrystallized metal approach those of the metal before it was cold
worked; on the other hand, recrystallization and the resulting mechanical
softening completely cancel the effects of cold working.
62

Figure 1.52 Recrystallization progression in low-carbon steel. (a) Recrystallized

10%. (b) Recrystallized 40%. (c) Recrystallized 80%.
 63

Figure 1.53 The influence of annealing temperature (for an annealing time of 1

h) on the tensile strength and ductility of a brass alloy. Grain size as a function of
annealing temperature is indicated. Grain structures during recovery, recrystalliza-
tion, and grain growth stages are shown schematically.

Figure 1.54 The variation of recrystallization temperature with percent cold

work for iron. For deformations less than the critical (about 5% cold work, CW),
recrystallization will not occur.
64

Plastic deformation operations are often carried out at temperatures above

the recrystallization temperature in a process termed hot working
(Fig.1.55), described in last paragraph of Chapter 9. The material remains
relatively soft and ductile during deformation because it does not strain
harden, and thus large deformations are possible.

Figure 1.55 Recrystallization during hot rolling.

Mechanical behavior of metals by macroscopic approach

The mechanical behavior of a material is its response to an applied load or

force. Important mechanical properties are strength, hardness, stiffness,
and ductility. There are three principal ways in which a load may be ap-
plied: tension, compression, and shear. Large number of mechanical prop-
erty tests have been developed to determine a material response to applied
loads or forces.

Tensile test
The tensile test is the most commonly used mechanical property test. Its
chief use is to determine the properties related to the elastic design of
structures. In addition, the tensile test gives information on the plasticity
and fracture of a material. A typical stress-strain curve for a metal is
shown in Fig. 1.55. The parameters used to describe the stress-strain curve
of a metal are the tensile strength, yield strength or yield point, percent
elongation, and reduction in area. The first two are strength parameters,
and the last two are indications of ductility. As long as the specimen is
loaded within the elastic region, the strain is totally recoverable. However,
when the load exceeds a value to the yield stress, the specimen undergoes
plastic deformation and is permanently deformed when the load is re-
moved. The stress to produce continued plastic deformation increases with
increasing strain, thus obeying to work hardening phenomenon, discussed
 65

above as one of strengthening mechanism active in metals. To a good en-

gineering approximation, the volume remains constant during plastic de-
formation (Al=A0l0), and as the specimen elongates, it decreases uniformly
in cross-sectional area along its gage length. Initially,
strain hardening more than compensates for this decrease in area, and the
engineering stress continues to rise with increasing strain. However, even-
tually, a point is reached where the decrease in area is greater than the in-
crease in deformation load from strain hardening. This condition will be
reached first at some point in the specimen that is slightly weaker than the
rest. All further plastic deformation is then concentrated in this region, and
the specimen begins to neck or thin locally. Because the cross-sectional ar-
ea is now decreasing far more rapidly than the deformation load is being
increased by strain hardening, the engineering stress continues to decrease
until fracture occurs.

Figure 1.55 Typical stress-strain curve.

Figure 1.56 Different stress-strain responses.

66

With most metals, there is a gradual transition from elastic to plastic be-
havior, and the point at which plastic deformation actually begins is diffi-
cult to define with precision. The transition from elastic to plastic defor-
mation is illustrated in Fig. 1.57.

Figure 1.57 Elastic and plastic behavior during tensile loading.

Metals that yield discontinuously have a stress-strain curve similar to that

shown in Fig. 1.58a, instead of a continuous gradual yield point as in Fig.
1.58b. While in the former case the yield point is univocally identified as
lower and higher yield point (see Fig.1.58a), for the metals with indefinite
yield point, yield strength is determined by drawing a straight line parallel
to the initial straight line portion of the stress-strain curve. The line is nor-
mally offset by a strain of 0.2% (0.002).

(a) (b)

Figure 1.58 (a) Transition from elastic to plastic behavior; (b) Discontinuous
yielding in plain carbon steels.
 67

Ductility
Measures of ductility that are obtained from the tension test are the engi-
neering strain at fracture (f) and the reduction of area at fracture. Both are
usually expressed as percentages, with the engineering strain at failure of-
ten reported as the percent elongation. Both of these properties are ob-
tained after fracture by putting the specimen back together and taking
measurements of the final length, lf, and final specimen cross section at
fracture, Af. Percent elongation can be determined by:

where l0 is the original gage length, and lf is the final length of the gage
section. Likewise, reduction in area can be determined by:

where A0 is the original area of the gage section, and Af is the final area of
the gage section at fracture.

Resilience
Resilience is the capacity of a material to absorb energy when it is de-
formed elastically and then, upon unloading, to have this energy recovered.
The associated property is the modulus of resilience, Ur , which is the
strain energy per unit volume required to stress a material from an unload-
ed state up to the point of yielding. The modulus of resilience for a speci-
men subjected to a uniaxial tension test is just the area under the engineer-
ing stressstrain curve taken to yielding:

(. 1.27) =
0

Assuming a linear elastic region, we have:

68

1
(. 1.28) = = [ ]
2
1 2
=
2

in which y is the strain at yielding (see scheme in Fig.1.59). The units of

resilience are the product of the units from each of the two axes of the
stressstrain plot. For SI units, this is joules per cubic meter (J/m3, equiva-
lent to Pa).

Figure 1.59 Schematic representation showing how modulus of resilience (corre-

sponding to the shaded area) is determined from the tensile stressstrain behavior
of a material.

Toughness
Although there are a number of approaches to defining toughness, one of
the oldest is to consider it as the total area under the stress-strain curve.
This area is an indication of the amount of work per unit volume that can
be done on a material without causing it to fail. As shown in Fig. 1.60, this
definition of toughness implies that toughness is a function of both
strength and ductility.
Another way of defining toughness is as the ability of a material to absorb
energy and plastically deform before fracturing. For dynamic (high strain
rate) loading conditions and when a notch (or point of stress concentration)
is present, notch toughness is assessed by using an impact test (Fig.1.61).
 69

Figure 1.60 Area under stress-strain curve as a measure of toughness.

Figure 1.61 Impact test machine (Charpy test) conducted onto notched speci-
men.
70

Box Stress concentration

Geometrical features, such as holes, fillets, and radii, produce higher local
stresses than encountered in the body of the material. For example, the tensile
stresses at the top and bottom of the hole shown in Fig. 1.62 are three times
greater than they are in the body of the material. These higher stresses are a re-
sult of the inability of the stresses to pass through the hole.

Figure 1.62 Stress-concentration effect around a hole.

Such stress increases are described by the stress-concentration factor, K:

K = Maximum actual stress/ Nominal stress

While the stress-concentration factor K for a round hole is 3, much higher stress
concentration factors occur when there is a sharp notch in the material. Values
for a wide range of geometries can be found in handbooks dealing with stress
analysis.

Hardness
Hardness is the resistance to penetration, and the majority of hardness test-
ers force a small sphere, pyramid, or cone into a specimen by means of an
applied load. A number is obtained, and the hardness can often be correlat-
ed to the tensile strength of the metal. This proportional relationship de-
pends on the fact both tensile strength and hardness are indicators of a
metals resistance to plastic deformation, that occurs on same micro-
mechanical mechanisms of dislocation movement. Consequently, they are
roughly proportional, as shown in Figure 1.63 for tensile strength as a
 71

function of the HB for cast iron, steel, and brass. As a rule of thumb, for
most steels, the HB and the tensile strength are related according to:

UTS (MPa) = 3.34 x HB (or HV for hardness higher than 500 HB)

In any case, the same proportionality relationship does not hold for all
metals, as Figure 1.63 indicates. This depend, in fact, by micro-
mechanisms of dislocation movement in different matrix of different met-
als.

Figure 1.63 Relationships among hardness and tensile strength for steel, brass,
and cast iron.
72

Box Hardness test, the basics.

Resuming the main contents, defining the main paradigm for mechan-
ical response of metals

On an atomic scale level, plastic deformation corresponds to the motion of

dislocations in response to an externally applied shear stress. For example,
an edge dislocation moves by the successive and repeated breaking of
atomic bonds and shifting by interatomic distances of half planes of atoms.
For dislocation edge, in particular, dislocation line motion and direction of
the applied shear stress are thus parallel. We call slip the motion of dislo-
cations in response to an externally applied shear stress. It occurs on spe-
cific crystallographic planes and within these planes only in certain direc-
tions, depending on crystal structure of the metal. The combination of slip
planes and slip direction, expressed by the Schmids Law, is defined slip
system. The slip plane is that plane that has the densest atomic packing,
and the slip direction is the direction within this plane that is most closely
packed with atoms. Operable slip systems, namely the planes where dislo-
cation are active, depend on the crystal structure of the material.
 73

A resolved shear stress is the shear stress resulting from an applied tensile
stress that is resolved onto a plane that is neither parallel nor perpendicular
to the stress
direction. For polycrystalline materials, slip occurs within each grain along
those slip systems that are most favorably oriented with the applied stress.
As favorable oriented we mean that in such grains the resolved shear stress
is highest and it can achieve the critical shear stress, namely the shear
stress necessary to activate dislocation slip along slip plane and in the slip
direction. During deformation, grains change shape and extend in those di-
rections wherein there is gross plastic deformation.
The basic concept is that the ease with which a material is capable of plas-
tic deformation is a function of dislocation mobilitythat is, restricting
dislocation motion leads to increases hardness and strength.
Various modes are practicable to inhibit dislocation mobility. We call
these modes strengthening mechanisms:
- Grain Size Reduction: as grain boundaries are barriers to disloca-
tion motion for two reasons: a) when crossing a grain boundary, a
dislocations direction of motion must change; b) there is a discon-
tinuity of slip planes within the vicinity of a grain boundary. A
metal that has small grains will be stronger than one with large
grains because the former has more grain boundary area, and, thus,
more barriers to dislocation motion. For most metals, yield
strength depends on average grain diameter according to the Hall
Petch equation.
- Solid-Solution Strengthening: the strength and hardness of a
metal increase with increase of concentration of impurity atoms
that go into solid solution (both substitutional and intersti-
tial).Solid-solution strengthening results from lattice strain interac-
tions between impurity atoms and dislocations; these interactions
produce a diminishment in dislocation mobility.
- Strain Hardening: strain hardening is just the enhancement in
strength (and decrease of ductility)of a metal as it is plastically de-
formed. Degree of plastic deformation may be expressed as per-
cent cold work, which depends on original and deformed cross-
sectional areas. Yield strength, tensile strength, and hardness of a
metal increase with increasing percent cold work; ductility dimin-
ishes. During plastic deformation dislocation density increases, the
average distance between adjacent dislocations decreases, and
because dislocationdislocation strain field interactions, are, on
average, repulsivedislocation mobility becomes more restricted;
thus, the metal becomes harder and stronger.
74

On the opposite, mechanisms that tend to recover the dislocation mobility,

driven by heating up structure, are:
- Recovery: There is some relief of internal strain energy by dislo-
cation motion. Dislocation density decreases, and dislocations as-
sume low-energy configurations. Some material properties revert
back to their precold-worked values.
- Recrystallization: During recrystallization, a new set of strain-
free and equiaxed grains form that have relatively low dislocation
densities. The metal becomes softer, weaker, and more ductile.
The driving force for recrystallization is the difference in internal
energy between strained and recrystallized material. For a cold-
worked metal that experiences recrystallization, as temperature in-
creases (at constant heat-treating time), tensile strength decreases
and ductility. The recrystallization temperature of a metal alloy is
that temperature at which recrystallization reaches completion in
one hour. Two factors that influence the recrystallization tempera-
ture are percent cold work and impurity content. Furthermore, re-
crystallization temperature diminishes with increasing percent cold
work.
- Grain growth is the increase in average grain size of polycrystal-
line materials, which proceeds by grain boundary motion. The
driving force for grain growth is the reduction in total grain
boundary energy.

The most important conclusion we point out is the full understanding the
strengthening mechanisms for metals and the resulting high or low me-
chanical properties on the microscopic scale is easily explained by a
high or low dislocation motion resources. The higher is dislocation mobili-
ty, the lower is the onset to which plastic deformation occurs, namely the
yield strength (YS) and the higher is the plastic deformation capacity under
static or impacting loads that we expressed respectively by: a) the elonga-
tion percentage at break E% (alternatively or adding to % reduction of area
at break) and b) the energy stored (i.e. the Joule absorbed) by breaking a
standard notched sample by an impact test machine.
Summarizing, we can quickly measure by tensile test and impact test some
macroscopic mechanical parameters by which we can state whether metal-
lic materials behave either by ductile and tough safe mode or brittle unsafe
mode. To understand why we can correlate the ductile and tough behavior
to a safe operating mode of a metal for structural application, consider
whether you would be happy to know the axle of your car is so low ductile
and tough that its mechanical behavior is like a ceramic material.
 75

Basing on the 3 basic mechanical tests we have discussed so far, tensile

test, hardness test and impact test, we therefore can group the main me-
chanical features we obtain by 3 type of tests, distinguishing in mechanical
resistance properties and ductile properties, as shown in following
Fig.1.65.

Hardness (hardness test) E%, A% (tensile test)

YS; UTS (tensile test) KV (Impact test, e.g. Charpy)

Fig.1.65 Basic mechanical properties from tensile test, hardness test and impact
test grouped into: a) resistance capability (left side); b) ductility capability ( right
side).

As we already learned, the left side and right side properties for metal are
strictly correlated, because of the following causal relationship:

i) Dislocations move and reach grain boundary grain boundary

perimeter modifies macroscopic plastic deformation occurs(1)
Note 1: For example macroscopic deformation is observed in surpassing
the onset yield strength, necking occurs in tensile tests; indenting of test
material by penetrator in the hardness test; highly plastically deformed
regions in the notched section area of Charpy test specimen broken.

And its own counteracting relationship :

ii) Dislocations are temporarily locked dislocation motion is

inhibited critical resolved shear stress crss increases in-
(2)
crease magnitude of external load to unlock dislocation dislo-
cation move and reach grain boundary

Note 2: Refer to eq.1.22.

What happens in metals is that, as well as dislocations are inhibited in their

movement (independently of reasons, namely whichever strengthening
mechanism is established), the yield strength increases, the ultimate tensile
strength increases, the hardness increases, as we expect because of the in-
76

crease of such magnitude of external load capable to unlock dislocation;

but at the same time, in strengthened matrix, mobility of dislocations de-
creases, thus resulting in decrease of ductile properties.
The basic framework of such mutual relationships of a metal is shown in
Fig.1.64. For example, a high hardness and consequently lack of ductility
of one phase found in steel, the martensite, is explained by a solid-solution
strengthening effect, that leads to an increase of resolved critical shear
stress and consequently external load necessary to unlock dislocations.
But, in addition, the martensite structure has very few slip systems. These
double conditions leads on one hand to a very high critical resolved shear
stress, responsible of high hardness and the high strength of martensite; on
the other hand very few possibilities offered to dislocation to move (few
slip planes) causes few plastic deformation capability, that lead macro-
scopically to very low ductility and toughness.

Strong, stiff and brittle Strong and low-tough High-tough and ductile
material material material

High stiffness

Low stiffness

UTS High strength

UTS
UTS
Low strength

Low toughness High toughness

r r r
Low ductility high ductility

Fig. 1.65 - Understanding basic material properties and their mutual correlations.
For example, a high stiffness material (scheme on the left side) is a material with
high slope measured in the origin - of the (stress) and (deformation) curve
obtained by a tensile test on the material. This slope is called the elastic modulus
of the material. Such a high stiffness material usually exhibits further high me-
chanical strength (i.e. Ultimate Tensile Strength, UTS), low ductility (i.e. defor-
mation at break, r) and low toughness (i.e. energy stored to break, proportional to
area below the tensile test diagram).
 77

Microstructural features of fracture in metallic materials

The dislocation motion or their inhibition to movement plays a determi-

nant role in the metal fracture. We mean as fracture in metals the same for
any layman persons, not a metallurgist (actually you will be surprised in
the following how much intuitive is the vocabulary of a metallurgist!).
Thus, fracture is simply the separation of a solid body made of metal into
two or more pieces, under the action of external load.
For metals, fracture can be classified into two broad categories: a) ductile
fracture and b) brittle fracture. The ductile or brittle mode depends pri-
marily on the macroscopic appearance of the fractured material. More pre-
cisely, the Fig. 13.1 shows a schematic comparison between two ductile
fractures - on the right side that are both characterized by extensive plas-
tic deformation, prior to and during crack propagation.

Fig. 1.66 - Comparison of brittle and ductile fracture modes.

On the opposite, a brittle fracture occurs with little or no gross plastic de-
formation and usually occur suddenly, without warning (thus in unsafe
mode - remind the ceramic vehicle axle!).
The tendency for brittle fracture increases as well as any external or inter-
nal conditions work for: a) locking dislocations and/or b) reduce slip
planes. Thus, the tendency for a material that has sufficient slip planes
(this is not the case of the Hexagonal Close Packing crystal structure) to
brittle behavior increases as well as its own dislocation population is inhib-
ited in motion. This can happen, for example:
78

with decreasing temperature; as temperature decreases, the atomic

vibration reduces and thus atomic planes tend to compact; this fact
results unfavorable for dislocation slip;
increasing strain rate, namely under strain-hardening mechanisms
for dislocation locking;
under triaxial stress conditions; remember that in the Mohrs dia-
gram a triaxial tensile state of stress is represented by a point, not
circles; in this special case, shear stresses are zero; no shear stress
causes no dislocation slip can occur (refer to scheme in Fig.1.24);
In the following we go in depth in two modes as they appear to microscop-
ic observations.

Ductile Fracture
Ductile fracture normally occurs in a transgranular manner (through the
grains) in metals that have good ductility and toughness. Often, a consider-
able amount of deformationincluding neckingis observed in the failed
component.
The deformation occurs before the final fracture. Ductile fractures are usu-
ally caused by simple overloads, or by applying too high a stress to the ma-
terial. In a simple tensile test, ductile fracture begins with the nucleation,
growth, and coalescence of microvoids near the center of the test bar (Fig-
ure 1.67). Microvoids form when a high stress causes separation of the
metal at grain boundaries or interfaces between the metal and small impu-
rity particles (inclusions). As the local stress increases, the microvoids
grow and coalesce into larger cavities. Eventually, the metal-to-metal con-
tact area is too small to support the load and fracture occurs.
 79

Fig. 1.67 - When a ductile material is pulled in a tensile test, necking begins and
voids formstarting near the center of the barby nucleation at grain boundaries
or inclusions. As deformation continues, a 45 shear lip may form, producing a fi-
nal cup and cone fracture.

Deformation by slip also contributes to the ductile fracture of a metal. We

know that slip occurs when the resolved shear stress reaches the critical re-
solved shear stress and that the resolved shear stresses are highest at a 45
angle to the applied tensile stress (ref. to Schmids Law). These two as-
pects of ductile fracture give the failed surface characteristic features.
In thick metal sections, we expect to find evidence of necking, with a sig-
nificant portion of the fracture surface having a flat face where microvoids
first nucleated and coalesced, and a small shear lip, where the fracture sur-
face is at a 45 angle to the applied stress. The shear lip, indicating that slip
occurred, gives the fracture a cup and cone appearance (Figure 1.68).
80

Fig. 1.68 Dimples form during ductile fracture. Equiaxed dimples form in the
center, where microvoids grow. Elongated dimples, pointing toward the origin of
failure, form on the shear slip.

Simple macroscopic observation of this fracture may be sufficient to iden-

tify the ductile fracture mode. Examination of the fracture surface at a high
magnificationperhaps using a scanning electron microscopereveals a
dimpled surface (Figure 1.69). The dimples are traces of the microvoids
produced during fracture. Normally, these microvoids are round, or equi-
axed, when a normal tensile stress produces the failure (see Figure 1.69a);
however, on the shear lip, the dimples are oval-shaped, or elongated, with
the ovals pointing toward the origin of the fracture (see Figure 1.69b).
 81

Fig. 1.69 Scanning electron micrographs of an annealed 1018 steel exhibiting

ductile fracture in a tensile test. (a) Equiaxed dimples at the flat center of the cup
and cone, and (b) elongated dimples at the shear lip.

Brittle Fracture
Brittle fracture occurs in high-strength metals and alloys or metals and al-
loys with poor ductility and toughness. Furthermore, even metals that are
normally ductile may fail in a brittle manner at low temperatures, in thick
sections, at high strain rates (such as impact), or when flaws play an im-
portant role. Brittle fractures are frequently observed when impact, rather
than overload, causes failure. In brittle fracture, little or no plastic defor-
mation is required. Initiation of the crack normally occurs at small flaws,
which cause a concentration of stress. The crack may move at a rate ap-
proaching the velocity of sound in the metal. Normally, the crack propa-
gates most easily along specific crystallographic planes by cleavage.
Cleavage fractures are characterized by a planar crack that changes planes
by the formation of discrete steps. River patterns are formed at grain
boundaries (Fig. 1.70) where the cleavage plane in one grain is not parallel
to the plane in the adjacent grain, the difference being accommodated by a
series of steps. The river patterns eventually diminish as the crack propa-
gates and adopts the cleavage plane of the new grain before being re-
formed at the next grain boundary.
Brittle fracture can be identified by observing the features on the failed
surface.
82

Normally, the fracture surface is flat and perpendicular to the applied

stress in a tensile test. If failure occurs by cleavage, each fractured grain is
flat and differently oriented, giving a crystalline or rock candy appear-
ance to the fracture surface (Fig. 1.71).

Fig. 1.70 Facetted brittle failure with river lines.

 83

Fig. 1.71 Scanning electron micrograph of a brittle fracture surface of a

quenched 1010 steel.

Another common fracture feature is the Chevron pattern (Figure 1.72), that
appears at naked eye. They are produced by separate crack fronts propa-
gating at different levels in the material. A radiating pattern of surface
markings, or ridges, fans away from the origin of the crack (Figure 1.73).
Since the Chevron pattern is visible with the naked eye or a magnifying
glass and helps us identify both the brittle nature of the failure process as
well as the origin of the failure. Actually we can say that the Chevron pat-
tern are the naked eye result of the microscopic cleavage fractures, thus
observed at grain scale.

Fig. 1.72 The Chevron pattern in quenched 4340 steel. The steel failed in a brit-
tle manner by an impact blow.
84

Fig. 1.73 The Chevron pattern forms as the crack propagates from the origin at
different levels. The pattern points back to the origin.

In some cases, however, the crack may take an intergranular (along the
grain boundaries) path, when grain boundaries are abnormally weak
(Fig.1.74).

Transgranular fracture Intergranular fracture

(NORMAL ) (ABNORMAL )

Fig. 1.74 The patter of: transgranular fracture (left side) and intergranular frac-
ture (right side).
 85

Chapter 2 - Damage mechanisms and root cause failure

analysis basics

Introduction

The failure of engineering materials is almost always an undesirable event

for several reasons; these include putting human lives in jeopardy, causing
economic losses, and interfering with the availability of products and ser-
vices. Even though the causes of failure and the behavior of materials may
be known, prevention of failures is difficult to guarantee.
The usual causes are improper materials selection and processing and in-
adequate design of the component or its misuse. Also, damage can occur to
structural parts during service, and regular inspection and repair or re-
placement are critical to safe design. It is the responsibility of the engineer
to anticipate and plan for possible failure and, in the event that failure does
occur, to assess its cause and then take appropriate preventive measures
against future incidents.
Various modes of failure are covered in the next, distinguishing in 6 failure
modes (fast brittle fracture, fatigue, creep, wear, contact fatigue and corro-
sion), thus excluding the overloading failure of component that brings to
plastic ruptures.

Fast fracture in metals

Brittle failures are particularly dangerous as abnormal for mechanical

components and structures made of metal alloys. It has been already ad-
dressed how hazardous are brittle fractures in metal structures, since it oc-
curs suddenly without any warnings. But similar behavior are also possible
in non-brittle materials, when they are subjected to such conditions that
lead to fast fracture failures. As brittle fracture, also fast fracture is sudden
and it does not experience any external plastic deformation that can warn
about imminent material collapse. Let us consider a simply example. All
we may have experienced the aggravation of having to expend considera-
ble effort to tear open a small plastic package that contains nuts, candy, or
some other confection. And we have also noticed that when a small inci-
sion (or cut) has been made into an edge, as appears in photograph (a), a
minimal force is required to tear the package open. This phenomenon is re-
lated to one of the basic tenets of fracture mechanics we will deal with in
86

the next: an applied tensile stress is amplified at the tip of a small incision
or notch. Instead this little home-made experience, take a look in the pho-
tograph in Fig. 2.1a that shows an oil tanker that fractured in a brittle man-
ner as a result of the propagation of a crack completely around its girth.

(a)

(b)
Fig.2.1 Brittle fracture of: a) an US oil tanker ship during WWII; b) the ship-
wreck of M V Kurdistan oil tanker ship in 1979.
 87

This crack started as some type of small notch or sharp flaw. The cata-
strophic nature of brittle fracture was dramatically exemplified with fre-
quent brittle failures of Liberty ships during World War II that broke in
half while just sitting at dock. To produce ships quickly for the war effort,
all-welded construction was used for the hulls instead of the traditional
riveted design. Of the 2700 Liberty ships built, approximately 400 sus-
tained fractures, 90 of which were considered serious. In 20 of these, the
hull fractured in half. When the hatch covers were retrofitted with rounded
reinforcements and riveted structures replaced some of the welded struc-
tures, the incidence of fracture was greatly reduced. Even if a crack initiat-
ed at a defective weld, it would be arrested at a rivet hole before it reached
catastrophic dimensions. After the war, G.R. Irwin and his staff at the Na-
val Research Laboratory laid the foundation for what is known today as
fracture mechanics.
Liberty ships are just one example of catastrophic brittle fracture. It has al-
so been a recurring problem in aircraft, bridges, train wheels, and other
heavy equipment. Although brittle fracture does not occur today with the
frequency it once did, it can still be a problem if proper design and manu-
facturing practices are not used. Two important failings of the require-
ments for ships as First Year Ice Class vessels brought to shipwreck of the
M V Kurdistan oil tanker ship in 1979 South of the Cabot Strait, off Nova
Scotia (Fig.2.1b).
Presence of defect in bilge keel welds combined with high thermal stresses
was the cause of brittle fracture. Studying relationships between material
properties, stress level, the presence of crack-producing flaws, and crack
propagation mechanisms had led in past Century to development of the
discipline named as fracture mechanics. By advancements in fracture me-
chanics, design engineers are now better equipped to anticipate, and thus
prevent, structural failures. Here in the following some of the fundamental
principles of the mechanics of fracture are addressed.
88

Box Griffith experience and the theoretical critical stress for brittle
materials

In a first attempt to calculate the strength of such a crystalline material,

one atomic plane perpendicular to the tensile load is considered. The bond-
ing force f between
two atoms in two neighboring planes depends on their distance r, as it is
shown in Fig.2.2 (refer to the upper curve that decreases progressively and
asymptotically to zero value for large r distance).

Fig. 2.2 - Atomic bond strength between atom in a lattice.

By first approximation, Griffith modelled the f=f(r) force with a sine func-
tion, by using the equilibrium distance a0, the half wavelength and the
maximum force fmax (refer to the embedded curve in the same Fig.2.2. that
ends with zero value at r = 1/2 distance).

2
(eq.2.1) () = sin ; = 0

With this approximation it is easy to calculate that interaction force is zero

and the bond is broken, when:
1
(eq.2.2) = 0 +
2

Thus consider the Fig.2.3: it shows scheme of rupture of some atoms

bonds in an area of S (namely, the formation of a S length crack) of the
two lattice planes that are loaded in tension by applied force f.
 89

Fig. 2.3 Schematic representation of braking of atoms bonds in the lattice

and the formation of a S length crack as the a0+/2 distance is reached (re-
fer to eq.2.2 and scheme in Fig.2.2).

Since the stress is defined as the ratio of the total force f applied to an
area S, it can be directly derived by the eq.2.1. by:

2
(2.3) () = sin ; = 0

Griffith focused on the calculation of the (theoretical) max stress, also

named critical stress c, for achieving debonding in brittle materials.
He assumed that:

a) a brittle material exhibits until fracture a linear elastic relation-

ship; thus, during crack formation it is valid also the Hook Law,
= E , or = E(x/r0), if referred to diagram in Fig.2.2.;
b) in the diagram f(x) in Fig.2.2, the variation of distance x to
achieve to rupture (i.e. maximum max value) are so small that the
2
relationship () = sin can be approximated by the

2
() = , thus exploiting the relationship for small an-

gles: sin ;

By the two a) and b) assumption, Griffith wrote the relationship between

the stress s and deformation e (i.e. x/r0) for small distance variation in brit-
tle materials as:
2
(2.4) =
0

Or, rewriting it:

2
(2.5) =
0
90

Furthermore, by the eq.2.3 he therefore calculated the total (elastic) energy

per surface unit (Nm-1) necessary to brake link between two atoms; it is
approximated by the area under the curve representing the force f(x) be-
tween atoms (refer again to eq.2.1):

2
(2.6) = 0 2
sin = [1 ]

Actually to form a crack inside material, two surfaces are created: a factor
of 2 is therefore necessary to exploit the result of eq.2.6 to account the to-
tal energy per surface unit required for creating two opposite faces for-
mation by atoms debonding:

(2.7) U = 2 = [1 ] , or = [1 ]
2

Finally Griffith wrote the 2.7 eliminating the parameter /2 considering

the eq.2.5:

(2.8) = =
0

That represents the Griffith theoretical critical stress value for the fracture
of brittle material (i.e. atoms debonding).
What it was observed experimentally, however, was a great discrepancy
between the theoretical value above calculated and the experimental meas-
ured values. For example, The surface energy does not differ much for
various brittle solid materials and approximately equals 1 Jm2 (diamond
is an exception with = 5 Jm2.) The equilibrium distance a0 between at-
oms, is also almost the same for solids (about 1010 m). The table below
lists values of theoretical strength th and experimental fracture stress b
for some materials. It is clear that there is a large discrepancy between the
two values : the theoretical strength is much too high.
 91

The reason for this deviation has been discovered by Griffith in 1921. In
1921 Griffith determined experimentally the fracture stress b of glass fi-
bers as a function of their diameter. For d > 20 m the bulk strength of 170
MPa was found. However, b approached the theoretical strength of 14,000
MPa in the limit of zero thickness (namely zero defect, considering such a
low thickness material do ot contain defects). Griffith was aware in 1913
of work of Inglis 5 who calculated stress concentrations at circular holes in
plates, being much higher than the nominal stress. He concluded that in his
glass fibers such stress concentrations probably occurred around defects
and caused the discrepancy between theoretical and experimental fracture
stress. He reasoned that for glass fibers with smaller diameters, there was
less volume and less chance for a defect to exist in the specimen. In the
limit of zero volume there would be no defect and the theoretical strength
would be found experimentally. However, the Inglis solution poses a
mathematical difficulty: in the limit of a perfectly sharp crack, the stresses
approach infinity at the crack tip. This is obviously nonphysical (actually
the material generally undergoes some local yielding to blunt the cracktip),
and using such a result would predict that materials would have near zero
strength: even for very small applied loads, the stresses near crack tips
would become infinite, and the bonds there would rupture. Rather than fo-
cusing on the crack-tip stresses directly, Griffith employed an energy-
balance approach that has become one of the most famous developments
in materials science. Griffith published his work in 1921 and his paper can
be seen as the birth of Fracture Mechanics. The ingenious insight that
strength was highly influenced by defects has lead to the shift of attention
to the behavior of cracks and the formulation of crack growth criteria.

5 Ref. Inglis, C.E. Stresses in a plate due to the presence of cracks and sharp
corners. Transactions of the Institute of Naval Architects, Vol 55, 1913, pp 219-
241
92

The contributing factor: the stress concentration

The measured fracture strengths for most brittle materials are significantly
lower than those predicted by theoretical calculations based on atomic
bonding energies (refer to box Griffith experience and the theoretical crit-
ical stress for brittle materials ) .
While the theoretical cohesive strength of a brittle elastic solid can be es-
timated to be in the range of E/10, where E is the modulus of elasticity, the
true fracture strengths of real materials are much lower, normally 10 to as
much as 1000 times below their theoretical values. This discrepancy is ex-
plained by the presence of microscopic flaws or cracks that always exist
under normal conditions at the surface and within the interior of a body of
material. These flaws are a detriment to the fracture strength because an
applied stress may be amplified or concentrated at the tip, the magnitude of
this amplification depending on crack orientation and geometry. This phe-
nomenon is demonstrated in Figure 9.8a stress profile across a cross sec-
tion containing an internal crack. As indicated by this profile, the magni-
tude of this localized stress decreases with distance away from the crack
tip. At positions far removed, the stress is just the nominal stress 0, or the
applied load divided by the specimen cross-sectional area (perpendicular to
this load). Because of their ability to amplify an applied stress in their lo-
cale, these flaws are sometimes called stress raisers (see also Fig.1.62).

Fig.2.2 - (a) The geometry of surface and internal cracks. (b) Schematic stress pro-
file along the line XX in (a), demonstrating stress amplification at crack tip posi-
tions.
 93

To model and simplify discussion, it is assumed that a crack is similar to

an hole through a plate and is oriented perpendicular to the applied stress,
the maximum stress, m, occurs at the crack tip and may be approximated
by:

1/2
(eq.2.9) = 0 1 + 2

where 0 is the magnitude of the nominal applied tensile stress, t is the

radius t=b2/a is the radius tangential at the tip (Figure 2.1a), and a repre-
sents the length of a surface crack, or half of the length of an internal
crack. Note that for a round hole (a=b), the quantity [1+2a/b] reduces to 3,
which is the same stress-concentration factor that was introduced in
Fig.1.62.
For a relatively long microcrack that has a small tip radius of curvature,
the factor (a/t)1/2 may be very large, and it brings to a simplification:

1/2
(eq.2.10) 2 0

This will yield a value of m that is many times the value of 0. If we want
to represent how much higher is the actual m than nominal stress 0, we
can calculate the ratio between the former and latter values accordingly
with:

1/2
(eq.2.11) = 0
= 2

The quantity Kt is denoted by engineers as the stress concentration factor

Kt. because it represent the increased magnitude of actual stress at crack
tip over the nominal stress far . However, the above solution poses a math-
ematical difficulty to define the analytical solution for defining material
behavior in presence of small and sharp cracks, thus the conditions real-
ized by Griffith experience. In the limit of a perfectly sharp crack, the
stresses as defined by eq.2.9 alternatively by eq.2.10 for approach infinity
at the crack tip. This is obviously nonphysical.
Rather than focusing on the crack-tip stresses directly, Griffith employed
an energy-balance approach that has become one of the most famous de-
velopments in materials science.
94

The energy criterion for fast fracture

If you blow up a balloon, energy is stored in it. There is the energy of the
compressed gas in the balloon, and there is the elastic energy stored in the
rubber membrane itself. As you increase the pressure, the total amount of
elastic energy in the system increases. If we then introduce a flaw into the
system, by poking a pin into the inflated balloon, the balloon will explode,
and all this energy will be released. The membrane fails by fast fracture,
even though well below its yield strength. But if we introduce a flaw of the
same dimensions into a system with less energy in it, as when we poke our
pin into a partially inflated balloon, the flaw is stable and fast fracture does
not occur. Finally, if we blow up the punctured balloon progressively, we
eventually reach a pressure at which it suddenly bursts. In other words, we
have arrived at a critical balloon pressure at which our pin-sized flaw is
just unstable, and fast fracture just occurs. Why is this?
To make the flaw grow, say by 1 mm, we have to tear the rubber to create
1 mm of new crack surface, and this consumes energy. We can increase
the energy in the system by blowing the balloon up a bit more. The crack
or flaw will remain stable until a critical pressure for fast fracture of a
pressure vessel containing a crack or flaw of a given size.
But how do we calculate this critical stress?
We can write down an energy balance which must be met if the crack is
to advance, and fast fracture is to occur. Suppose a crack of length a in a
material of thickness t advances by da, then we require that: work done by
loads is higher than change of elastic energy plus the energy absorbed at
the crack tip, i.e.:

(eq.2.12) +

Where:
= elastic energy
= the energy absorbed per unit area of crack
= the is the crack area formed.

Now, consider a cracked plate of material loaded so that the displacements

at the boundary of the plate are fixed. This is a common mode of loading a
material - it occurs frequently in welds between large pieces of steel, for
example - and is one which allows us to calculate quite easily.
 95

Fig.2.3 - Fast fracture in a fixed plate.

Since the ends of plate cannot move, the forces acting on them can do no
work, and W = 0.
Accordingly, our energy formula in eq.2.12 gives, for the onset of fast
fracture (i.e. sudden crack grow in plate):

(eq.2.13) =

Now, as the crack grows into the plate, it allows the material of the plate
near the crack to relax and loses elastic energy. We can estimate in
the way shown in Fig. 2.4.

Fig.2.4 - The release of stored strain energy as a crack grows. The shaded area is
the relaxed area once crack advances from a to a+a.

Each unit cube is has strain energy:

96

(eq.2.13) Uel = = 2/2E.

If we now introduce a crack of length a, we can consider that the material

in the dotted region relaxes (to zero stress) so as to lose all its strain ener-
gy. The energy change for each surface (two are the surfaces formed) is:

2 2
(eq.2.14) =
= 2
2

The critical condition of eq.2.13 therefore becomes:

(eq.2.15) = 2 2
= 2 2

And it represents the onset of fast fracture.

Since two surfaces are formed, the onset value must be corrected by exact-
ly a factor of 2. Thus, correctly, we have:

(eq.2.16) = 2

The eq.2.16 is also well known in the form:

(eq.2.17) =

The left-hand side of our equation says that fast fracture will occur when,
in a material subjected to a stress , a crack reaches some critical size a,
or, alternatively, when material containing cracks of size a is subjected to
some critical stress .
The right-hand side of our result depends on material properties only; E is
obviously a material constant, and Gc the energy required to generate unit
area of crack, again must depend only on the basic properties of our mate-
rial. Thus, the important point about the equation is that: the critical com-
bination of stress and crack length at which fast fracture commences is a
material constant.
The term is usually abbreviated to a single symbol, K, having units
MPa m; it is called, the stress intensity factor. Fast fracture therefore oc-
curs when:

(eq.2.18) =
 97

Where = is the critical stress intensity factor, more usually

called the fracture toughness 6.

Micromechanisms of fast fracture

As stated above, if a material contains a crack, and is sufficiently stressed,
the crack becomes unstable and grows - at up to the speed of sound in the
material - to cause catastrophically rapid fracture, or fast fracture at a stress
less than the yield stress. We are also aware now to quantify this phenom-
enon and obtained a relationship for the onset of fast fracture by the
eq.2.17 or equivalent 2.18.
Some materials, like glass, have low G, and K, and can crack easily with
very short cracks at low stress. Ductile metals have high G, and K, and are
very resistant to fast-fracture, so that very long cracks are required to fast
fracture.
How can we explain these peculiarities?

Mechanisms of crack propagation by ductile tearing

Whenever a crack is present in a material, we already known the stress
close to the crack is greater than the average stress applied to the piece of
material, as it is shown by the eq.2.9 (here below reported for the sake of
readability):

(eq.2.9bis) = 0 1 + 2

The eq.2.9bis states that the stress at crack tip increase theoretically at in-
finite value as the crack tip radius t (see scheme in Fig.2.2) approximates
zero value, as actually happens in case of sharp crack.
Furthermore if we are interested to the mathematical relation of the local
stress versus the distance r ahead of a sharp crack in an elastic material
(see the scheme of Fig.2.5), we find that the closer one approaches to the
tip of the crack, the higher the local stress becomes accordingly with the
eq.2.19:

6 Strictly speaking, this result is valid only for a crack through the center of a wide plate of
material. In practice, the problems we encounter seldom satisfy this geometry, and a numer-
ical correction to required to get the strain energy calculation right. In general we
write: = where Y is the numerical correction factor (Values of Y can be found
from tables in standard reference books).
98

(eq.2.19) = 1 +
2

Notice that the mathematical expression here above representing the local
stress versus distance from crack tip is similar to the mathematical expres-
sion of the stress at crack tip as function of the crack tip radius and crack
length a (i.e. eq.2.9bis); on the other and they shall not be confused, be-
cause the former may have non-infinite solutions as the crack tip radius
approaches to a non zero value 7, while the latter we read in eq.2.19 has
always infinite values as we want to calculate the stress at crack tip. This
fact means that the expression cannot represent what in reality happens in
regions close to crack tip, namely r equal to zero. This discrepancy with
reality is well solved whether we superimpose to stress curve in eq.2.19
the plastic behavior of ductile material. This implies that, as we consider a
ductile material, until at some distance from the crack tip we call ry the
theoretical stress calculated by the eq.2.19 cannot exceed the yield stress
y of the material: in fact in this area plastic flow occurs and stress here are
fully relaxed, as it is shown in Fig.2.5a.

(a) (b)

Fig.2.5 - Crack propagation by ductile tearing: a) forming of plastic zone; b) ad-

vancement of crack for ductile tearing occurring in plastic zone.

Notice we already verified that for crack tip radius equal to a in the scheme of
7

Fig.2.2, the value is 3, namely the value typical for a circular hole in a large plate.
 99

This distance ry can be easily calculated by setting local = y in eq. 2.19,

thus we obtain the following result:

(eq.2.20) = 1 +
2

Assuming ry to be small compared to the crack length, a, the result can be

simplified by:

2
(eq.2.21) =
2 2

and by the following eq.2.22 where the fracture toughness K = a has

been included:

2
(eq.2.22) = 2 2

The crack propagates by fast fracture mode when K is equal to Kc; the
width of the plastic zone, ry, is then given by eq.2.22 with K replaced by
Kc.
And now, note that the zone of plasticity shrinks rapidly as y increases:
cracks in soft metals have a large plastic zone; cracks in hard ceramics
have a small zone, or none at all. Coming back to ductile metals, most
metals contain tiny inclusions (or particles). Within the plastic zone, plas-
tic flow takes place around these inclusions, leading to elongated cavities
(fracture by microdimple, see the scheme in Fig. 2.5b). As plastic flow
progresses, these cavities link up, and the crack advances by means of this
ductile tearing. The plastic flow at the crack tip naturally modifies original
sharp crack (see Fig.2.5a) into a blunt crack (Fig.2.5b): the local stress at
crack tip therefore decrease to values that are just sufficient to keep on
plastically deforming the work-hardened material there, as the scheme in
Fig.2.5b shows.
Moreover, the important thing about crack growth by ductile tearing is that
it consumes a lot of energy by plastic flow: the bigger the plastic zone, the
more energy is absorbed. High energy absorption means that G, is high,
and so is K,. This is why ductile metals are so tough.
100

Mechanisms of crack propagation, 2: cleavage

If you now examine the fracture surface of something like a ceramic, or a
glass, you see a very different aspect. Instead of a very rough surface, you
see a rather flat surface as produced by the cleaveage fracture mode (refer
to Chapter 1) that indicates very little or usually no plastic deformation oc-
curred. How do cracks in brittle materials spread?
In case of brittle materials, the calculated local stress ahead of the crack tip
as it is given by the eq.2.19 can clearly approach very high values close to
the crack tip: this fact provides that blunting of a sharp crack tip does not
occur. Due to very high yield strengths y, very little plastic deformation
takes place at crack tips in these materials, as it is easily demonstrated by
applying the eq.2.21, here shown again for convenience:

2
(eq.2.21) =
2 2

The local stress at the crack tip is still in excess of the ideal strength and is
thus large enough to literally break apart the interatomic bonds there; the
crack then spreads between a pair of atomic planes giving rise to an atomi-
cally flat surface by cleavage, as shown by the scheme in Fig.2.6. The en-
ergy required simply to break the interatomic bonds at crack sharp tip is
much less than that absorbed by ductile tearing in a tough material, and
this is why materials like ceramics and glasses are so brittle. It is also why
some steels become brittle and fail like glass, at low temperatures. At low
temperatures in fact metals having b.c.c. and h.c.p. structures become brit-
tle and fail by cleavage, even though they may be tough at or above room
temperature. Only those metals with an f.c.c. structure (like copper, lead,
aluminium, austenitic stainless steel) remain unaffected by temperature in
this way. In metals not having an f.c.c. structure, the motion of dislocations
is assisted by the thermal agitation of the atoms. At lower temperatures
this thermal agitation is less, and the dislocations cannot move as easily as
they can at room temperature in response to a stress. The result is that the
yield strength rises, and the plastic zone at the crack tip shrinks until it be-
comes so small that the fracture mechanism changes from ductile tearing
to cleavage. This effect is called the ductile-to-brittle transition DBTT; for
steels it can be as high as 0C, depending mainly on the carbon content of
the steel); steel structures like ships, bridges and oil rigs are much more
likely to fail in winter than in summer.
 101

Ductile to Brittle Transition Temperature (DBTT)

The ductile to brittle transition temperature is the temperature at which the
failure mode of a material changes from ductile to brittle fracture. This
temperature may be defined by the average energy between the ductile and
brittle regions, at some specific absorbed energy, or by some characteristic
fracture appearance. A material subjected to an impact blow during service
should have a transition temperature below the temperature of the materi-
als surroundings.

(a)

(b)

Fig.2.6 a) Temperature dependence of the Charpy V-notch impact energy (curve

A) and percent shear fracture (curve B) for an A283 steel; b) Photograph of frac-
ture surfaces of Charpy V-notch specimens tested at indicated temperatures (in
C).

Not all materials have a distinct transition temperature (Figure 2.7). BCC
metals have transition temperatures that increases for steesl as the carbon
content increases (see Fig.2.8) , but most FCC metals do not. FCC metals
have high absorbed energies, with the energy decreasing gradually and,
102

sometimes, even increasing as the temperature decreases. The effect of this

transition in steel may have contributed to the failure of the Titanic as a re-
cent discoveries in metallurgical analysis conducted onto steel constituting
the rivets of the sunk ship (Fig.2.9).

Fig.2.7 Schematic curves for the three general types of impact energy
versustemperature behavior.

Fig.2.8 Influence of carbon content on the Charpy V-notch energyversus

Temperature behavior for steel.
 103

(a) (b)

Fig. 2.9 - a) The Titanic in the shipyard during her construction. Note the hull
plates, fastened on all sides to the ship's main structure by thousands of rivets; b)
a layout of the watertight compartments and the damage from the collision. The
thick black lines below the waterline indicate the approximate locations of the
damage to the hull.
104

Fatigue failure

Fatigue is a form of failure that occurs in structures subjected to dynamic

and fluctuating stresses (e.g., bridges, aircraft, and machine components).
Under these circumstances it is possible for failure to occur at a stress level
considerably lower than the tensile or yield strength for a static load. The
term fatigue is used because this type of failure normally occurs after a
lengthy period of repeated stress or strain cycling. Fatigue is important in-
asmuch as it is the single largest cause of failure in metals, estimated to
comprise approximately 90% of all metallic failures. Furthermore, fatigue
is catastrophic and insidious, occurring very suddenly and without warn-
ing. Fatigue failure is brittlelike at naked eye observation even in normally
ductile metals, in that there is very little, if any, gross plastic deformation
associated with failure.
The first known catastrophic fatigue failure, involving major loss of life,
was the Versailles (France) railway accident in 1842 (Fig.2.10).
The train was 17 carriages hauled by two steam engines. The front axle of
the leading, four wheeled engine failed due to metal fatigue and the body
of the leading engine fell to the ground.
Fatigue testing of specially designed laboratory specimens started in the
1850s. It is generally accepted that the first fatigue tests on laboratory
specimens were carried out by Wohler. In 1870 Wohler published a final
report. This is cited in Schultz (1996) and contains the conclusions known
as Whlers 8 laws:
Materials can be induced to fail by many repetitions of stress, all
of which are lower than the static strength;
The stress amplitudes are decisive for the destruction of the cohe-
sion of the material;
The maximum stress is of influence only in so far as the higher it
is, the lower are the stress amplitudes which lead to failure.

8 August Whler, chief superintendent of rolling stock on the Lower Silesia-

Brandenberg Railroad, is known for his investigation on the causes of fracture in
railroad axles that led to definition of bending rotating fatigue tests, the work that
is basis of experimental tests today conducted onto materials for the definition of
the S-N curve, also known as Wohler Diagram, in the next described.
 105

(a)

(b)

Fig.2.10 a) Paint showing Versailles (France) railway accident in 1842; b) de-

scription of rupture occurred on train axle.

Investigation on phenomena (early 1900s) led to understand fatigue fail-

ures may because of the application of fluctuating stresses that are much
lower than the stress required to cause failure during a single application of
stress. A test apparatus was therefore designed to to duplicate as nearly as
possible the service stress conditions, like stress level, time frequency,
106

stress pattern, etc (Fig.2.11a). A schematic diagram of a rotating-bending

test apparatus today frequently used is shown in Figure 2.11b (the com-
pression and tensile stresses are imposed on the specimen as it is simulta-
neously bent and rotated).

(a)

(b)

Fig.2.11 a) Scheme of possible cyclic load for test specimens; from left to right
and up to down: axial test, rotating bending with varying bending stress; rotating
bending with constant bending stress; b) schematic diagram of fatigue-testing ap-
paratus for making rotating-bending tests.

A series of tests are commenced by subjecting a specimen to the stress cy-

cling at a relatively large maximum stress amplitude (max) below the
 107

tensile strength and yield strength (see exemplifying scheme in Fig.2.12).

The number of cycles to failure is therefore counted and this this procedure
is repeated on other specimens at progressively decreasing maximum
stress amplitudes. Data are plotted as stress S versus the logarithm of the
number N of cycles to failure for each of the specimens. The values of S
are normally taken as stress amplitudes a (refer to scheme Fig.2.12); on
occasion, max or min values may be used (refer to scheme Fig.2.12).
Two distinct types of SN behavior are observed, which are represented
schematically in Fig. 2.13. As these plots indicate, the higher the magni-
tude of the stress, the smaller the number of cycles the material is capable
of sustaining before failure. For some ferrous (iron base) and titanium al-
loys, the SN curve (Fig.2.13a) becomes horizontal at higher N values; or
there is a limiting stress level, called the fatigue limit (also sometimes the
endurance limit), below which fatigue failure will not occur. This fatigue
limit represents the largest value of fluctuating stress that will not cause
failure for essentially an infinite number of cycles.
108

Fig.2.12 Variation of stress with time that accounts for fatigue failures. (a) Re-
versed stress cycle, in which the stress alternates from a maximum tensile stress
() to a maximum compressive stress (min) of equal magnitude. (b) Repeat-
ed stress cycle, in which maximum and minimum stresses are asymmetrical rela-
tive to the zerostress level; mean stress m, range of stress r, and stress ampli-
tude a are indicated. (c) Random stress cycle.
 109

Fig.2.13 Stress amplitude (S) versus logarithm of the number of cycles to fa-
tigue failure (N) for (a) a material that displays a fatigue limit and (b) a material
that does not display a fatigue limit.

For many steels, fatigue limits range between 35% and 60% of the tensile
strength. Most nonferrous alloys (e.g., aluminum, copper, magnesium) do
not have a fatigue limit, in that the SN curve continues its downward
trend at increasingly greater N values (Fig.2.13b).Thus, fatigue will ulti-
mately occur regardless of the magnitude of the stress. For these materials,
110

the fatigue response is specified as fatigue strength, which is defined as the

stress level at which failure will occur for some specified number of cycles
(e.g., 107 cycles). The determination of fatigue strength is also demonstrat-
ed in Fig.2.13b. Another important parameter that characterizes a materi-
als fatigue behavior is fatigue life Nf. It is the number of cycles to cause
failure at a specified stress level, as taken from the SN plot (Figure
2.13b).
Unfortunately, there always exists considerable scatter in fatigue data
that is, a variation in the measured N value for a number of specimens test-
ed at the same stress level. This variation may lead to significant design
uncertainties when fatigue life and/or fatigue limit (or strength) are being
considered. The scatter in results is a consequence of the fatigue sensitivity
to a number of test and material parameters that are impossible to control
precisely. These parameters include specimen fabrication and surface
preparation, metallurgical variables, specimen alignment in the apparatus,
mean stress, and test frequency. Fatigue SN curves similar to those shown
in Figure 2.14 represent best fit curves that have been drawn through av-
erage-value data points. It is a little unsettling to realize that approximately
one-half of the specimens tested actually failed at stress levels lying nearly
25% below the curve (as determined on the basis of statistical treatments).

Fig.2.14 Fatigue SN probability of failure curves for a 7075-T6 aluminum

alloy; P denotes the probability of failure.
 111

The three stages of fatigue failure

Fatigue failures typically occur in three stages, as illustrated by the simpli-
fied scheme in Fig.2.15:
- STAGE I - Fatigue Crack Nucleation;
- STAGE II - Fatigue Crack Growth;
- STAGE III - Fast Fracture r catastrophic rupture.

Fig.2.15 - Schematic representation of a fatigue fracture surface in a steel shaft,

showing the initiation region, the propagation of the fatigue crack (with beach
markings), and catastrophic rupture when the crack length exceeds a critical value
at the applied stress.

Stage I Fatigue crack nucleation

First, a tiny crack initiates or nucleates often at a time well after loading
begins. Normally, nucleation sites are located at or near the surface, where
the stress is at a maximum, and include surface defects such as scratches or
pits, sharp corners (see example in Fig.2.16) due to poor design or manu-
facture, inclusions, grain boundaries, or dislocation concentrations that
lead to high local stresses ahead the defects (refer to mechanism described
in the previous section Mechanisms of crack propagation by ductile tear-
ing). In the absence of a surface defect, crack initiation will eventually
occur due to the formation of persistent slip bands (PSBs), as illustrated by
the scheme in Fig.2.17b.
112

Fig.2.16 - Fatigue crack nucleation at notched region in the sharp corners of com-
ponent.

(a)

(b)

Fig.2.17 a) Schematic view of early stage of crack initiation; b) development of

initiation site onto defect-free surface by extrusions and intrusions phenomena.
 113

STAGE II - Fatigue Crack Growth.

Next, the crack gradually propagates as the load continues to cycle. Final-
ly, a sudden fracture of the material occurs when the remaining cross-
section of the material is too small to support the applied load. The fracture
surfaceparticularly near the originis typically smooth. The surface be-
comes rougher as the original crack increases in size and may be fibrous
during final crack propagation. Microscopic and macroscopic examina-
tions reveal a fracture surface including a beach mark pattern and stria-
tions, respectively observable by naked-eye macroscopic inspection (see
Fig.2.18a and Fig.2.18; also represented in the scheme in Fig.2.19) and by
microscopic fractographic analysis conducted at Scanning Electron Micro-
scope (see Fig.2.18b).

Fig.2.18 - Fatigue fracture surface: (a) at low magnifications, the beach mark pat-
tern indicates fatigue as the fracture mechanism. The arrows show the direction of
growth of the crack front with the origin at the bottom of the photograph; b) at
high magnification by Scanning Electron Microscope.

Fig.2.19- Fatigue crack growth in the origin of crack initiation in a high-strength

steel: notice beach marks observable at the naked eye.
114

Specifically, beach or clamshell marks as shown are normally formed

when the load is changed during service or when the loading is intermit-
tent, perhaps permitting time for oxidation inside the crack.

Striations, which are on a much finer scale, show the position of the crack
tip after each cycle as represented by the scheme of crack propagation in-
side ductile metal in Fig.2.20. This is in accordance with the microme-
chanics involving the crack opening and its propagation, as it has been de-
scribed in the section Mechanisms of crack propagation by ductile
tearing. Each marks always suggest a fatigue failure, but
unfortunatelythe absence of beach marks does not rule out fatigue fail-
ure.

(a)

(b)

Fig.2.20 a) Schematic view of crack propagation stage; b) development of stria-

tions due to mechanisms of ductile tearing driven by plastic radius formation at
crack tip.
 115

Cracks grow from an initial size, a0, to a critical size, ac, corresponding to
failure as a function of the number of load cycles (Fig. 2.21). The crack
growth rate, da/dn, can be determined from the slope of the curve. Initial-
ly, the crack growth rate is slow but increases with increasing crack length.
Of course, the crack growth rate is also higher for higher applied stresses.

Fig.2.21 Crack length as a function of cycles.

In the fracture mechanics approach we have already learnt a crack can

grow because of the role played by the stress-intensity parameter, K (refer
to previous section Mechanisms of crack propagation by ductile tear-
ing) is determined by:

(eq.2.22) =

Stated the above expression, we also know that specimens containing a

sharp crack like that shown in Fig. 2.22 and subjected to cyclic loading at
constant nominal stress , cycle by cycle increase the K value at crack tip,
meanwhile the condition for plastic tearing are maintained (see Fig.2.23).
116

Fig.2.22 Fatigue-crack growth in pre-cracked components.

Fig.2.23 Fatigue cracks grow mechanisms in tough materials.

 117

More specifically, we observe that during a cycle the K value will cyclical-
ly vary, due to variation ranging from max to min (refer to Fig.2.22).
Thus, over one cycle, the expression for intensity factor can be represented
by:

(eq.2.22) = =

The cyclic stress intensity K increases with time (at constant load) be-
cause the crack grows in tension. It is found that the crack growth per cy-
cle, da/dN, increases with K in the way shown in Fig. 2.24.

Fig.2.24 Fatigue crack-growth rates for pre-cracked material.

Particularly, in the regime for the crack growth, the crack grows at a con-
stant rate, da/dn, accordingly with the mathematical expression:

(eq.2.23)

=
118

where C and m are material constants. The relationship in eq.2.23 is

known as Paris Law or Paris equation and it is experimentally plotted for
pre-cracked test specimen of various metals as illustrated in Fig.2.24.
Obviously, if a0 (the initial crack length) is given, and the final crack
length af at which the crack becomes unstable and runs rapidly is known or
can be calculated, then the safe number of cycles can be estimated by inte-
grating the equation:

(eq.2.24)

Substituting the K with expression in eq.2.22, it is possible to write:

(eq.2.25)

That is valid for alternate stress (for average stress m different from zero
value, the Paris Law and the eq.2.25 should be corrected by further fac-
tors).

STAGE III - Fast Fracture

A subcritical crack of a length a higher than non-propagating threshold (re-
fer to Fig.2.24) will eventually grow to a length at which the metal imme-
diately fails, that is (refer to previous section on fast fracture):

(eq.2.18bis) =

Or:

(eq.2.22bis) =

That is, solving for ac:

2
(eq.2.26) = 2 2


 119

Note that even if a component contains a detectable crack, it can remain in

service, provided that it is periodically inspected. This philosophy forms
the basis for what is known as the damage-tolerance design approach.
Finally, in region III, the crack growth rate accelerates, since the fracture
toughness of the material is approached, and there is a local tensile over-
load failure.

Contact fatigue9
Damaging phenomena developing in several mechanical component, such
as cams, gears, and bearings, are related to surface contact. Substantial dif-
ferences exist in various failure modes, the appearance of worn surface is
different, and the type of contact interaction changes (as for pure rolling,
rolling with sliding, linear sliding). In general, wear modes are basically
classied into four categories, such as: fatigue wear, adhesive wear, abra-
sion wear, and corrosion wear. Most commonly, fatigue wear is such fail-
ure mode that occurs, for example, in a lubricated contact realized between
two parts engaged in gearing. Since in many lubricated contacts surface
adhesion is prevented and adhesive wear ideally avoided, a certain amount
of wear is caused by surface asperities interaction, as discussed in the fol-
lowing. In literature, contact fatigue failure (also called surface fatigue) is
considered a subcategory of fatigue wear, and it includes all those fatigue
surface damaging caused by a repeated rolling contact. In contact fatigue,
cracks are promoted by reversal stress eld generated below the contact
area formed when two elastic bodies are pressed together and they roll.
Depending on various operative conditions, either pure rolling or slid-
ing rolling can be realized. In any case, contact fatigue damage consists
in craters forming (namely, pits) on surface. In literature, it is common to
distinguish in shallow (less than 10 m) or deeper craters (from 10
,m to 200 m); in the rst case, this type of surface damage is called
pitting, in the second case spalling. According to these denitions, it must
be highlighted that pitting and spalling should be distinguished only in
terms of the average dimensions of the craters, that is, they should be dis-
tinguished on the basis of the surface damage appearance. Since it is not
easy to clearly distinguish whether surface ruptures result from either in-
creasing damage level (of a single rupture mode) or pitting changing into
spalling, these two terms are frequently used indiscriminately. With re-

9 Main reference: G.Stachowiak and A.W. Batchelor, Engineering Tribology,

Third Edition, Elsevier, 2005
120

gards to possible evolving of a failure mode, small surface cavities often

may enlarge because cracks branch and they evolve more deeply beneath
the surface. The result is the formation of larger craters, i.e., a spall results
from small pit degeneration. In this case, to distinguish whether spalling
was induced by pitting degeneration, this failure mode is better called pro-
gressive pitting (also called destructive pitting).
On the other hand, many authors prefer to classify spalling and pitting ac-
cording to Tallian, distinguishing them with regards to either the surface or
the subsurface origin of rupture. According to this denition, spalling is
better identied as damage caused by fatigue crack started in subsurface
layers and then propagated. While the propagated cracks re-emerge, mate-
rial portions detach inducing the spall formation; in a similar way, pitting
is associated to most supercial damaging, which originates at the top sur-
face.

Figure 2.25 Voids created on top surface on gear tooth by cyclic loading (spall-
ing rupture mechanisms).

Figure 2.26 Subsurface crack propagation mechanism below hardened layer of a

tooth gear: once subsurface crack emerges, entire pieces of top layer surface are
broken away.
 121

Theories on failure mechanisms involved in fatigue contact: the Hertzian

theory of contact between elastic bodies
Uncertain identication of pitting or spalling is prevalently due to such in-
sufcient assumptions to clarify damage mechanisms by the Hertzian
scheme of contact on a macroscale.
When two solid surfaces are loaded together there will always be some
distortion of each of them.
Deformations may be purely elastic or may involve some additional plas-
tic, and so permanent, changes in shape. Such deflections and modifica-
tions in the surface profiles of the components can be viewed at two differ-
ent scales, either at macroscopic and microscopic scales.

Hertzian stress status in no sliding static contact

Consider two bodies in contact under a static load and with no movement
relative to each other. Since there is no movement between the bodies,
shearing does not occur at the interface and therefore the shear stress act-
ing is equal to zero. According to the principles of solid mechanics, the
planes on which the shear stress is zero are called the principal planes.
Thus the interface between two bodies in a static contact is a principal
plane on which a principal stress 1 is the only stress acting. It is also
known from solid mechanics that the maximum shear stress occurs at 45
to the principal plane, as shown in Fig. 2.27.

Figure 2.27 Stress status in a static contact; 1, 3 are the principal stresses, p is
the hydrostatic pressure, k is the shear yield stress of the material.
122

If the contact load is sufficiently high then the maximum shear stress will
exceed the resolved shear stress in polycrystalline material, i.e. max > 1/3
y 10, and plastic deformation takes place. Material will then deform (slip)
along the line of action of maximum shear stress. The maximum shear
stress max, also referred to in the literature as 45 since it acts on
planes inclined at 45 to the interface (in static contacts), is given by:

1 3
(eq.2.27) = 45 = 2

The stresses x, z and vary with depth below the interface. An ex-
ample of the stress field beneath the surface of two parallel cylinders in
static contact is shown in Fig. 2.28.

Figure 2.28 Subsurface stress field for two cylinders in static contact; pmax is the
maximum contact pressure, b is the half width of the contact rectangle.

10 Refer to Chapter 1, section Slip in polycrystalline crystal; in polycrystalline crystal

e bcc and fcc materials, the Taylor factor (namely the factor that correlates yield strength to
resolved shear strength) is about 3.06. Converting shear strength to an equivalent uniaxial
yield strength, the Taylor factor of 3.06 is the most appropriate parameter. Note that values
of 1.73 and 2.0 are frequently used, but they are result of a misunderstanding about the
proper application of the von Mises and Tresca yield criteria.
 123

Hertzian stress status in sliding contact

The most critical influence on subsurface stress fields, however, is exerted
by sliding. To illustrate the effect of sliding on the stress distribution, con-
sider two bodies in contact with some sliding occurring between them.
Frictional forces are the inevitable result of sliding and cause a shear stress
to act along the interface, as shown in Figure 2.29. The frictional stress
acting at the interface is balanced by rotating the planes of principal stress-
es through an angle from their original positions when frictional forces
are absent (the magnitude of the angle depends on the frictional stress q
acting at the interface). The variation with depth below the interface of the
principal shear stress max for a cylinder and the plane on which it slides
is shown in Figure 2.30. The contours show the principal shear stress due
to the combined normal pressure and tangential stress for a coefficient of
friction = 0.2. It can clearly be seen that as friction force increases, the
maximum shear stress moves towards the interface. Thus there is a gradual
increase in shear stress acting at the interface as the friction force increas-
es. This phenomenon is very important in crack formation and the subse-
quent surface failure and will be discussed later.

Figure 2.29 - Stresses in a contact with sliding; 1, 3 are the principal stresses, p
is the hydrostatic pressure, k is the shear yield stress of the material, is the coef-
ficient of friction, q is the stress normal to the interface or compressive stress due
to load, is the angle by which the planes of principal stress are rotated from the
corresponding zero friction positions to balance the frictional stress.
124

Figure 2.30- Subsurface stress field for a cylinder sliding on a plane; pmax is the
maximum contact pressure, b is the half width of the contact rectangle.

Box Contact Between Two Parallel Cylinders

The configuration of two elastic bodies with convex surfaces in contact was
originally considered by Hertz in 1881 and is shown in Figure 2.31 and it is
based on the following assumptions:
i. The surfaces are continuous, smooth, nonconforming and frictionless;
ii. The size of the contact area is small compared to the size of the bod-
ies, i.e., the strains associated with the deformations are small;
iii. Each solid can be considered to behave as an elastic half-space in the
vicinity of the contact zone;
iv. The gap h between the undeformed surfaces can be approximated by
an expression of the form: h = Ax2+By2;

Figure 2.31 - Geometry of two Hertzian elastic bodies with convex surfaces in
 125

contact.
The reduced radius of curvature for this case is defined by Hertzian theory as:

The contact area between two parallel cylinders is circumscribed by a narrow

rectangle. The geometry of parallel cylinders in contact is shown in Figure
2.32 and the formulae for the main contact parameters are summarized in Ta-
ble 2.1.

Figure 2.32 - Geometry of the contact between two parallel cylinders.

Table 2.1 - Formulae for contact parameters between two parallel cylinders.

Where:
b is the half width of the contact rectangle [m];
l is the half length of the contact rectangle [m];
E' is the reduced Young's modulus is defined as:

R' is the reduced radius of curvature for the two parallel cylinders in
126

contact [m]. For the cylinders: Rax = RA, Ray = , Rbx = RB, Rby =
where RA and RB are the radii of the cylinders A and B re-
spectively:

where:

The rest of the parameters are as defined for Table 2.1.

EXAMPLE
Find the contact parameters for two parallel steel rollers. The normal force is
W = 5 [N], radii of the rollers are RA = 10 10-3 [m] and RB = 15 10-3 [m],
Young's modulus for both rollers is E = 2.1 1011 [Pa] and the Poisson's ratio
is = 0.3. The length of both rollers is 2l = 10 10-3 [m].

Reduced Radius of Curvature

Since the radii of the cylinders are Rax = RA = 10 10-3 [m], Ray= and
Rbx = RB = 15 10-3 [m], Rby= respectively, the reduced radii of curva-
ture in the x and y directions are:

Since 1/Rx > 1/Ry condition is satisfied, the reduced radius of curvature is:

Reduced Young's Modulus:

Contact Area Dimensions:

Maximum and Average Contact Pressures:

 127

Maximum Deflection:

Maximum Shear Stress:

Depth at which Maximum Shear Stress Occurs:

Hertzian stress status in sliding and lubricated contacts by elasto-

hydrodynamic film

In a lubricated rolling contact, the contact stresses are affected by the lu-
bricating film separating the opposing surfaces and the level of rolling and
sliding. The hydrodynamic film (for more details, see the box Basic
principles of hydrodynamic lubrication in the next) generated under these
conditions and the relative movement of the surfaces cause significant
changes to the original static stress distribution as shown in the scheme of
Fig.2.33.

Figure 2.33 - Hydrodynamic pressure distribution in an elasto-hydrodynamic con-

tact; hc is the central film thickness, h0 is the minimum film thickness.
128

A subsequent modification of the Hertzian stress field in EHL lubricated

conditions, is below described.

Traction and elasto-hydrodynamic lubrication (EHL) condition

Traction is the application of frictional forces to allow the transmission of
mechanical energy rather than its dissipation. The most common example
of the distinction between traction and friction is the contact between a
wheel and a road. When the wheel rolls without skidding, traction is ob-
tained and the frictional forces available enable propulsion of a vehicle.
When skidding occurs, the same frictional forces will now dissipate any
mechanical energy applied to the wheel. Thus the difference between trac-
tion and friction is in the way that the mechanical energy is processed, e.g.
in the case of traction this energy is transmitted between the contacting
bodies (i.e. one body is driving another) whereas with friction it is dissi-
pated. Traction can also be applied to lubricated contacts in spite of the
relatively low coefficients of friction involved. EHL contacts can provide
sufficiently high traction to be used as interfaces for variable speed trans-
missions. When traction is applied, there is a small but non-zero
sliding speed between the contacting surfaces. This non-zero sliding speed
is inevitable since all the tractional force in an EHL contact is the result of
viscous shear. The envisaged simplified film geometry and velocity pro-
files of the sheared lubricant are shown in Fig. 2.34.

Figure 2.34 - Simplified film geometry and generation of traction in an EHL con-
tact.
 129

The traction force has the same effect of increasing the shear stress on top
surface, as shown in the previous scheme of Fig.2.30 (refer to previous
section Hertzian stress status in sliding contact).
Particularly, it is important to note that this condition can occurs not only
at macroscopic scale, namely considering opposite lubricated surfaces as
homogeneous, but the EHL scheme is applicable to microscopic scale.
Consider the effective roughness of a lubricated surface that is put, for ex-
ample, into rolling contact (as it happens actually for lubricated gears). The
effect of surface roughness on partial EHL is illustrated in Fig.2.35. It has
been found that the sharp peaks, i.e. asperities with high slope or low ra-
dius sustained a higher proportion of the contact load than flat peaks, i.e.
asperities with a low slope or large radius. Improved surface finish enables
a diminished fraction of contact load supported by the asperities and the
likelihood of a perfect elasto-hydrodynamic film is enhanced 11.

Figure 2.35 - Effect of roughness and asperity shape on survival of EHL films.

At high levels of surface roughness (see Fg.2.35, left side), the EHL film sustains
a reduction in minimum film thickness and rapid wear of the contact occurs that
produces a corrective wearing of surface in early lifespan of contact system bod-
ies. When asperities are sufficiently smooth, or smoothed after corrective surface
wearing, they are prevented from contacting each other, due to the mechanism of
micro-elastohydrodynamic lubrication or micro-EHL, as schematically
shown in Fig.2.36.

11
When surfaces are polished to an extreme smoothness, however, a contrary trend to
lowered load capacity is probable. It has often been observed in engineering practice that if
the surface is too smooth, e.g. with a surface roughness of 0.001 [m] Ra, then there is a
risk of sudden seizure. In this instance it is commonly believed that small asperities play a
useful role as a reservoir for the lubricant by entrapment between asperities. Under ex-
tremes of contact pressures the trapped lubricant can be expelled by asperity deformation to
provide a final reserve of lubricating oil.
130

Figure 2.36 - Mechanism of micro-elasto-hydrodynamic lubrication.

Box Basic principles of hydrodynamic lubrication

The principle of hydrodynamic pressure generation between moving non-

parallel surfaces is schematically illustrated in Figure 2.33. It can be assumed
that the bottom surface, sometimes called the runner, is covered with lubri-
cant and moves with a certain velocity. The top surface is inclined at a certain
angle to the bottom surface. As the bottom surface moves it drags the lubricant
along it into the converging wedge. A pressure field is generated as otherwise
there would be more lubricant entering the wedge than leaving it. Thus at the
beginning of the wedge the increasing pressure restricts the entry flow and at
the exit there is a decrease in pressure boosting the exit flow. The pressure
gradient therefore causes the fluid velocity profile to bend inwards at the en-
trance to the wedge and bend outwards at the exit, as shown in Figure 2.33.
The generated pressure separates the two surfaces and is also able to support a
certain load, as for example occurs in the Pivoted Pad Bearing (Fig.2.34).

Figure 2.33 - Principle of hydrodynamic pressure generation between non-

parallel surfaces.
 131

Figure 2.34 - Schematic diagrams of the pivoted bearings: a) a offset line piv-
ot, b) a button point pivot.

Subsurface crack initiated fatigue contact failure

Due to the cyclic nature of the 45 shear stress, despite it is below the yield
stress, it is capable to initiate a subsurface crack, accordingly with most of
mechanisms discussed as valid for fatigue failure (refer to previous sec-
tion Fatigue failure).
Similarly to the S-N approach, it is possible to generalize the fatigue con-
tact failure by the scheme in Fig.2.35:
As the maximum shear stress exceeds the shear fatigue limit for ma-
terial, the condition for crack initiation occurs;
the crack initiates and, due to increasing of stress intensity factor,
grows submerged;
crack remerges toward surface, pieces of materials detached, thus
micro-voids is created;
on top surface micro-voids act as stress intensity factor for enhance
failure mechanism.
132

W
Pmax
Pmax

2a

Time
tau max

Depth below surface

(a)

f (A)
f (B)
micropitting
(pitting/spalling)

(b)

Figure 2.35 (a) Subsurface shear stress produced during cycling of external load
contact; (b) condition that leads to crack initiation (lifetime depends on loading
condition, surface roughness, lubrication conditions, etc.) within the surface, pro-
ducing subsurface propagation toward surface and void creation (pitting or spall-
ing mechanisms).
 133

It is important to note that when materials contain inclusions (Fig.2.36a)

and other imperfections which act as nuclei for void formation under plas-
tic deformation (Fig.2.36b). These voids form a plentiful supply of initia-
tors for crack growth.. The development of voids by plastic deformation is
a result of dislocation pile up at hard inclusions. These voids enlarge with
further deformation since they act as traps for dislocations. All these fac-
tors favour the growth of a crack parallel to but beneath the surface. As
stated, at some unspecified point the crack finally turns upwards to the sur-
face and a long thin laminar particle is released.

(a)

(b)
Figure 2.36 (a) Material imperfection as the cause for contact fatigue; (b) illus-
tration of a process of subsurface crack formation by growth and link up of voids.

Surface crack initiated fatigue contact failure

When some sliding is present, maximum shear stress could localize most
probably at the surface; in this condition the crack is expected to initiate
from surface, instead of subsurface regions. In severe sliding conditions
(as it is in not lubricated contacts or in the presence of lubrication errors),
134

with friction coefcient approximates unity, the material within the 0.1
mm of the surface is stretched along the sliding direction. In these regions,
microstructure becomes hardly oriented, and this severe plastic defor-
mation makes the dislocation density increase. Subsequent work hardening
occurs in these high stretched layers, as they are schematically illustrated
in Fig.2.37.

Figure 2.37 Strain levels in a deformed surface.

The high strain induced by traction in EHL contact (or sliding in dry con-
tact) eventually breaks down the original grain structure at the surface to
form dislocation cells, as it occurs in severe work hardening processes.
The example of such a work-hardened like deformed material is shown in
the micrograph of Fig.2.38.

Figure 2.38 Accumulation of material on the surface due to the passage of a

blunt wedge and the resulting plastic deformation.
 135

The mechanism of surface crack initiated fatigue wear is illustrated sche-

matically in Fig. 2.39. A primary crack originates at the surface at some
weak point and propagates downward along weak planes such as slip
planes or dislocation cell boundaries. A secondary crack can develop from
the primary crack or alternatively the primary crack can connect with an
existing subsurface crack. When the developing crack reaches the surface
again a wear particle is released.

Figure 2.39 Schematic illustration of the process of surface crack initiation and
propagation.

It is not infrequent that during unlubricated sliding, in particular reciprocal

sliding, wear particles can form due to the growth of surface initiated
cracks; planes of weakness in the material become orientated parallel to
the surface by the already discussed deformation processes, and laminar
wear particles are formed by a surface crack reaching a plane of weakness
as illustrated in Fig.2.40.
136

Figure 2.40 Schematic illustration of mechanism of wear particles formation due

to growth of surface initiated cracks and an example of fatigue wear particle for-
mation on cast iron.

To complete the preliminary analysis of cyclically loaded bodies in lubri-

cated contact, typical of gears, the model in the Fig.2.35 is capable to ex-
plain also the singular cases of case-crushing failure shown in Fig.2.26. As
shown in Fig.2.41, the case-crushing condition occurs when the shear
stress Herztian profile exceed somewhere at interface case-core interface
the fatigue limit shear stress f of the material.
 137

f (C) f (A)

Case-crushing

Figure 2.41 Condition that leads to crack initiation in depth, at the interface be-
tween the hardened layer, also named case, and the base material, also named
core.
138

Friction and wear damage

When two materials are placed in contact, any attempt to cause one of the
materials to slide over the other is resisted by a friction force (Fig. 25.1).
The force that will just cause sliding to start, Fs , is related to the force P
acting normal to the contact surface by:

(eq.2.28) F = sP

where s is the coefficient of static friction. Once sliding starts, the limit-
ing frictional force decreases slightly and we can write:

(eq.2.29) F = kP

where k (< s), is the coefficient of kinetic friction (Fig. 25.1). The work
done in sliding against kinetic friction appears as heat.

(static s ) (dynamic k )

Figure 2.42 Static and kinetic coefficients of friction.

How is it that the friction between two surfaces can depend only on the
force P pressing them together and not on their area? In order to under-
stand this behavior, we must first look at the geometry of a typical sur-
face.

Actual surface contact between solids

Surface roughness limits the contact between solid bodies to a very small
portion of the apparent contact area. The true contact over most of the ap-
parent contact area is only found at extremely high contact stresses; con-
tact between solid bodies at normal operating loads is limited to small are-
as of true contact between the high spots of either surface. The random
nature of roughness prevents any interlocking or meshing of surfaces. True
 139

contact area is therefore distributed between a number of microcontact ar-

eas. If the load is raised, the number of contact areas rather than the aver-
age individual size of contact area is increased, i.e. an increase in load is
balanced by newly formed small contact areas. A representation of contact
between solids is shown schematically in Figure 10.12.

ai

Fig. 2.43 - Real contact area of rough surfaces in contact; ar = ai is the true area
of contact.

Even if the surface is polished for a long time using the finest type of
metal polish, micro-asperities still survive.
The load pressing the surfaces together is supported solely by the contact-
ing asperities. The real area of contact, a, is very small and because of this
the stress P/ a (load/ area) on each asperity is very large. Initially, at very
low loads, the asperities deform elastically where they touch. However, for
realistic loads, the high stress causes extensive plastic deformation at the
tips of asperities. If each asperity yields, forming a junction with its part-
ner, the total load transmitted across the surface (Fig. 25.3) is:

(eq.2.30) P ay

where y is the compressive yield stress. The real area of contact is there-
fore given by:

(eq.2.31) a P/y
140

Obviously, if we double P we double the real area of contact, a.

Fig. 2.44 - The real contact area between surfaces is less than it appears to be, be-
cause the surfaces touch only where asperities meet.

Let us now look at how this contact geometry influences friction. If you at-
tempt to slide one of the surfaces over the other, a shear stress Fs / a ap-
pears at the asperities. The intense plastic deformation in the regions of
contact presses the asperity tips together so well that there is atom-to-atom
contact across the junction. The junction, therefore, can withstand a shear
stress as large as k approximately, where k is the shear-yield strength of
the material. The asperities will give way, allowing sliding, when Fs/a k.
The distinction between a static and a sliding contact is thought by modern
theory as due to differences in structure and physical processes that occurs.
It was found that while a static contact can be described in terms of a ran-
dom distribution of point contacts as above described, this model is not
applicable to a sliding contact. A basic feature of sliding contact is that it is
distributed over a lesser number of larger contact areas rather than a large
number of contact points. These areas do not have a fixed location inside
the contact but instead move slowly across the surface as sliding progress-
es. The frictional interaction appears to be controlled by mechanical inter-
locking between lumps on opposing surfaces as schematically illustrated
in Figure 2.45.
 141

Fig. 2.45 - A comparison between static and dynamic contact.

Data for coefficients of friction

If metal surfaces are thoroughly cleaned in vacuum it is almost impossible
to slide them aver each other. Any shearing force causes further plasticity
at the junctions, which quickly grow, leading to complete seizure ( > 5).
This is a problem in outer space, and in atmospheres (e.g. H2 ) which re-
move any surface films from the metal. A little oxygen or H2O greatly re-
duces by creating an oxide film which prevents these large metallic junc-
tions forming. Experimentally, it is found that for some metals the junction
between the oxide films formed at asperity tips is weaker in shear than the
metal on which it grew (Fig. 2.46). In this case, sliding of the surfaces will
take place in the thin oxide layer, at a stress less than in the metal itself,
and lead to a corresponding reduction in to a value between 0.5 and 1.5.
142

Fig. 2.47 - Oxide-coated junctions con often slide more easily than ones
which are clean.

Referring to data in Fig. 2.47, it can be generally observed that:

1. When soft metals slide over each other (e.g. lead on lead), the
junctions are weak but their area is large so is large;
2. When ceramics slide on ceramics friction is lower: ceramics are
very hard, stable in air and water so they have less tendency to
bond and shear more easily.
3. Metals slide on bulk polymers, friction is still caused by adhesive
junctions, transferring a film of polymer to the metal: any plastic
flow tends to orient the polymer chains parallel to the sliding sur-
face, and in this orientation they shear easily, so is low - 0.05 to
0.5.
 143

Fig. 2.47 - Bar chart showing the coefficient of static friction for various
material considerations.

Lubrication
Friction absorbs a lot of work in machinery and as well as wasting power,
this work is mainly converted to heat at the sliding surfaces, which can
damage and even melt the bearing. In order to minimize frictional forces
we need to make it as easy as possible for surfaces to slide over one anoth-
er. The obvious way to try to do this is to contaminate the asperity tips
with something that: (a) can stand the pressure at the bearing surface and
so prevent atom-to-atom contact between asperities; (b) can itself shear
easily.
Polymers and soft metal, as we have said, can do this; but we would like a
much larger reduction in than these can give, and then we must use lub-
ricants. The standard lubricants are oils, greases and fatty materials such as
soap and animal fats. These 'contaminate' the surfaces, preventing adhe-
sion, and the thin layer of oil or grease shears easily, obviously lowering
the coefficient of friction. What is not so obvious is why the very fluid oil
is not squeezed out from between the asperities by the enormous pressures
generated there. One end of each molecule reacts with the metal oxide sur-
face and sticks to it, while the other attracts one another to form an orient-
ed 'forest' of molecules (Fig. 2.48). These forests can resist very large forc-
144

es normal to the surface (and hence separate the asperity tips very effec-
tively) while the two layers of molecules can shear aver each other quite
easily. This type of lubrication is termed partial or boundary lubrication,
and is capable of reducing by a factor of 10 (Fig. 2.47). As described in
the previous section Contac fatigue, hydrodynamic lubrication is even
more effective, since it aims to separate surfaces.

Fig. 2.48 - Boundary lubrication.

Wear of materials
Even when solid surfaces are protected by oxide films and boundary lubri-
cants, some solid-to-solid contact occurs at regions where the oxide
film breaks down under mechanical loading, and adsorption of active
boundary lubricants is poor. This intimate contact will generally lead to
wear. Wear is normally divided into two main types: adhesive wear and
abrasive wear.

Adhesive wear
Figure 2.49 shows that, if the adhesion between A atoms and B atoms is
good enough, wear fragments will be removed from the softer material A.
If materials A and B are the same, wear takes place from both surfaces -
the wear bits fall off and are lost or get trapped between the surfaces and
cause further trouble (see below). The size of the bits depends on how far
away from the junction the shearing takes place: if work hardening extends
well into the asperity, the tendency will be to produce large pieces.
 145

In order to minimize the rate of wear we obviously need to minimize the

size of each piece removed. The obvious way to do this is to minimize the
area of contact a.
Since a = P/y, reducing the loading on the surfaces will reduce the wear,
as would seem intuitively obvious. The second way to reduce a is to in-
crease y, i.e. the hardness.

Fig. 2.49 - Adhesive wear.

Abrasive wear
Wear fragments produced by adhesive wear often become detached from
their asperities during further sliding of the surfaces. Because oxygen is
desirable in lubricants (to help maintain the oxide-film barrier between the
sliding metals) these detached wear fragments can become oxidized to
give hard oxide particles which abrade the surfaces in the way that sand-
paper might. Figure 2.50 shows how a hard material can 'plough' wear
fragments from a softer material, producing severe abrasive wear. Abra-
sive wear is not, of course, confined to indigenous wear fragments, but can
be caused by dirt particles (e.g. sand) making their way into the system, or
- in an engine - by combustion products: that is why it is important to filter
the oil.
The wear rate W related to the wear path s is proportional to the normal
load FN and the hardness of the worn surface HW and a factror k, accord-
ingly with experimental Archard equation:

(2.31)
146

The rate of abrasive wear can be reduced by reducing the load - just as in a
hardness test. The particle will dig less deeply into the metal, and plough a
smaller. Increasing the hardness of the metal will have the same effect.

Fig. 2.50. Abrasive wear.

 147

Corrosion 12

Corrosion is a form of degradation caused by chemical and electrochemi-

cal reactions that take place at the interface between the surface of a mate-
rial and the environment with which it is in contact: the result is a gradual
decay of integrity of the metal surface occurring when the main constitu-
ents of the alloy (Fe, C, Cr, Ni, etc.) combine with the aggressive agents
present in the environment, thus forming corrosion products.
The corrosion of metals can cause several problems. In the case of piping
and tanks, the degradation can give rise to punctures that lead to leakage of
the fluids contained within; in structural elements corrosion can cause the
reduction of the resistant part with the consequent loss of the components
load capacity. Other problems are also linked to the formation of corrosion
products, which can lead to the alteration of the aesthetic features of the
surfaces or the contamination of the processed substances (for example, in
the case of foods, possible alteration to their organoleptic characteristics).
The corrosion of metals can be divided into two basic forms:
electrochemical corrosion also called wet corrosion in which
the metal alloy undergoes an oxidation reaction in the presence of
an electrolyte (usually water); the oxidation reaction is coupled with
a reduction reaction of the substances present in the environment
(usually oxygen): the combination of the two reactions, anodic (ox-
idation) and cathodic (reduction), involve both chemical species
(ions and molecules) and electrons;
chemical corrosion (also called high temperature oxidation or dry
corrosion) in which the metal alloy undergoes an oxidation reaction
upon contact with a gaseous atmosphere (usually air); the phenome-
non usually occurs at temperatures well above ambient temperature
(>300C) and the corrosion products are oxides and salts with low
melting points.
Wet corrosion and electrochemical corrosion

Main references:
12

M. Boniardi, A. Casaroli, Stainless Steels, Lucefin Group, 2014 (free Eng-

lish version avaliable at:
http://www.lucefin.com/wp-content/files_mf/stainlesssteels_low.pdf );
M.F.Ashby and M.F.Jones, Engineering Materials 1, Engineering Materi-
als 1, Second Edition. Butterworth Heineman, Oxford, 1996.
148

Wet corrosion of metals can be described using the electrochemical model:

the mechanism that governs the phenomenon depends on the presence of a
process as the result of the metal transforming in its ionic state.
It is caused by a flow of electricity from one metal to another metal (Gal-
vanic corrosion) or from one part of a metal surface to another part of the
same surface (cathode-anode areas).
For current to flow, a complete electrical circuit is required. In a corroding
system, this circuit is made up of four components:
The anode is the electrode where electrons flow away;
The electrolyte is an electrical conducting solution that contains
ions; water, especially saltwater, is an excellent electrolyte; in pure
water, there are positively charged H+ and negatively charged OH-
in equal amounts;
The cathode is the electrode at which electrons flow toward;
The metallic path, thus an external circuit to complete the con-
nection between anode and cathode.
To understand the problem further, refer to the diagram shown in figure
2.51, in which an iron plate is placed in contact with a copper plate and the
drop of water is the electrolyte.

Figure 2.51 Electrochemical diagram of the corrosive phenomenon of an iron

plate in contact with a copper plate.

As the copper is a nobler metal than iron (copper has a greater electro-
chemical potential than iron), a potential difference is established be-
tween copper and iron, i.e. an electromotive force that allows the circula-
tion of current (see Box for more details). The analogy using the galvanic
cell is clear: the iron behaves as an anode and the copper as a cathode and
 149

the potential difference between the two metals allows the circulation of
current. The oxidation reaction occurs to the anode (iron) and the reduction
reaction of oxygen occurs to the cathode (copper) at the same time.

Box Voltage differences (electrochemical potential difference) as a driv-

ing force for wet oxidation

Wet oxidation in metals involves electron flow, as metals are electron conduc-
tors. Thus, it is easier to measure the tendency of a metal to oxidise in a solu-
tion by using a voltage scale, namely a measure of such a flow rate of elec-
trons. Figure 2.52 shows the voltage differences that would just stop various
metals oxidising in aerated water.

Figure 2.52 - Wet corrosion voltages (at 300 K).

What do these voltages mean? Suppose we could separate the cathodic and the
150

anodic regions of a piece of iron, as shown in Fig. 2.53. Then at the cathode,
oxygen is reduced to OH-, absorbing electrons, and the metal therefore be-
comes positively charged. The reaction continues until the potential rises to
+0.401 V. Then the coulombic attraction between the +ve charged metal and
the -ve charged OH- ion becomes so large that the OH- is pulled back to the
surface, and reconverted to H2O and O2; in other words, the reaction stops. At
the anode, Fe++ forms, leaving electrons behind in the metal which acquires a
negative charge. When its potential falls to -0.440V, that reaction, too, stops
(for the same reason as before). If the anode and cathode are now connected,
electrons flow from the one to the other, the potentials fall, and both reactions
start up again. The difference in voltage of 0.841V is the driving potential for
the oxidation reaction. The bigger it is, the bigger the tendency to oxidise.

Figure 2.53 - The voltages that drive wet corrosion.

Obviously, it is not very easy to measure voltage variations inside a piece of

iron, but we can artificially transport the 'oxygen-reduction reaction' away
from the metal by using a piece of metal that does not normally undergo wet
oxidation (e.g. platinum) and which serves merely as a cathode for the oxy-
gen-reduction reaction. The corrosion voltages also tell us what will happen
when two dissimilar metals are joined together and immersed in water. If cop-
per is joined to zinc, for instance, the zinc has a larger corrosion voltage than
the copper. The zinc therefore becomes the anode, and is attacked; the copper
becomes the cathode, where the oxygen reaction takes place, and it is unat-
tacked. Such couples of dissimilar metals can be dangerous: the attack at the
anode is sometimes very rapid.
 151

The two reactions are:

(eq.2.32) Fe Fe+2 + 2e- (anodic reaction of oxidation)

(eq.2.33) O2 + H2O + 2e- 2OH- (cathodic reaction of reduction)

overall obtaining:

(eq.2.34) O2 + H2O + Fe Fe (OH)2

In summary: the iron gradually transforms into solution under the form of
Fe+2 ions, corroding due to the effect of the presence of the copper cathode
where the reduction of oxygen occurs. In the example shown previously,
the anodic and cathodic zones are clearly distinct: the corrosive phenome-
non occurs due to a galvanic coupling that creates a potential difference
E because of the different nature of the two metals involved.
However, it should not be believed that corrosion only occurs in these
conditions: the case of degradation phenomena on metal alloys not in con-
tact with dissimilar metals is much more common.
To understand the problem better the experience of Evans should be con-
sidered, as shown in Fig. 2.54: his experiment is especially significant as it
explains the phenomenon of corrosion of homogenous metal materials.

Figure 2.54 Experience of Evans; phenomenon of electrochemical corrosion

in a homogenous metal material [Pedeferri, 2010].

By taking an iron plate on which a deaerated drop of water is placed as the

electrolyte, after a short time corrosion phenomena are only observed near
the central area of the drop: this can be explained by considering the pro-
cess of oxygen diffusion in the water drop, also called differential aeration
corrosion.
152

Initially, the chemical composition of the drop is constant and the oxygen
is totally absent: over time however, due to contact with air, diffusive phe-
nomena will occur near to the external surfaces of the drop (which is the
surface of exchange with the surrounding air) and a variation of the oxy-
gen concentration will take place in the drop. The different concentration
of O2 in the drop will create an anodic zone, i.e. the zone lacking in oxy-
gen in the center of the drop, and a cathodic zone, i.e. the zone rich in ox-
ygen on the outside of the drop. Therefore, a local anode-cathode micro
bond is created which is able to trigger the corrosion process. The E po-
tential existing between the anode and cathode is a kind of electromotive
force that allows the corrosive process to take place: it is called free cor-
rosion potential.
The anodic reaction and the cathodic reaction are all the same as those ob-
served previously for galvanic contact:

(eq.2.35) Fe Fe+2 + 2e- (anodic reaction of oxidation)

(eq.2.36) O2 + H2O + 2e- 2OH- (cathodic reaction of reduction)

overall obtaining:

(eq.2.37) O2 + H2O + Fe Fe(OH)2

with the formation of corrosion products (iron oxides/hydroxides).

If the oxidation reaction of iron occurs in an acid environment (such as
when an iron plate is immersed in chloride acid), the cathodic process will
be the reduction of the hydrogen ion to hydrogen gas (hydrogen evolu-
tion), i.e.:

(eq.2.38) Fe Fe+2 + 2e- (anodic reaction of oxidation)

(eq.2.39) 2H+ + 2e- H2 (cathodic reaction of reduction)

overall obtaining:

(eq.2.40) 2H+ + Fe Fe+2 + H2

For corrosion to occur, the two reactions, anodic and cathodic, must hap-
pen at the same time: during the oxidation reaction of the iron, a certain
number of electrons are generated on the anode which, following the re-
duction reaction, are consumed by the cathode.
 153

The above reactions are very common in all metal materials subject to cor-
rosion: the presence, for any reason, of an anodic-cathodic micro bond
provides the electromotive force required to trigger and supply the degra-
dation process.
However, the phenomenon of differential aeration corrosion is not the on-
ly type to give rise anodic-cathodic micro bonds able to trigger degrada-
tion: often in the corrosive material environment combination there are
already particular local conditions suitable for generating zones with dif-
ferent electrical potential.
The problem arises for various reasons: heterogeneity of chemical compo-
sition of the metal mass, in homogenous phases of the microstructure of
the matrix (inclusions, carbides, etc.), Tensile residual stress of high entity
traction, local defects of the piece (micro cavities, blowholes, accentuated
roughness etc.) All these areas act as the anode of the surrounding metal
mass acting as a cathode, causing local micro bonds with preferential cor-
rosion triggers.
Similar situations also arise due to the variability of the electrochemical
characteristics of the corrosive environment, such as that which occurs, for
example, in solutions with various concentrations of noxious species, in
electrolytes with greater or smaller stagnation zones or with non-uniform
temperatures.

Box Potentiodynamic curves

During a corrosive process there is always a certain number of ions in solution

in the electrolyte and a concomitant movement of electrons in the metal, i.e. a
circulation of electrical current, as what occurs in a cell.
The mechanism described is concatenated: the higher the quantity of iron ions,
which will dissolve in the solution, the greater the number of electrons circulat-
ing per surface unit exposed to the corrosive environment. This causes the in-
crease of the surrounding current density ic and the corrosion rate Vcorr of
this material will increase in that given environment, i.e.:

corrosion rate: (Vcorr) ic = ianodic = icathodic

It should be repeated that the corrosive phenomenon is a degradation process

that occurs when there is an anodic zone and a cathodic zone: among these two
zones a potential difference E is established (called free corrosion potential in
the case of short circuits between anodes and cathodes) which ensures the circu-
lation of a current density i proportional to the corrosion rate of the system.
The correlation between potential E and current density i of the anode-
cathode bond depends on both the electrochemical characteristics of the anodic
154

process (i.e. how quickly the metal dissolves) and the electrochemical charac-
teristics of the cathodic process (i.e. how quickly the oxygen or the hydrogen
evolves). If the two contributions are separated, i.e. if the correlation E i is
studied separately for the anodic reaction and the cathodic reaction, it is possible
to estimate what the trend of the surrounding current density i will be, in order
to change the applied electromotive force E. This is exactly what Evans did
experimentally and which is still possibly to recreate in the laboratory: to trace
the curves that describe the anodic reaction and cathodic reaction with the varia-
tion of the tension conditions E applied, or the reaction existing between the
set tension E and the surrounding current density i both in the anodic area
and in the cathodic area.
The curves obtained experimentally are shown in fig.2.55: they are called poten-
tiodynamic curves, or Evans diagrams, due to the anodic process (anodic char-
acteristics, metal/alloy that is corroded) and the cathodic process (cathodic char-
acteristics, oxygen reduction and hydrogen evolution).
In the very simple case of common carbon steel in an aerated aqueous solution
(the cathodic process is oxygen reduction), the two curves are as shown in
fig.2.55a, whereas for a stainless steel, again in the same solution, the situation
shown in fig.2.55b occurs.

Figure 2.55 - Indicative potentiodynamic curves (anodic characteristic A: mate-

rial cathodic characteristic B: environment) in aqueous solution 0.05 M of
H2SO4: (a) for a material with active conduct and b) for a material with active-
passive conduct.

The intersection point of curves A and B shown in fig.2.55 represents the condi-
tion of equivalence between the surrounding current densities (the rate of the
two reactions, anodic and cathodic, is equal): it establishes the functioning point
of the material-environment system and allows the determination of the free cor-
 155

rosion potential Ec and the surrounding current density ic, as well as esti-
mating the corrosion rate of the material in that particular environment (Vcorr
ic).In the case of carbon steels, for example, the anodic curve (curve A
fig.2.55a) increases monotonically: the current increases with the increasing ten-
sion applied and with it, the corrosion rate increases. With regards to In the case
of carbon steels, the anodic curve (curve A fig.2.55a) increases monotonically:
the current increases with the increasing tension applied and with it, the corro-
sion rate increases. Concerning stainless steels the curve is that represented in
fig.2.55b, and its different behaviors will be explained in Chapter 5 that is de-
voted to stainless steels. For the moment, note the effect of the difference of the
two potentio-dynamic behaviors represented in figure 2.55a and fig.2.55b that
represent respectively a carbon steel and a stainless steel: because the surround-
ing current ic of case a is much greater than the surrounding current ic of
case b, the corrosion rate of a carbon steel, in that determined environment,
will be a lot greater than that of a generic stainless steel.

The corrosion morphology

Corrosive phenomena can also be classified based on the morphology with
which the degradation occurs in the components, or rather in relation to the
aspect of chemical aggression as it appears upon simple visual observation
or using magnification microscopy.
An initial distinction can be made between generalized or uniform corro-
sion and localized corrosion:
in the first case the whole surface of the material is subject to corro-
sive attack (generalized), with penetration of the degradation quite
consistent along the whole section of the component (uniform);
in the second case the aggressive action is only expressed in some
areas of the surfaces (localized), with penetrating attacks, craters or
cracks.

Uniform or generalized corrosion

A whole surface area of the metal material exposed to the aggressive envi-
ronment is affected with very limited local variations of the degree of pen-
etration of the damage along the thickness of the component.
In the cases of generalised corrosion, the corrosion rate Vcorr can be
suitably expressed in terms of mass loss (m) per surface unit (A) over
time (t), or rather:

(eq.2.41) Vcorr = m/At

usually measured in mg per day in dm2 (namely, mdd).

156

In industrial applications it is often more interesting to talk about penetra-

tion or thinning rate Vthin of the corrosive phenomenon. To convert cor-
rosion rate to the thinning rate simply add the material density (), accord-
ing to the formula:

(eq.2.42) Vass = Vcorr/ = m/ A t

The formula is commonly used to predict the so-called additional thick-

ness for corrosion, i.e. a thickness in excess on the component which,
during operation, will be gradually removed due to the corrosive action of
the environment.

Galvanic corrosion
An early form of localized corrosion is galvanic corrosion or corrosion due
to galvanic coupling. It occurs when a metal and a metal alloy is connected
(i.e. is in electrical contact) with another metal/metal alloy with greater or
lower thermodynamic nobility: if there is a significant potential difference,
a redox reaction may develop with consequent corrosion phenomena, even
in the presence of just a mildly aggressive environment. The mechanism is
very similar to that shown in Fig.2.51. Every metal or metal alloy has its
own potential that depends on its nature, its chemical composition and on
the environment in which it is placed (temperature, pH, agitation, presence
of oxidants or other harmful species, etc.).
If the difference between the various potentials exceeds a certain threshold,
a significant passage of electrons is created between the donor (the an-
ode, the less noble metal) and the receiver (the cathode, the nobler met-
al). The intensity of this movement of electrons (actually an electric cur-
rent) will be greater as the potential difference increases: as a consequence,
the corrosion rate will be higher the further distance between the two mate-
rials on the nobility scale. Another relevant aspect that governs the phe-
nomenon of galvanic corrosion is the relationship between the areas of the
two materials in contact: the rate of degradation increases with the increase
of the ratio between the area of the cathodic zone (nobler) to that of the
anodic zone (less noble) exposed to the environment.
In order to assess whether the conditions of galvanic contact between the
two metals/metal alloys can cause problems practically, it is better NOT to
refer to the standard electrical potential scales: this is because there is a
great variability in the behavior of the same material between one corro-
sive environment and another (and at times also within the same environ-
 157

ment) and also because there are never conditions of equilibrium in the ac-
tual environments and electrochemical system. Therefore the saltwater
scale of nobility is used (figure 2.56), which is a scale of the potentials
measured under conditions close to actual operation. A typical example of
galvanic corrosion is when it occurs on carbon steel sheet metal (also gal-
vanized) or on aluminum alloy sheet metal in contact with stainless steel
fasteners, placed in marine environments, in aerate aqueous solutions or in
mildly aggressive environments (see fig.2.57).
The opposite situation would be much more serious, i.e. that of stainless
steel sheets fastened with carbon steel or galvanized steel rivets: in this
second case, in addition to the nobility difference between the two materi-
als, the relationship between the areas would be very negative, in favor of
stainless steel.

Figure 2.56 Saltwater scale of nobility [from ASM-H.13 1992].

158

Figure 2.57 Galvanic corrosion of a carbon steel plate with stainless steel fasten-
ers.

The most correct solution to eliminate the corrosion phenomenon from

galvanic contact is to avoid putting it into electrical contact (or direct
contract with electronic continuity) with metal materials of different no-
bility or, if impossible, providing for electrical insulation of the parts (see
figure 2.58).

Figure 2.58 Electric insulation with a non conductive material between

two plates and the relative connection bolt.

A particular type of galvanic corrosion is corrosion by superficial contam-

ination.
 159

The degradation occurs when the surface of the stainless steel is sullied
by foreign particles, such as dust from ferrous material that is often gener-
ated during grinding operations and from common steel.
The particles deposited on the surface can create conditions for localized
corrosive attacks, even in not very aggressive environments. Marks appear
on the surface (rust-colored in case of ferrous contamination, whitish in the
case of contamination from aluminum or zinc) as a consequence of the
rapid oxidation of the contaminant (steel, aluminum or zinc) and not, as
wrongly believed, of the stainless steel. In the most extreme situation, the
contaminant substance can also cause damage to stainless steel, as it can
hinder the passivation phenomenon, as well as constitute a preferential
trigger zone for other forms of corrosion.
If surface contamination is suspected, the foreign particles must be re-
moved through a chemical passivation operation, using nitric acid based
dilute solutions.

Pitting corrosion
Pitting is the phenomenon of localized corrosion; it produces serious pene-
trating damage and dangerous holes in the components during operation.
Characteristic elements of pitting are the presence on the surface of the
work piece of multiple small pits (hence the name of this corrosion); pit-
ting usually leads to even deeper pits, i.e. grooves, ulcers, craters etc. The
surface size of the holes is small, between 0.1 and 2 mm, as in the pitting
phenomena the extent of the corrosion products is very limited.
The greatest problem related to this form of corrosion is not the loss of
mass affected by the degradation phenomenon, but rather the damage
caused by penetrating through the resistant section of the component. For
example, consider the case of a stainless steel tank affected by the pitting
phenomenon: the pitting could lead to the creation of a hole in the recipi-
ent, the subsequent spilling of the process fluid and the overall disruption
of the system.
Degradation due to pitting has various aspects; fig. 2.59 shows some mor-
phologies typical in sections, as classified by the American standard
ASTM G46.
160

Figure 2.59 Typical morphologies of degradation due to pitting [from ASTM

G46].

Pitting occurs when discrete areas of a material undergo rapid attack while
most of the adjacent surface remains virtually unaffected. Although the to-
tal metal loss may be small, the part may be rendered useless due to perfo-
ration. In addition to the localized loss of thickness, corrosion pits can also
act as stress raisers, leading to fatigue or stress-corrosion cracking typical
of austenitic stainless steels (refer to Chapter 5).
Pitting occurs when the anodic or corroding area is small in relation to the
cathodic or protected area. Pitting can occur in protected metals when
there are small breaks in the continuity of the metal coating. Pitting can al-
so occur on bare, clean metal surfaces as a result of irregularities in their
physical or chemical structure. The rate of penetration into the metal by
pitting can be 10 to 100 times that caused by general (uniform) corrosion.
Pitting can cause structural failure from localized weakening while consid-
erable sound metal still remains. Pitting usually requires a rather long initi-
ation period before attack becomes visible. However, once a pit has start-
ed, the attack continues at an accelerating rate. Pits tend to grow in a
manner that undermines or undercuts the surface. Typically, a very small
hole is seen on the surface. Poking at the hole with a sharp instrument may
reveal a much larger hole under what had looked like solid metal. Pitting
can cause visible pits, or they may be covered with a semipermeable mem-
brane of corrosion products. Pitting corrosion may assume different
shapes.
Pitting normally occurs in a stagnant environment. Concentration cells can
accelerate pitting. Concentration cells are areas on the metal surface where
the oxygen or conductive salt concentrations in water differ. As a pit be-
comes deeper, an oxygen concentration cell is started by depletion of oxy-
gen in the pit. The rate of penetration of such pits is accelerated propor-
 161

tionately as the bottom of the pit becomes more anodic. Pitting attack in-
creases with temperature. Variations in soil conditions can also trigger pit-
ting.

Crevice corrosion
Crevice corrosion is another form of localized aggression: it occurs in the
presence of cracks, crevice, incrustations, deposits and geometrical discon-
tinuities in which the electrolyte (generally water) is in stagnation with re-
gards to the surrounding environment. A typical case of degradation due to
crevice corrosion regards the seals of flanged piping or in the contact
zones between bolted or riveted plates (fig. 2.60). Similar situations can
occur in welded plates for points on cars, in arc welded seals where pene-
tration is incomplete, between the strands of metal cables, underneath lu-
bricating films such as graphite or molybdenum graphite and on surfaces
coated with Teflon or polyethylene.

Figure 2.60 Schematic of a constructive solution which could cause crevice cor-
rosion.

The presence of the geometric discontinuities create a macro bond due to

differential aeration between the interstitial area, i.e. the anodic zone where
the diffusion of oxygen is limited, and the surrounding metal mass which
represents the cathodic zone in which the oxygen saturation is ensured
(figure 2.61). It should be noted that in the interstices, the same critical
factors occur that are in a pit formed by corrosion, i.e. gradual consump-
162

tion of oxygen, accumulation of positive metal ions, chloride ions attracted

and acid hydrolysis with pH decrease.

Figure 2.61 Schematic of crevice corrosion.

A particular form of crevice corrosion is corrosion under a deposit. The

degradation occurs in the presence of lime scale accumulations and/or de-
posits (such as in household pipes penetrated by water rich in limestone):
in the vicinity of the deposit and below it clogged cells are established
with the formation of anodic- cathodic macro bonds and degradation phe-
nomena characterized by mechanisms similar to those of the interstitial
corrosion (see figure 2.62).

Figure 2.62 Schematic of corrosion phenomenon under deposit in a pipe.

Further important corrosion mechanisms are integranular corrosion and

stress corrosion cracking corrosion, both wet corrosion mechanisms, and
the hot temperature corrosion, a form of dry corrosion mechanisms.
 163

Creep 13

At high temperatures, permanent deformation can occur over a period of

time at stresses well below the yield strength. This time-dependent defor-
mation is known as creep and occurs at temperatures greater than approx-
imately 0.3 to 0.5 of the absolute melting point Tm. In creep, thermal acti-
vation enables plastic deformation at stresses below those needed to
deform the lattice without thermal activation. When a metal is placed un-
der a constant load, it stretches elastically but also gradually extends plas-
tically. Thus, a metal subjected to a constant tensile load at elevated tem-
perature will creep and undergo a time-dependent increase in length. Since
the mobility of atoms increases with increasing temperature, diffusion-
controlled mechanisms become active. Dislocation mobility increases, slip
becomes easier, new slip systems become available, and dislocation climb
is aided by both increases in temperature and the presence of a greater
number of vacancies. Creep occurs in any metal or alloy at a temperature
where atoms become sufficiently mobile to allow the time-dependent rear-
rangement of structure. Since the elevated-temperature strength of metals
is closely related to their melting points, it is normal practice to specify the
homologous temperature, which is the ratio of the exposure temperature to
the melting point (T/Tm), on an absolute scale. Creep behavior of a poly-
crystalline metal or alloy often is considered to begin at approximately 1/3
to 1/2 of its melting point (~0.3 to 0.5 Tm).

The Creep Curve

In a creep test, the time-dependent strain is measured under long-term ele-
vated temperature. Engineering creep is measured by applying a constant
load on a tensile specimen at a constant temperature and measuring the
strain, or extension, of the specimen as a function of time. A schematic of
a test setup for a creep test is shown in Fig. 2.63. Creep tests may be run
for as short as several months to as long as 10 years. Creep tests are usual-
ly conducted at constant load rather than constant stress, and, as the speci-
men elongates, the cross-sectional area decreases, so the applied stress in-
creases with time.

13 Main reference: Flake C. Campbell, Elements of Metallurgy and Engineering

Alloys, ASM International, 2008.
164

Figure 2.63 - Typical creep test fixture

Constant load creep curves typically consist of three distinct stages, as

shown in Fig. 2.64.

Primary Creep. During primary creep, the specimen undergoes an initial

elongation, 0, and then the creep rate ( = d/dt ) rapidly decreases with
time. Primary creep, also known as transient creep, represents a stage of
adjustment in the metal during which rapid, thermally activated plastic
strain occurs. The competing processes of strain hardening and recovery
eventually lead to a somewhat stable dislocation configuration. Primary
creep occurs in the first few moments after initial strain and decreases in
rate as crystallographic imperfections within the metal undergo realign-
ment. This realignment leads to secondary creep.

Secondary Creep. Being nominally constant at a minimum rate, generally

known as the minimum creep rate, secondary creep it is also known as
steady-state creep. It occurs when there is a balance between the compet-
ing processes of strain hardening and recovery.
 165

Figure 2.64 - Typical creep curve.

Since creep is a thermally activated process, it is not surprising that steady-

state creep obeys an Arrhenius-type rate equation. The steady-state creep
rate, , in this intermediate temperature range (0.4 Tm<T<0.6 Tm) can be
expressed as a power law function:

(eq.2.43)

where Q is the activation energy for creep; A is the pre-exponential con-

stant; n is a constant, usually between 3 and 10; R is the universal gas con-
stant; and T is the absolute temperature. This equation describes the de-
pendence of creep rate on the key variables, temperature and This equation
describes the dependence of creep rate on the key variables, temperature
and stress. A correlation of creep and diffusion data for pure metals shows
that the activation energy for creep, Q, is equal to the activation energy for
166

self-diffusion, as shown in Fig.2.65.

Figure 2.65 - Correlation between diffusion and creep activation energies.

The minimum creep rate during steady-state creep is usually the most im-
portant design parameter obtained during a creep test. Two criteria are
common: (1) the stress to produce 1% creep in 10,000 h, or (2) the stress to
produce 1% creep in 100,000 h. The first criterion is often used for jet en-
gine components and the second for steam turbines.

Tertiary creep. It is a region of drastically increasing strain rate with rapid

extension to fracture. Tertiary creep is dominated by a number of weaken-
ing metallurgical instabilities, such as localized necking, corrosion, inter-
crystalline fracture, microvoid formation, precipitation of brittle second-
phase particles, and dissolution of second phases that originally contribut-
ed to strengthening of the alloy. When designing components for service at
elevated temperatures, the steady-state creep rate is usually the significant
design parameter. However, the duration of tertiary creep is also important,
because it constitutes a safety factor that may allow detection of a failing
component before catastrophic fracture.
 167

Creep Deformation Mechanisms

The major classes of creep mechanisms are those that are governed by dis-
location motion and those that are diffusion controlled. The dominating
mechanism is determined by both the stress and temperature; however,
several mechanisms may be active at the same time. In general, the ones
governed by dislocation motion are more prevalent at lower temperatures
and higher stresses, while those controlled by diffusion occur at higher
temperatures and lower stresses.

Dislocation motion induced creep is the result of dislocations, in combina-

tion with vacancies and thermal activation, climbing over obstacles that
would normally impede their motion at lower temperatures.
The relevant dislocation mechanisms are dislocation glide and climb. As
the temperature is increased, slip systems that were not available at room
temperature become active, promoting dislocation glide. When disloca-
tions encounter an obstacle, they are blocked and tend to pile up against
the obstacle.
At low stress levels, the applied stress is insufficient to enable the disloca-
tions to bow around or cut through the obstacle. However, at elevated tem-
perature, a dislocation may climb by diffusion to a parallel slip plane
(Fig.2.66 and Fig.2.67). Having climbed, the dislocation proceeds along
the new slip plane until it encounters another resistant obstacle, whereupon
it climbs (or descends) to another parallel plane and the process repeats.
Since dislocation motion depends on both dislocation glide and climb, the
term climb-glide creep is used to describe this form of creep. Climb-glide
creep depends more strongly on stress than does diffusion creep.

Figure 2.66 - Thermally activated dislocation climb.

168

Figure 2.67 - Dislocations can climb (a) when atoms leave the dislocation line to
create interstitials or to fill vacancies or (b) when atoms are attached to the dislo-
cation line by creating vacancies or eliminating interstitials.

Diffusion creep is often the dominating mechanism at high temperatures

and low stresses. Under the driving force of an applied stress, atoms dif-
fuse from the sides of the grains to the tops and bottoms in the manner
shown in Fig. 2.68. The grain becomes longer as the applied stress does
work, and the process will be faster at high temperatures because there are
more vacancies. It should be noted that atomic diffusion in one direction is
the same as vacancy diffusion in the opposite direction.

Figure 2.68 - Diffusion creep mechanisms.

 169

Grain size plays a role in creep of metals. The finer the grain size, the more
rapid the mass transport, causing permanent deformation. Thus, under
conditions where creep is solely due to diffusion, the creep resistance is
improved by increasing the grain size. Note that this is different from low-
temperature behavior, where a fine grain size is almost always beneficial
to strength and ductility.

Creep Life Prediction

A frequent problem encountered in materials selection for component de-
sign is that it may be desirable to use a new alloy in a high temperature
structure; however, the alloy is so new that there are not sufficient data to
substantiate its long-term creep resistance. Therefore, it is necessary to ex-
trapolate higher temperature. In order to extrapolate the data to the re-
quired times, a considerable amount of effort has been expended in devel-
oping empirical prediction methods. One of the most widely used is the
Larson-Miller parameter, P:

(eq.2.44)

where T is the absolute temperature, t is the time to rupture in hours, Q is

the activation energy for creep, R is the universal gas constant, and C is
the Larson-Miller constant, which typically has a value in the range of 30
to 65.
If P is evaluated for pairs of t and T for a number of different stress levels,
a single master curve can be plotted for the material.
An actual set of stress-rupture data is shown for the nickel-base alloy In-
conel 718 as log stress versus log time to rupture in Fig. 2.69a. The data
are then replotted as constant-time curves on coordinates of stress versus
temperature in Fig. 2.69b. Dashed horizontal lines have been added at
stress levels of 550, 620, 760, and 830 MPa (80, 90, 110, and 120 ksi).
Values for T at the intercepts of these dashed lines and the constant-time
curves are then determined and plotted in Fig. 2.69c on coordinates of log t
versus 104/TA. By extending the data in Fig. 2.69c, a set of converging
isostress lines meeting on the ordinate at a value of log t = -25 can be ob-
tained. The Larson-Miller equation for this set of data is:

(eq.2.45)
170

where absolute temperature, TA, is in units of the Kelvin temperature

scales. The final master Larson-Miller curve is shown in Fig. 2.69d.

Figure 2.69 - Larson-Miller curve generation for Inconel 718.

One of the dangers of any of the extrapolation methods is an unanticipated

structural instability in the material that may go undetected. Since the in-
stabilities usually occur at higher temperatures, several tests should be
conducted at substantially higher temperatures than the actual part will see
in service.

Design Against Creep

Design against creep can take several approaches. First, it makes sense to
use a material with a high melting temperature in high-temperature appli-
cations since, to a good approximation, diffusion coefficients on which the
creep rate depends are proportional to the homologous temperature
(T/Tm). Face-centered cubic (fcc) metals generally have superior creep re-
sistance to body-centered cubic (bcc) metals at equivalent homologous
 171

temperatures, because the slightly more open bcc structure results in great-
er diffusivities.
Design against creep may also involve first determining the dominant
creep mechanism. If diffusion creep dominates, then increasing the grain
size is a beneficial microstructural alteration. Further, for diffusion creep,
improved creep resistance can sometimes be obtained by placing inert par-
ticles, such as carbides, on grain boundaries. This helps to pin the grain
boundaries, enhancing creep resistance.
As it will better discussed in Chapter 6, creep-resistant alloys include car-
bon steels, chromium-molybdenum steels, chromium molybdenum-
vanadium steels, stainless steels, nickel and cobalt alloys, and superalloys
(a comparison of the stress-rupture properties for a number of different
metallic alloy families is shown in Fig. 2.70).

Figure 2.70 - rupture comparison for several classes of alloys.

172

Chapter 3 Special Steels

Introduction

Ferrous alloys, which are based on iron-carbon alloys, include plain carbon
steels, alloy and tool steels, stainless steels, and cast irons. These are the
most widely used materials in the world. In the history of civilization,
these materials made their mark by defining the Iron Age. Steels typically
are produced in two ways: by refining iron ore or by recycling scrap steel.
In the Chapter 9 it is discussed in depth steelmaking processes for produc-
ing primary steel either from iron ore (early pig iron is produced from iron
ore, secondarily it is converted into steel by removing the excess of car-
bon) or from steel scraps that are melted in an electric arc furnace, while in
the last section of Chapter 9 some examples of metalworking operations
employed in industry to produce semifinished products.
In this section it is discussed the property of special steels, namely such
steels that are available on market - produced into finished or semifinished
shape to be employed by designer for special machine construction pur-
poses. Firstly we will necessarily build confidence in classification and
designation of special construction steels (hereinafter, special steels), ac-
cordingly two main classifications systems:
the SAE/AISI classification originally developed by the SAE, Soci-
ety of Automotive Engineers (SAE) and later refined in conjunction
with the American Iron and Steel Institute (AISI); hereinafter, for
the sake of brevity, we refer to AISI classification;
the European Standard EN 10027-1, hereinafter EN classification.
Since we could indifferently refer to steels classified in the AISI or EN
classifications, it is useful to learn the basics of these two classification
systems.

The European Standard classification and designation for steels

The EN 10027-1 standard defines the classification and designation sys-

tem. Firstly it is necessary to distinguish the classification system from the
designation, as below described.

Designation of steels
 173

The EN 10027-1 standard defines how to designate a steel that is included

in any of the above classes. Designating a steel means writes its own code
by which a steel is univocally identified. We can talk about designation
system as the way to give a name to steels accordingly to specific code.
Below the four possibilities to designate a steel by the European Standard
EN 10027-1.

i) Plain carbon steel for general purpose are designated by the generalized
code:

X nnn
that can be completed by optional further digits. The designation is therefore com-
posed by: a) a single letter X that designates the application (see the list of
letter in Table 3.1), b) then a three digit number nnn signifying the me-
chanical property (often yield strength) dictated in the standard for that ap-
plication designation (see again Table 3.1).

Example: the S355 steel refers to structural application with minimum

guaranteed yield strength of 355 MPa.

Application sym-
Meaning Mechanical Property
bol
S Structural steel Minimum Yield Strength
P Steel for pressure lines and vessels Minimum Yield Strength
L Steel for pipe and tube Minimum Yield Strength
E Engineering steels Minimum Yield Strength
B Steel for reinforced concrete Characteristic Yield Case
R Steel for rail use Minimum Yield Case
H High Strength Cold Rolled Minimum Yield Case

D Flat Products for Cold Forming

T Tinmill Products Nominal Yield Case

M Electrical Steel

Table 3.1 Common application code and mechanical properties contemplated by

three digit numbers.
174

The heat-treated steels, namely all such steels of any classes other than
general purpose steels type, can be designated by three different codes,
depending on the chemical composition, as below described:

ii) Carbon steel, namely steels where no alloying elements are added in
chemical composition:
C nn
where nn is the approximate carbon content multiplied by 100.
For example, C40, means 0.4% of carbon content.

iii) Alloying steel where more alloying elements have been added to chem-
ical composition, but with all the alloying elements less than 5% weight:

nn A B C a b c

where:
- nn is the approximate carbon content multiplied by 100;
- A, B, C, etc. represent the alloying elements; elements are ordered
from left to right as they are sorted by higher to lower content;
- a, b, c (but often only at least two digit number is present) whole
numbers that represent by a multiplying factor the percentage of
the A, B and C elements respectively. Factor is:
o 4 referring to Cr, Co, Mn, Si, W, Ni;
o 10 referring to Al, Be, Cu, Mo, Ti, Pb, V, etc.;
o 100 referring to N, P, S, Ce;
o 1000 referring to B.

For example, a UNI EN 40CrMnNiMo8-6-4 is a low-alloyed steel with

0.40 %C, 2%Cr (=8/4), 1.5% Mn (=6/4), 1% Ni (=4/4) and some percent-
age of Mo lower than 1%.

iv) High alloying steel with at least one of alloying element more than 5%:

X nn A B C a.b.c

where:
nn is carbon content multiplied by 100;
A, B, C, etc. represent the alloying elements; elements are ordered
from left to right as they are sorted by higher to lower content;
 175

a, b, c (but often only at least two digit number is present) whole

numbers that represent the actual percentage of the A, B, C ele-
ments respectively approximate to whole number.
For example, an UNI EN X4CrNiMo17.12.2 is a high alloyed steel with
0.04 %C, 17%Cr, 12% Ni, 2% Mo steel.

Classification of steels
When we talk about classification, we intend to refer to how steels are
classified into families or groups accordingly with their specific purposes.
The EN 10027-1 groups steels by their functional uses for specific engi-
neering purposes, as below illustrated.

General purpose steels (non-heat treated steels); they are low-cost steels
that are used for construction purposes, not alloyed and non-heat treat-
ed. The chemical composition is thus not the distinguishing factor for
their own designation. They are classified into three main types:
o Low strength, plain low carbon steel;
o Medium strength, with Si between 0.15-0.35% and
1%Mn;
o High strength, with higher Mn content up to 1.65%;

Special steels, that are heat-treated steels, classified into 5 sub-

categories:
Quenched and tempered steels
Carburizing steels
Nitriding steels
Spring steels
Self-quenching steels
Steel for special applications, that are also heat-treated steels that are
distinguished for specific applications. Several families are grouped un-
der such larger class (e.g. high fracture toughness steels, tool steels, low
temperature steels, high temperature steels, etc.);

The Stainless Steels grade, classified into 4 types:

Austenitic stainless steels;
Ferritic stainless steels;
Martensitic stainless steels;
176

Duplex stainless steels;

Precipitation hardening stainless steels.

The SAE-AISI classification and designation for steels

In the following, the basics of SAE-AISI classification and designation of
steels is described.

Designation of steels
The combined SAE/AISI numbering system uses a numerical code. It dis-
tinguish:

i) Plain carbon steels:

either 10xx or 10xxx for plain carbon steels; the prefix 10 indicates
that the steel is a plain carbon steel, while the subsequent xxxs
specify the nominal carbon content in points of carbon (1
point=0.01% C). For example, 1045 steel would nominally contain
0.45% C (which actually varies between 0.43 and 0.50%). Typical-
ly, compositions run from 1005 to 1095, but the designation 10125
would indicate a plain carbon steel containing 1.25% C (see exam-
ples in Table 3.2).
12xxseries, are rephosphorized and resulfurized steels (steels with
an increased machinability, S addition, and increased ferrite
strength because of P addition; small quantity of P strengthens fer-
rite crystal lattice by solid solution) 14;
13xxseries, are carbon steels that contain more than 1wt% Mn and
also have a minimum Si of 0.15 to 0.35 wt% (Si and Mn increase
ferrite lattice strength by solid solution mechanisms) 14;
15xx series, are high Mn content carbon steels contain higher Mn
levels (up to 1.65 wt%) than the 10xx series of carbon steels. Notice
that Mn lowers the A3 temperature thus refining the resulting fer-
rite-pearlite structures; Mn also contribute some solution-hardening
of the ferrite, but it is limited compared to that of C, N and Si14.
ii) Alloy steels:
40xx series, are Molybdenum steels14; Molybdenum is added in
small amounts, increases both the strength and hardenability of

14 The subsequent xxxs specify the nominal carbon content in points of carbon
(1 point=0.01% C).
 177

steels. Steels containing molybdenum are less susceptible to temper

brittleness (i.e. Krupp brittleness).
41xx series, are Chromium-Molybdenum steels14; Chromium is
added to increase hardenability and strength; however, the addition
of chromium can also make this series susceptible to temper embrit-
tlement;
43xx, 47xx, 81xx, 86xx, 87xx and 94xx designates the Nickel-
Chromium-Molybdenum Steels series (refer to Table 3.2 for de-
tails).

Table 3.2 Summary of AISI/SAE designations for carbon and low-alloy steels.
178

Classification of steels
The AISI standard groups steels into following main classes:
Plain carbon steels (10xxx series) A plain carbon steel is essentially
an alloy of Fe-C that also contains manganese and a variety of re-
sidual elements, in particular S, P (impurities) and Si (Si is added
during the production process for deoxydation stage, refer to
steelmaking section). AISI defines plain carbon steels as Fe-C with:
o 1.65 wt% maximum Mn,
o < 0.6 wt% Si,
o < 0.6 wt% Cu
o no other deliberately added alloying element.
The carbon steels are classified as follows:
o Nonresulfurized carbon steels (10xx or 10xxx series
steels); low, medium and high carbon content steels;
o Resulfurized steels (11xx series);
o Rephosphorized and resulfurized steels (12xx series);
o High manganese carbon steels (15xx series);
Alloy steels, namely Fe-C alloys with the addition of one or more of
the following elements15: Mn, Cr, Ni, Mo, Ti, Co, W, V, Si, Al, B.
Despite plain carbon steels are widely used, they are not adequate
for all engineering applications because of the following limitations:
o They cannot be strengthened beyond approximately 700
MPa without a significant loss in toughness and ductility;
o They are not hardenable to great depths, thus limiting the
maximum cross section that can be through hardened;
o Severe quench media (i.e. water) is required greatly in-
creasing the susceptibility to distortion and cracking;
o They have poor corrosion resistance and readily oxidize at
elevated temperatures.
Stainless steels (Austenitic, Ferritic, Martensitic, Duplex and Precipitation
Hardening Steels) in order to prevent corrosion.
Tool steels, to prevent wear phenomena.

15As better described in the next section, metallurgical basic effects of alloying
elements are: a) lowering A3 and A1, thus shifting CCT curves (e.g. increase har-
denability); b) stabilize interstitial carbides (e.g. CrxCy, TiC, etc.) formed during
tempering (e.g. increase tempering temperature to increase toughness not decaying
strength).
 179

Fig.3.1 - Classification of ferrous alloys.

Relationship between microstructure and properties of steels

Firstly it is worth of notice that strengthening mechanisms we discussed in

the Chapter 1 are here fundamental to comprehend the relationship be-
tween mechanical properties and microstructures - namely how micro-
structures can exert control on dislocation mobility which are the result
of specific heat treatments specifically designed for the chemical composi-
tion of special steel chosen for realize the part component for its specific
engineering purpose.

Microstructures and heat treatment in steels

Almost all of the heat treatments of steel are directed toward producing the
mixture of ferrite and cementite that gives the proper combination of
properties. Figure 3.2 shows the three important microconstituents, or ar-
rangements of ferrite and cementite, that are usually sought. Pearlite is a
microconstituent consisting of a lamellar mixture of ferrite and cementite.
180

In bainite, which is obtained by transformation of austenite at a large un-

dercooling, the cementite is more rounded than in pearlite. Tempered
martensite, a mixture of very fine and nearly round cementite in ferrite,
forms when martensite is reheated following its formation.

Fig.3.2 - Micrographs of (a) pearlite, (b) bainite, and (c) tempered martensite, il-
lustrating the differences in cementite size and shape among the three microcos-
tituents.

The microstructures mentioned above in steels are produced by the trans-

formation of the austenite microstructure (obtained by heating up structure
over A1 and A3 temperatures) throughout: a) isothermal transformation
that occurs below A1 temperature; b) continuous cooling from austeinitiz-
ing temperature to ambient temperature.

Box - Isothermal transformation treatments for bainite or fine perlite for-

mation

The isothermal transformation heat treatment used to produce bainite, called

austempering, simply involves austenitizing the steel, quenching to some tem-
perature below the nose of the TTT curve, and holding, at that temperature until
all of the austenite transforms to bainite (Fig.3.3). Very fine pearlite can be also
formed by an isothermal anneal (Figure 3.3), with more uniform properties,
since the cooling rates and microstructure obtained during continuous cooling
can vary across the cross-section of the steel.
 181

Fig.3.2 - The austempering and isothermal anneal heat treatments in a 1080

steel.

Continuous cooling transformation treatments

Four simple heat treatments process annealing, annealing, normalizing,

and spheroidizing are commonly used for steels to produce mixture of
ferrite and perlite structure (Figure 3.3). These heat treatments are used
therefore to accomplish one of three purposes: (1) eliminating the effects
of cold work, (2) controlling dispersion strengthening, or (3) improving
machinability.
- Process AnnealingEliminating Cold Work The recrystallization
heat treatment used to eliminate the effect of cold working in
steels with less than about 0.25% C is called a process anneal. The
process anneal is done 80C to 170C below the A1 temperature.
The intent of the process anneal treatment for steels is similar to
the annealing of inorganic glasses in that the main idea is to signif-
icantly reduce or eliminate residual stresses.
- Annealing and NormalizingDispersion Strengthening Steels can
be dispersion-strengthened by controlling the fineness of pearlite.
The steel is initially heated to produce homogeneous austenite
(FCC -phase), a step called austenitizing.
- Annealing, or a full anneal, allows the steel to cool slowly in a
furnace, producing coarse pearlite. Normalizing allows the steel to
cool more rapidly, in air, producing fine pearlite. Figure 3.4 shows
182

the typical properties obtained by annealing and normalizing plain

carbon steels 16.

Fig. 3.3 - Schematic summary of the simple heat treatments for (a) hypoeutectoid
steels and (b) hypereutectoid steels.

16
For annealing, austenitizing of hypoeutectoid steels is conducted about 30C above
the A3, producing 100% ; however, austenitizing of a hypereutectoid steel is done at
about - 30C above the A1, producing austenite and Fe3C. This process prevents the
formation of a brittle, continuous film of Fe3C at the grain boundaries that occurs on slow
cooling from the 100% region. In both cases, the slow furnace cool and coarse pearlite
provide relatively low strength and good ductility. For normalizing, austenitizing is done at
about 55C above the A3 or Acm; the steel is then removed from the furnace and cooled in
air. The faster cooling gives fine pearlite and provides higher strength.
 183

Fig. 3.4- The effect of carbon and heat treatment on the properties of plain carbon
steels.

- SpheroidizingImproving Machinability. Steels that contain a

large concentration of Fe3C have poor machining characteristics.
It is possible to transform the morphology of Fe3C using spheroi-
dizing. The microstructure, known as spheroidite, has a continuous
matrix of soft, machinable ferrite due to the presence of round
small Fe3C carbides (Fig.3.12).

Fig. 3.12 - The microstructure of spheroidite with Fe3C particles dispersed in a

ferrite matrix.
184

Strengthening of ferritic-perlitic structure

Fe3C phase is much harder but more brittle than ferrite. Thus, increasing
the fraction of Fe3C in a steel alloy while holding other microstructural el-
ements constant will result in a harder and stronger material. This is
demonstrated in Figure 3.13a, in which the tensile and yield strengths and
the Brinell hardness number are plotted as a function of the weight percent
carbon (or equivalently as the percentage of Fe3C) for steels that are com-
posed of fine pearlite. All three parameters increase with increasing carbon
concentration. Inasmuch as cementite is more brittle, increasing its content
will result in a decrease in both ductility and toughness (or impact energy).
These effects are shown in Figure 3.13b for the same fine pearlitic steels.
The layer thickness of each of the ferrite and cementite phases in the mi-
crostructure also influences the mechanical behavior of the material.

Figure 3.13 - (a) Yield strength, tensile strength, and Brinell hardness versus car-
bon concentration for plain carbon steels having microstructures consisting of fine
pearlite. (b) Ductility (%EL and %RA) and Izod impact energy versus carbon
concentration for plain carbon steels having microstructures consisting of fine
pearlite.

Fine pearlite is harder and stronger than coarse pearlite, as demonstrated

by the upper two curves of Figure 3.14a, which plots hardness versus the
carbon concentration. The reasons for this behavior relate to phenomena
 185

that occur at the Fe3C phase boundaries. First, there is a large degree of
adherence between the two phases across a boundary. Therefore, the
strong and rigid cementite phase severely restricts deformation of the soft-
er ferrite phase in the regions adjacent to the boundary; thus the cementite
may be said to reinforce the ferrite. The degree of this reinforcement is
substantially higher in fine pearlite because of the greater phase boundary
area per unit volume of material. In addition, phase boundaries serve as
barriers to dislocation motion in much the same way as grain boundaries
(see Chapter 1). For fine pearlite there are more boundaries through which
a dislocation must pass during plastic deformation. Thus, the greater rein-
forcement and restriction of dislocation motion in fine pearlite account for
its greater hardness and strength. Coarse pearlite is more ductile than fine
pearlite, as illustrated in Figure 3.14b. This behavior results from the
greater restriction to plastic deformation of the fine pearlite.

Figure 3.14 (a) Brinell and Rockwell hardness as a function of carbon concentra-
tion for plain carbon steels having fine and coarse pearlite as well as spheroidite
microstructures. (b) Ductility (%RA) as a function of carbon concentration for
plain carbon steels having fine and coarse pearlite as well as spheroidite micro-
structures.
186

Box The Continuous Cooling Transformation (CCT) Diagrams for steels

and effect of alloying elements.

We can develop a continuous cooling transformation (CCT) diagram by deter-

mining the microstructures produced in the steel at various rates of cooling. Let
us consider the CCT diagram of Fig.3.15. If we cool a 1080 steel at 5C/s, the
CCT diagram tells us that we obtain coarse pearlite; we have annealed the steel.
Cooling at 35C/s gives fine pearlite and is a normalizing heat treatment. Cool-
ing at 100C/s permits pearlite to start forming, but the reaction is incomplete
and the remaining austenite changes to martensite. We obtain 100% martensite
and thus are able to perform a quench and temper heat treatment, only if we
cool faster than 140C/s. Other steels, such as the low-carbon steel in Fig.3.16
have more complicated CCT diagrams (in various handbooks, you can find a
compilation of TTT and CCT diagrams for different grades of steels).

Figure 3.15 The CCT diagram (solid lines) for a 1080 steel (the dashed lines
represent the compared line transformation for the TTT diagram).

Referring to heat treatment and CCT diagrams, main effect of alloying elements
that are added to steels: (a) provide solid-solution strengthening of ferrite, (b)
cause the precipitation of alloy carbides rather than that of Fe3C, and (c) im-
prove hardenability. The term hardenability describes the ease with which
steels can form martensite. Plain carbon steels have low hardenability; only very
high cooling rates produce all martensite, despite medium carbon and alloy
steels, which have high hardenability (even cooling in air may produce marten-
site). This is visible if the CCT curves of low carbon and alloyed steels are
compared (Fig.3.17). The effect of alloying elements, including carbon, is to
shift CCT curves to the right and down in the temperature versus log time dia-
gram.
 187

Figure 3.16 The CCT diagram for a low-alloy, 0.2% C steel.

Figure 3.17 CCT diagrams for: (a) red lines, a low-carbon steel; (b) a medium
carbon steel.

It is worth to notice hardenability does not refer to the hardness of the steel. A
low-carbon, high-alloy steel may easily form martensite but, because of the
low-carbon content, the martensite is not hard (Fig.3.18).
188

Figure 3.18 Relationship between hardness of quenched martensite and car-

bon content; the effect of presence of retained austenite and self-tempering is al-
so considered.

Furthermore, in practical cases, the final hardness developed onto piece is relat-
ed to how easily we can form martensite in a thick section of steel that is
quenched. While with a more hardenable steel we can get away with a rela-
tively slow cooling rate and still form martensite, in case of low hardenability
steel it is possible that thicker sections cannot be transformed to martensite.
This is caused by the shifting of the cooling curves on thicker sections, as
shown by two different round sections illustrated in Fig.3.19.

Figure 3.19 Shifting of cooling curves for small and large diameters round bar
quenched from austenitizing temperature.

The problem of quenching thicker sections of low hardenability steel is there-

fore illustrated in Fig.3.20. As it is shown, the smaller radius section piece is
transformed into martensite and bainite structure, across the cross section. How-
ever, increasing the section radius causes shift of cooling curves - accordingly
with the Fig.3.19 - thus provoking the formation across the round section of
 189

mixture of soft structure, as perlite and ferrite, together with hard martensite and
bainite.

Figure 3.20 Shifting of cooling curves for small and large diameters round bar
quenched causes development of soft structure (perlite and ferrite) mixed with
hard structure (martensite and bainite).

Residual Stresses and Cracking

Further complication we have in the practical case of Fig.3.20. When the aus-
tenite in the center later transforms, the hard surface is placed in tension, while
the center is compressed. If the residual stresses exceed the yield strength,
quench cracks form at the surface (Figure 3.21). To avoid this, we can first cool
to just above the Ms and hold until the temperature equalizes in the steel; subse-
quent quenching permits all of the steel to transform to martensite at about the
same time. This heat treatment is called marquenching or martempering (Figure
3.22). Note that as discussed presently, strictly speaking, the CCT diagrams
should be used to examine non-isothermal heat treatments.

Figure 3.21 Formation of quench cracks caused by residual stresses produced

during quenching. The figure illustrates the development of stresses as the aus-
tenite transforms to martensite during cooling.
190

Figure 3.22 The marquenching (or martempering) heat treatment, designed to

reduce residual stresses and quench cracking.

Evaluation of steel hardenability: the standard quench-end Jominy test

In order to separate the effect of thickness dimension of a quenching piece from

the right-shifting of CCT curves obtained by alloying elements, a standard
Jominy test is used to compare hardenabilities of steels. A steel bar 4 in. long
and 1 in. in diameter is austenitized, placed into a fixture, and sprayed at one
end with water (Fig.3.23a). This procedure produces a range of cooling rates
very fast at the quenched end, almost air cooling at the opposite end. After the
test, hardness measurements are made along the test specimen (Fig.3.23b) and
plotted to produce a hardenability curve (Fig.3.23c). The distance from the
quenched end is the Jominy distance and is related to the cooling rate (Fig.3.24).

Fig.3.23 - Schematic diagram of Jominy end-quench specimen (a) mounted dur-

ing quenching and (b) after hardness testing from the quenched end along a
ground flat; (c) the hardenability curve.
 191

Fig.3.24 - Correlation of hardenability and continuous-cooling information for

an ironcarbon alloy of eutectoid composition.

Quenching and tempering of steels.

Further continuous cooling transformation treatment is conducted for the

opposite purposes, that is to produce a high strength but tough microstruc-
ture. It is a double step treatment: a) cooling from austetizing temperature
a steel to transform austenite into martensite, a tetragonal structure pro-
duced because of lack of carbon atoms diffusion (Fig.3.25); b) tempering,
namely heating up quenched martensite below A1 temperature, to allow
carbon atom diffuse and tetragonal lattice transform into BCC.
Of the various microstructures that may be produced for a given steel al-
loy, martensite is the hardest and strongest and, in addition, the most brit-
tle; it has, in fact, negligible ductility. Its hardness is dependent on the car-
bon content, up to about 0.6 wt% as demonstrated in Figure 3.26, which
plots the hardness of martensite and fine pearlite as a function of weight
percent carbon (top and bottom curves). In contrast to pearlitic steels, the
strength and hardness of martensite are not thought to be related to micro-
structure. Rather, these properties are attributed to the effectiveness of the
interstitial carbon atoms in hindering dislocation motion and to the rela-
tively few slip systems (along which dislocations move) for the BCT struc-
ture.
192

(a) (b)

Fig. 3.25 (a) simple model for non-diffusional transformation from the FCC -
phase to the Body-Centered Tetragonal (BCT) structure of martensite (diagonal
centered rotated structure) the white atoms are Fe, distinguished from black
spheres representing carbon interstitial position; (b) Photomicrograph showing the
martensitic microstructure.

Fig. 3.26 - Hardness (at room temperature) as a function of carbon concentration

for plain carbon martensitic, tempered martensitic (tempered at 371C), and
pearlitic steels.
 193

Tempering martensite
In the as-quenched state, martensite, in addition to being very hard, is so
brittle that it cannot be used for most applications; also, any internal stress-
es that may have been introduced during quenching have a weakening ef-
fect. The ductility and toughness of martensite may be enhanced and these
internal stresses relieved by a heat treatment known as tempering. Temper-
ing is accomplished by heating a martensitic steel to a temperature below
the eutectoid for a specified time period. Normally, tempering is carried
out at temperatures between 250C and 650C; internal stresses, however,
may be relieved at temperatures as low as 200C. This tempering heat
treatment allows, by diffusional processes, the formation of tempered mar-
tensite, according to the reaction:

Martensite (BCT, single phase) tempered martensite (Fe + fine car-

bides)

where the single-phase BCT martensite, which is supersaturated with car-

bon, transforms into the tempered martensite, composed of the stable fer-
rite, cementite phases and carbides (in presence of alloying elements with
great affinity with carbon). The microstructure of tempered martensite
consists of extremely small and uniformly dispersed particles embedded
within a continuous ferrite matrix. The fine and hard particles reinforce the
ferrite matrix being barriers to dislocation motion during plastic defor-
mation. On the other hand, a continuous ferrite phase guarantee adequate
toughness; the double phenomena, hard particles dispersing and Fe ma-
trix formation accounts for the improvement of both two counteracting
properties, hardness and toughness, for an optimal balance. The size of the
precipitates influences the mechanical behavior of tempered martensite;
increasing the particle size decreases the ferritecementite phase boundary
area and, consequently, results in a softer and weaker material, yet one that
is tougher and more ductile. Furthermore, the tempering heat treatment de-
termines the size of the cementite particles. Because carbon diffusion is
involved in the martensitetempered martensite transformation, increasing
the temperature will accelerate diffusion, the rate of cementite particle
growth, and, subsequently, the rate of softening. The dependence of tensile
and yield strength and ductility on tempering temperature for an alloy steel
is shown in Figure 3.27.
194

Fig. 3.27 - Tensile and yield strengths and ductility (%RA) (at room temperature)
versus tempering temperature for an oil-quenched alloy steel (type 4340).

Box Temper Embrittlement

The tempering of some steels may result in a reduction of toughness as meas-

ured by impact tests; this is termed temper embrittlement. The phenomenon oc-
curs when the steel is tempered at a temperature above about 575C followed by
slow cooling to room temperature, or when tempering is carried out at between
approximately 375C and 575C. Steel alloyed with Cr are more susceptible to
temper embrittlement have been found to contain appreciable concentrations of
the alloying elements manganese, nickel, or chromium and, in addition, one or
more of antimony, phosphorus, arsenic, and tin as impurities in relatively low
concentrations. The presence of these alloying elements and impurities shifts
the ductile-to-brittle transition to significantly higher temperatures; the ambient
temperature thus lies below this transition in the brittle regime. It has been ob-
served that crack propagation of these embrittled materials is intergranular; that
is, the fracture path is along the grain boundaries of the precursor austenite
phase. Furthermore, alloy and impurity elements have been found to segregate
preferentially in these regions. Temper embrittlement may be avoided by (1)
Molybdenum addition and/or (2) tempering above 575C or below 375C, fol-
lowed by quenching to room temperature. Furthermore, the toughness of steels
 195

that have been embrittled may be improved significantly by heating to about

600C and then rapidly cooling to below 300C.

Prediction of hardenability
There are large quantities of Jominy hardenability curves available in the
literature, such as the ones shown in Fig. 3.28.
The hardenability of a steel can also be predicted from its composition and
grain size. The ideal diameter (DI) is defined as the diameter of a steel bar
that will harden to 50 vol% martensite when quenched in an ideal quench
medium. The significance of this value is that a bar with a diameter larger
than DI cannot be hardened all the way through its cross section, even in
an infinitely rapid quench. Grossman originally developed a method for
calculating hardenability. The DI calculation starts from the calculation of
the DB, the base diameter. DB is influenced only by the carbon content
and the grain size 17, and it can be read from plot in Fig. 3.29. The DB takes
into accounts only two contributing factors for hardenability of steel, car-
bon content and grain size, while it considers steel quenched in an ideal
quenching mean.

Fig. 3.28 - Typical Jominy hardenability curves for medium-carbon steels austen-
itized at 845 C from initial normalized condition.

17 The hardenability increases with larger austenite grain sizes, because larger grain siz-

es means there are fewer nucleation sites for diffusion-controlled phase transformations
(that is, pearlite, ferrite, or bainite). When the danger of quench cracking is remote (i.e., no
abrupt changes in section thickness) and engineering considerations permit, it may some-
times appear to be more practical to use a coarse-grained steel than a fine-grained steel to
obtain hardenability. However, this is not recommended, because the use of coarser-grained
steels usually involves a serious sacrifice in notch toughness.
196

Fig. 3.29 - Plot of base diameter, DB, used for calculating ideal diameter.

However, each of the alloying elements in the steel contributes by a multi-

plying factor that increases the depth of hardening. Such multiplying fac-
tors are given in Table 3.3.

Table 3.3 - Multiplying factors for alloying elements.

 197

Now, let us consider a steel containing 0.45 wt% C with an ASTM grain
size of 6 and an alloy content of 0.5 wt% Mn, 0.2 wt% Si, and 0.35 wt%
Cr. By the use of the plot in Fig. 3.29, firstly we can calculate the base di-
ameter (DB) of a steel with only 0.45 wt% C and a grain size of 6 ASTM,
obtaining DB= 6.5 mm.
Secondly, we can estimate the multiplying factors mf(element) from the Table
3.3, as it follows:

0.5 wt% Mn= 2.667 = mf(Mn)

0.2 wt% Si= 1.140 = mf(Si)
0.35 wt% Cr= 1.756 = mf(Cr)

By the following relationship, since we already know the DB and the mul-
tiplying factors, we can calculate the ideal diameter (DI) for the alloyed
steel:

DI=DB mf(Mn) mf(Si) mf(Cr) =

= (6.5mm) (2.667) (1.140) (1.756) = 34 mm

However, we know that the critical diameter DC depends on the quench

severity. The relationship between ideal diameter (DI) and critical diame-
ter (DC) for various quench severities is given by empirical diagram as it is
shown in Fig.3.30. To use the plot, we need to know the H factor. This is
possible by the use of the Table 3.4: for example, if the steel were
quenched in moderately agitated oil, an H=0.37 can be determined from
Table 3.4.
198

Dc = critical diameter
DI = ideal diameter

Fig. 3.30 - Relationship between ideal diameter and critical diameter.

Table 3.4 - Quench values for several quenching media.

For the sake of simplicity, in Fig. 3.31 is reproduced the same diagram of
Fig. 3.30, with all the curves removed except for the one we need for our
final calculation.
 199

Fig. 3.31 Simplified plot of Fig.3.30 for determination of critical diameter (DC).

As shown, with the calculated DI, the plot in Fig.3.31 allows us to calcu-
late the critical diameter DC for the specific quench severity factor
H=0.37: the DC is determined to be 7.5 mm.
As last analysis, the section size of bars with square cross sections and
plates can be compared with round bars, by the plot diagram in Fig. 3.32.
There is also an empirical relationship between the diameter of steel and
the Jominy distance at which there will be 50% martensite at the center, as
shown in Fig. 3.32.

(a) (b)

Fig. 3.32 (a) Comparison of different geometries with the same cooling rate at
the center; (b) Relationship between ideal diameter and Jominy position.
200

Review of phase transformations and mechanical properties for iron-

carbon alloys
In previous sections we have discussed several different microstructures
that may be produced in ironcarbon alloys, depending on heat treatment.
Figure 3.33 summarizes the transformation paths that produce these vari-
ous microstructures. Here, it is assumed that pearlite, bainite, and marten-
site result from continuous-cooling treatments. Microstructural characteris-
tics and mechanical properties of the several microconstituents for iron
carbon alloys are summarized in Table 3.5.

Fig. 3.37 - Possible transformations involving the decomposition of austenite. Sol-

id arrows, transformations involving diffusion; dashed arrow, diffusionless trans-
formation.

Table 3.5 - Microstructures and Mechanical Properties for IronCarbon Alloys.

 201

The creation of hard instead of soft structure in a thick section of steel

piece is dependent on steel hardenability. Such properties depends mainly
from chemical composition and austenite grain size achieved by structure
during austenitization temperature. Both these two factors have in fact di-
rect influence in retarding austenite transformation, delaying start of diffu-
sion-driven (i.e. ferrite, perlite and bainite) and diffusionless (i.e. marten-
site) austenite transformations. As a simplified and powerful method to
evaluate different hardenability of steels, the Jominy end-quench test,
gives immediate representation of the effect of alloying elements. A steel
of medium hardenability gives a hardness profile measured along the dis-
tance from the quenched-end - i.e. the hardenability curve as shown in
Fig. 3.38a; the hardness drops rapidly because the cooling curves intercept
the curves that represent the start of transformation of austenite into struc-
tures (bainite, perlite and ferrite) which are softer than martensite. On the
opposite, hardenability increases as amount of alloying elements increases
and this leads to formation of martensite at higher distances from the
quench-end, namely the end of Jominy sample directly cooled by water jet.

(a) (b)

Fig. 3.38 - Jominy test on a steel of: (a) low hardenability; (b) high hardenability.

Secondarily, it is important to notice that tempering treatment is often re-

quired to recover toughness. This is due to change of the high-strength and
high-brittle medium and high carbon BCT lattice into a tougher BCC ma-
202

trix with fine carbide particles here dispersed. Because of presence of such
particles, the -Fe BCC matrix is strengthened meanwhile it recovers
tough behavior (i.e. dislocations can move again, but small particles op-
pose to such movement, instead the previous situation of BCT lattice
where dislocations are unmovable).

Industrial quenching problems: distortions and quenching cracks

Quenching is generally considered as the most critical step of heat treat-
ment processes conducted onto steel parts. It may lead to failures that are
generally distortions and, in most severe cases, cracks. Both distortion and
cracks are due to high stresses which develop in the part during quenching.
This occurs because massive parts are subjected to rapid cooling, and this
determine mismatching among the temperatures on top surface and subsur-
face layers, cross the part sections.
We have already discussed about the variation of cooling curves diagram-
we call the cooling islands when two different diameters round bars
made of same steel are quenched in the same quenching mean. For the
reader convenience, here below is shown again the figure 3.20 with the
original caption.

Figure 3.20bis Shifting of cooling curves for small and large diameters round
bar quenched causes development of soft structure (perlite and ferrite) mixed with
hard structure (martensite and bainite).
 203

The above figure illustrates one main problem due to limited hardenability
of steels. Hardenability, we remember, is the ability of steels to penetrate
martensite in depth, which depends on the fact cooling curves occurring
inside the part section can intercept the Ms transformation, instead of
crossing other curves representing the transformations of austenite in
something other structures softer than martensite. Actually, for the sake of
precision, also the case illustrated in the Fig.3.20bis is not the ideal case of
fully quenched section; quenching the two steel bars reported in the figure
actually produce martensite mixed to bainite (for 28mm diameter bar) and
small fraction of martensite mixed with very varying structures that range
from ferrite to perlite and bainite (for the 95mm diameter bar).
As discussed, to increase hardenability, we need to increase the alloying
elements in the chemical composition of steel. Alloying elements produces
the lowering of all the critical temperatures and a delay in austenite trans-
formation is produced as a benefit for quenching. Shifting the CCT curves
toward the right, martensite can be obtained onto larger sections by
quenching. This is the basics of quenching operations.
However, one further beneficial effect obtained by alloying steel to in-
crease the hardenability must be highlighted. Let us consider the simplified
scheme in figure 3.39.

T
A3
A1 Water quenched

Oil quenched
1 2
Ms

Mf

Log t

Figure 3.39 - Comparison of two possible quenching operations for a high harden-
ability steels. Both the water and oil quenching is possible, in terms of martensite
production in part section. The faster is the quenching operation, the larger is the
instantaneous differences between surface and inner section temperatures.
204

The CCT curves in the fig.3.39 show the steel may be quenched either in
water or in oil. Even with water quenching is less expensive, it is not in-
dustrially suitable for such a steel; this fact is due observing the instanta-
neous temperatures achieved in the part sections. In case of water quench-
ing, the temperatures achieved at same time at surface and in the center of
a round section, for example, are very high if compared to the same bar
section when it is quenched in oil. The higher is instantaneous temperature
difference in part section, the higher is the differential volumetric expan-
sion of steel. The volumetric expansion actually accounts for two concur-
rent contributes (depending on temperatures investigated): a) thermal ex-
pansion that is only function of the temperature and the coefficient of
thermal expansion; b) the volumetric expansion due to transformation of
FCC -phase into body-centered tetragonal (BCT) martensite.
In any case, the results is the same: as the sections of a part are interested
by too much temperature variations, for reason a) or b) or both, they are
subjected to differential expansion. If the differential expansion remains in
the elastic regime, the only result is temporary thermal induced stresses.
However this case is very rare, while more frequent is the case that plastic
deformations occur inside the part due to mismatching volumetric expan-
sion. If the plastic deformation caused a beneficial drop of thermally-
induced stresses (the stresses induced by differential thermal expansion fi-
nally relax), such local plastic deformations are irreversible local volume
changes, that at least cause macroscopic part distortions (e.g. torsion,
bending, profile and hole ovalization, hole misalignments.
It is worth of noticing that such problems can occur also in heating phase,
especially for large parts; for high speed heating-up process, especially
large parts can suffer of temperature mismatching that can cause distor-
tions. For this reason the temperature ramp-up rate shall be controlled and
equalization stages (Fig.3.40).
 205

(a)
Austenitizing or quenching temperature

Surface
Temperature

Core

Time

Soaking

Equalization

(b)

Figure 3.40 - Schematic representation of heating during an austenitizing treat-

ment: a) with final temperatures equalization stage; b) with final and intermediate
equalization.

Quenching and tempering steels

They are steels with the carbon percentage ranging 0.20-0.60% with even-
tually some elements added to increase hardenability.
They are required when an optimum balance between toughness and
strength is required. Toughness is a very important mechanical property,
especially for components that must be able to withstand dynamic loading
or impact. Despite ductility, toughness of a material, is a two-
dimensional property because it is an integral (or product) of strength and
ductility, as schematically shown in Figure 3.41. Steels of the same ductili-
ty but different strength levels can differ in toughness. As Figure 3.41
shows, a normalized steel (N) having the same ductility as a hardened and
206

tempered steel (V) will have lower toughness because of its lower strength
level. Toughness is measured in separate tests as impact toughness (e.g.
KV, J/cm2) or as fracture toughness ( KIC, MPam ). The lower the ductili-
ty of a material, the more brittle it is. Total brittleness accordingly denotes
zero ductility of the material.

Figure 3.41 - Schematic presentation of ductility, toughness, and brittleness.

The aim of quenching (also called hardening) and tempering steels is to

achieve maximum toughness at a specified strength level.
The metallurgical mechanisms of tempering process is below described.
As the as-quenched martensite, a body-centered tetragonal (BCT) struc-
ture, is heated up, the prolonging staying at temperatures allow carbon at-
om diffusion. This leads carbon to abandon the BCT position allowing the
tetragonal lattice - a body centered structure - to shrink by transforming in-
to a body-centered cubic (BCC), namely a -Fe phase structure. The dif-
fusing carbon thus migrates into -Fe matrix capturing any alloying ele-
ments that are added in solid solution, particularly those elements that have
greater affinity to carbon than the affinity with Fe. Diffusion of carbon at-
oms therefore allow carbon itself to be available to form with high carbon-
affinity alloying elements so fine carbides (fine particles) which widely
disperse into the -Fe matrix. These carbides are capable to inhibit the
movement of dislocations (accordingly to precipitation hardening strength-
ening mechanism). The diffusion of carbon therefore have two concurring
effects: a) carbon atoms abandon positions that determined in the as-
 207

quenched BCT structure the high-strength but brittle behavior (remind that
dislocations cannot move in a BCT structure); b) in presence of alloying
elements carbon can form fine and more dispersed carbides, namely fine
particles that are visible to dislocations and that can inhibit them in their
own movement.
Due to such temperature-time driven metallurgical mechanisms, tempering
of martensite would be preferentially conducted at high temperatures, to
speed up the treatment; o the other hand, tempering temperature for
quenching and tempering steels shall be conducted at temperature lower
than 680-700C. In fact, if tempering temperatures are too much close to
A1 temperature of the steel, they would vanish any quenching effects: at
temperature higher than optimized, carbides formed (especially for carbon
steels) would grow and finally coarse instead of fine carbides will be dis-
tributed in -matrix. The bigger are carbides, the lower is their capability
to counteract dislocation movement. At least, we could also fail the tem-
pering object by accidentally overpassing the A1 temperature, so that the
microstructure will be turned into martensite mixed to soft structures 18.
This leads to tempering temperature for quenching and tempering steels
range from 600 to 680C to achieve the good balance of strength and
toughness.
The aim of the quenching and tempering process can also be explained by
means of the stressstrain diagram schematically shown in Fig. 3.41. As
hardened, a steel has high yield strength but low ductility, and a small area
below the stressstrain curve (curve 2) indicates low toughness. As-
hardened and tempered (curve 3) steel has higher yield strength than in its
normalized condition but also much higher ductility than in its hardened
condition. The greatest area below the stressstrain curve indicates a sub-
stantial increase in toughness compared to either normalized or hardened
conditions.
For a certain steel grade, the relation between mechanical properties and
the tempering temperature can be read off from a diagram as shown in
Figure 3.42 for the steel DIN EN 20CrNiMo2 (0.15% C, 0.20% Si, 0.88%
Mn, 0.53% Cr, 0.50% Mo, 0.86% Ni).

18 Some percentage of austenite may be produced by overpassing the A1; by

slow cooling after tempering, such an austenite fraction produced in such a wrong
tempering treatment will be therefore transformed into small quantities of ferrite
and perlite grains, namely softer microstructure than tempered martensite.
208

Figure 3.41 - Stressstrain diagram of a steel after different heat treatments. 1,

Normalized; 2, hardened; 3, hardened and tempered.

Figure 3.42 - Hardening and tempering diagram of DIN 20CrNiMo2 steel.

 209

It can be clearly seen from the lower part of the diagram in Fig.3.42 how
the impact toughness increases when the steel is tempered to a temperature
above 550C. Such diagrams enable precise optimization of the strength
level and toughness by selection of the proper tempering temperature.
Maximum toughness values are obtained when tempering a structure that,
after quenching, consists of fine-grained martensite. How different micro-
structures after different heat treatment processes influence the impact
toughness of 3.5% Ni steel at low temperatures is shown in Figure 3.43.
When testing the impact toughness at low temperatures, the so-called tran-
sition temperature (the temperature at which a substantial drop in impact
toughness begins) is of special interest. The lower is the transition temper-
ature, the higher is the toughness.

Figure 3.43 - Influence of different microstructure and respective heat treatments

on the impact toughness at low temperatures (ISO notch specimens) of a 3.5% Ni
alloyed steel. a, Hardened by quenching in water and tempered; b, normalized and
tempered; c, normalized only; d, hardened by quenching in water only.

Certainly, when quenching workpieces of big cross section, not only mar-
tensite is obtained, but also other constituents such as bainite, pearlite, and
even pre-eutectoid ferrite, depending on the decrease in cooling rate at
quenching, below the surface toward the core of the workpiece. So after
tempering, besides tempered martensite, other structural constituents hav-
ing lower toughness are present. From a series of tests with hardened and
tempered steels with about 0.4% C, Figure 3.44 shows a general relation
between the structural constituents and the properties characterizing ductil-
210

ity (elongation and reduction of area) and impact toughness, respectively,

for different levels of yield strength. It is clear that tempered martensite
always gives the best ductility and toughness.
If compared the tempered martensite with other structural constituents, it is
worth mentioning that especially for high strength values the superiority
of fine-grained martensite structure with respect to toughness is evident.

Figure 3.44 - Elongation; (b) reduction of area; and (c) impact toughness of hard-
ened and tempered steels having about 0.4% C, as a function of structure constitu-
ents and yield strength. F, Ferrite; P, pearlite; B, bainite; M, martensite. Grain
size: ASTM 67.
 211

When comparing the impact toughness of tempered martensite at different

strength levels (different hardness levels), one can perceive the influence
of carbon content. As shown in Figure 3.44, of steels for hardening and
tempering, those with 0.20.3% C have the best impact toughness 19.

Figure 3.44 - Impact toughness as a function of tensile strength and carbon content
for the structure of tempered martensite. Grain size: ASTM 67.

The great influence of the microstructure achieved after hardening and be-
fore tempering on the impact toughness of a steel is evident from Fig. 3.45.
Appearance of pre-eutectoid ferrite or ferrite and pearlite in the structure
results in a substantial decrease in the impact toughness.
When selecting a structural steel for hardening and tempering, the ex-
pected microstructure must be considered.
Unalloyed steels for hardening and tempering, because of their low har-
denability, exhibit a high degree of section sensitivity with respect to hard-
ness distribution after hardening as shown in Figure 3.46.

19 When testing the impact toughness of a steel, one should be aware that
toughness is usually higher in the longitudinal direction (rolling direction) than in
the transverse direction. That is because some phases or nonmetallic inclusions
that are present in every steel (carbides, oxides, and sulfides) are stretched during
rolling in the longitudinal direction. In this way a textured structure originates that
has lower impact toughness in the transverse direction than in the longitudinal di-
rection. As a measure of this effect, the factor of isotropy (the ratio of transverse
impact toughness to longitudinal impact toughness) is sometimes used.
212

Figure 3.45 - Influence of the microstructure after hardening (before tempering)

on the impact toughness of EN DIN 20CrMo4 steel.

After quenching a bar specimen of 30-mm diameter of the steel in question

in conventional quenching oil, a hardness of only 40 HRC was achieved at
the surface. When specimens of the same diameter were quenched in fast
quenching oil, the hardness was 45 HRC; when quenched in 10% aqua-
quench solution the hardness was 56 HRC; and when quenched in water
containing 5% Na2CO3, it was 58 HRC as shown in Fig. 3.47. This exam-
ple leads to two important conclusions:
1. By using different quenchants and quenching conditions, different hard-
ness distributions can be obtained with the same steel grade and same
cross-sectional size.
2. With an unalloyed steel, even when the most severe quenchant is used,
for large cross-sectional sizes, the depth of hardening will be small and the
core will remain unhardened.
Because of the second conclusion, when selecting a structural steel grade
for hardening and tempering, its hardenability must always be adapted to
the workpieces cross-sectional size and the required strength level.
Fig. 3.48 shows the preferred fields for the application of some common
steel grades for quenching and tempering according to the actual bar diam-
eter and the strength level required. This recommendation is based on the
 213

assumption that a minimum impact toughness of about 50 J/cm2 at room

temperature will be achieved.
As can be seen from Figure 3.48, for bigger cross-sectional sizes (bigger
diameters) and higher strength levels, steels of higher hardenability (i.e.,
with more alloying elements) are required.

Figure 3.46 - Hardness distribution (measured) on the cross section of bars of dif-
ferent diameters made of unalloyed steel (0.52% C, 0.24% Si, 0.90% Mn, 0.06%
Cr) quenched in conventional hardening oil from 860C.
214

Figure 3.47 Hardness distribution (measured) on the cross section of bars of 10

50-mm diameters made of unalloyed steel (0.52% C, 0.24% Si, 0.90% Mn, 0.06%
Cr) quenched from 860C in water containing 5% Na2CO3.

Figure 3.48 Applicability of steel grades for hardening and tempering according
to required strength level and bar diameter. Steel designations according to EN
10083.
 215

Basics of criteria selection

Form a metallurgical point of view, quenching and tempering steel selec-
tion should be driven by hardenability and hardness to be achieved, fur-
thermore considering importance of other features as weldability or possi-
bility to realize surface quenching.
Low carbon increases toughness and weldability, but with low mechanical
strength (e.g. C25; C30; C35). Generally, increasing carbon content (e.g.
C50, C55, C60) determine higher mechanical strength, but it lowers
toughness. The decrease of toughness however is counteracted increasing
alloying elements, especially those ones with great affinity to carbon (e.g.
Cr, Mo) that allow to keep carbon content at lower values than the range
0.45-0.50% to achieve high mechanical strength (e.g. 38Cr2; 35CrMo4;
42CrMo4). If high hardness is required, the carbon content shall be in-
creased (typically at 0.50% or higher), but obviously it causes the tough-
ness.
Percentage of alloying elements determine raw material price of quenching
and tempering steels. Among typical elements added, Ni is one of most
expensive: it is added to decrease the ductile-to-brittle transition tempera-
ture.
The alloying elements, as known, affect positively hardenability and the
hardenability influence the critical diameter Dc. This means that as the
homogenized tempered martensite structure is targeted in a large part sec-
tion (remember that mechanical properties, the toughness too, drop when
highly mixed and inhomogeneous microstructure is produced, as shown in
Fig.3.45), high-alloyed steels (e.g. 39NicrMo3, 30CrNiMo8, 40NiCrMo7)
shall be preferred.

The manufacturing cycle of quenching and tempering steels

The quench and temper step is the major step in the manufacturing cycle of
mechanical part made of quenching and tempering steels.
However, the whole manufacturing cycle for quenched and tempered parts
requires further upstream and downstream steps, as shown in Fig.3.49.
The additional steps are to allow:
- The correct homogenization of chemical composition and micro-
structure in preliminary phases, before shaping;
- The control of undesired geometrical distortions that may occur in
the quenching step, to respect the dimensional accuracy of parts.

The two main issues above are discussed below.

216

Full annealing (eventually

Pre-heat treatments Normalizing + soft annealing)

Machining
Machining operations
operations
Machining operations (e.g hot forging)

Quench

Heat treatments
Temper (600C)

Finishing operations
Finishing operations (e.g. surface finisihing,
hole drilling)

Figure 3.49 Manufacturing cycle for quenching and tempering steel part.

Reduction of microstructure and chemical composition inhomogeneity

Preliminary heat treatment (Fig.3.49) is necessary to achieve as possible
homogeneous local chemical composition in raw material which enters in
the manufacturing cycle. It is not possible in practice to obtain by
steelmaking process and/or secondary semifinished operations (to produce
for example, billets, see Fig.3.50) a highly homogeneous structure as de-
sired. For example, at the end of semifinished hot operations (Fig.3.50,
right side) the microstructure of rolled bars made of medium carbon steel
is typically an inhomogeneous structure of mixed ferrite and perlite grains.
Furthermore, despite to theoretic Fe-C binary phase diagram, in the semi-
finished steelmaking process products (i.e. billets, blooms, slabs), high
variation of local chemical composition is usual. For a deeper discussion
on the morphology of microstructure obtained in solidification of steel,
reader may refer to Chapter 9 that specifically deals with the steelmaking
process, the upstream steps shown in the Fig. 3.50 and steel microstructure
evolution in solidification. Here we aim just to introduce the problem of
local inhomogeneous chemical composition as residual into hot worked
products.
It is known that the Fe-C diagram allow to predict for an euctectoidic steel
a ferritic-perlitic structure, as well as formation of ferrite and perlite grains
 217

from austenitic grains occur in conditions where atoms can diffuse (Fe and
C predominantly). However, industrial solidification produces macroscop-
ic and microscopic partitioning of chemical elements between parent liq-
uid and the growing solid crystals. A generic scheme of such a problem is
shown in the Fig.3.54. As the grains of such segregated structures recrys-
tallize during secondary hot forming processes (e.g. forging, rolling, etc.;
see Fig.3.50), micro-segregations align with material flowing imposed by
hot working; for example, they align with rolling direction or forging ma-
terial flowing into dies, leading to appearance of fibers as shown in
Fig.3.55. Particularly, such fibers are macroscopically observable and they
are the result of aligned bands. They are the product of oriented micro-
segregations that are developed parallel to the main hot working material
flowing. Such bands are observed at microscopic scale by metallographic
analysis (conducted onto polished and acid pickled metallographic sam-
ples), as shown in Fig. 3.57.
Full annealing treatment - which means high temperature and prolonged
heating - usually is preferred when micro-segregations, responsible for
banding structures, are willing to be eliminated. Full annealing in fact, in-
stead of normalizing, may produce C and Mn (see box below) re-diffusion
in order to reduce micro-segregation phenomena.
Figure 3.50 Scheme of steel making process, upstream and downstream process steps. The right side of figure shows the semifin-
ished steel made products of larger size (billets, blooms, slabs) and lower size (bars, tubes, sheets, etc.).
 Figure 3.55 Forging fibers produced in hot forged connecting rod.

Figure 3.56 Forging fibers produced in hot forged crankshaft, compared to lon-
gitudinal fibers cut by fully-machined part from round bar.

Fig. 3.57 - Banding in a UNI EN 18CrNiMo7-6 (normalized condition): a) ac-

ceptable banding for post heat-treatments; b) non acceptable banding phenomena
after normalizing, due to too much high segregation occurred in solidification pro-
cess.
220

Control of quenching distortion

As above discussed, residual stresses and associated distortions might re-
sult in an unacceptable as-quenched shape of the part which could not re-
spect geometry and final dimensions. For this reason the quenching and
tempering step is interposed between the gross shaping (i.e. hot working
coupled with the following gross machining operations) and the final ma-
chining operations for the net-shaping. Additional material is therefore left
in order to ensure a positive material envelope to take into account the dis-
tortion and allow finishing operations to realize the final shape, as draw
specifications require for the final assembling.

Fig.3.58 Control of quench distortions by additional material left be-

fore the quenching.
 221

Box Equilibrium solidification of solid-solution alloy and non-equilibrium

solidification with segregation phenomena

In Fig.3.53 is shown a binary diagram of a Cu-Ni alloy. The Cu-40% Ni is

melted and cooled, and as known solidification requires both nucleation and
growth. If the freezing is conducted throughout equilibrium steps (i.e. atomic
diffusion is fully allowed as it is time-temperature driven), the nucleation and
growing of -phase grains proceed until the solidus temperature: all of the solid
grain will contain a uniform concentration of 40% Ni, as the melting phase orig-
inally contained. This is typical for a fully miscible solid solution.

Figure 3.53The change in structure of a Cu-40% Ni alloy during equilibrium solidifica-

tion. The nickel and copper atoms must diffuse during cooling in order to satisfy the
phase diagram and produce a uniform equilibrium structure.

On the opposite, if we consider the same simple system but we cool it too rapid-
ly, atoms cannot fully diffuse and produce equilibrium conditions: non-
equilibrium structures are therefore produced in the casting. Lets see what hap-
pens to our Cu-40% Ni alloy on rapid cooling and refer to Fig.3.54.
222

Figure 3.54 The change in structure of a Cu-40% Ni alloy during non-equilibrium so-
lidification. Insufficient time for diffusion in the solid produces a segregated structure.
Notice the non-equilibrium solidus curve.

The first solid, containing 52% Ni, forms on reaching the liquidus temperature.
On cooling to 1260C, the tie line tells us that the liquid contains 34% Ni and
the solid that forms at that temperature contains 46% Ni. Since diffusion occurs
rapidly in liquids, we expect the tie line to predict the liquid composition accu-
rately; however, diffusion in solids is comparatively slow. The first solid that
forms still has about 52% Ni, but the new solid contains only 46% Ni. We
might find that the average composition of the solid is 51% Ni. This gives a dif-
ferent nonequilibrium solidus than that given by the phase diagram. As solidifi-
cation continues, the nonequilibrium solidus line continues to separate from the
equilibrium solidus. When the temperature reaches 1240C (the equilibrium sol-
idus), a significant amount of liquid remains. The liquid will not completely so-
lidify until we cool to 1180C, where the nonequilibrium solidus intersects the
original composition of 40% Ni. At that temperature, liquid containing 17% Ni
solidifies, giving solid containing 25% Ni. The last liquid to freeze therefore
contains 17% Ni, and the last solid to form contains 25% Ni. The average com-
position of the solid is 40% Ni, but the composition is not uniform. The actual
location of the nonequilibrium solidus line and the final nonequilibrium solidus
temperature depend on the cooling rate. Faster cooling rates cause greater de-
partures from equilibrium.
 223

Box - Origin of banded structures

In hypoeutectoidic steels, the ferrite-perlite banding is explained often by the ef-

fect of manganese and phosphorous, mostly manganese. During solidification,
segregation of these two elements can occur. The secondary hot working pro-
cess tend to align and distribute such elements along material flow.
The Mn acts directly on A3, stabilizing austenite by lowering A3. This causes
that, during cooling from austenitizing temperature, full ferrite structure is stim-
ulated to form in low-content Mn zones in austenite grains. As ferrite grains
preferentially form in such areas, progressively carbon is rejected to adjacent
areas. Thus, conversely, the perlite grain forms in such new zones where high
carbon content has been reached.
During secondary heat treatment the austenitic grain size can play an important
role in the appearance of bands, accordingly with the scheme shown in Fig.3.58:
as the austenitic grain size is smaller than the microsegregation inter-
spacing, ferrite grains nucleate firstly on austenite grain boundaries (and
triple points) in Mn-poor regions (with high A3 temperatures); these
grains grow in alignment with those low-Mn content (i.e. the rolling di-
rection), and then proceed.
Conversely, as austenitic grain size is greater than the interspacing o
segregation, it could result in the disappearance of banding.

Fig.3.58 Scheme of potential disappearing of bands from macrosegregation

phenomena.
224

Self-quenching (Air-quenching) steels

The UNI EN 36NiCrMo16 is a special steel of the category quenching and

tempering type series. Despite it is classified in UNI EN 10083 as quench-
ing and tempering steel, historically it has been referred as an air-
quenching steel.
As the name states, such a steel has capability to be quenched in air. This
is clearly visible by the Jominy quench-end test of this steel, which is
shown in Table 3.6.

YS min. UTS

Table 3.6 - Jominy test results and main mechanical properties for UNI EN
36NiCrMO16 round bars, various diameters.

As shown by Jominy curve, the hardness is kept at high value also at far-
end of Jominy test specimen, where normally quenching and tempering
steels exhibit a drop in hardness (at high distances from the quenched end,
the cooling curves cross the austenite-ferrite and austenite- perlite trans-
formations areas on the CCT).
In such a particular case, the high percentage of alloying elements, particu-
larly Ni, Cr and Mo (Ni ranges 3.63-4.27%; Cr ranges 1.55-2.05%; Mo
0.26-0.64) shifts the CCT curves to the right so that air-cooling curve cross
only the Ms and Mf.
 225

It is worth noticing that the chemical composition of such a steel is identi-

fied in a specific range. Particularly, the sum of percentage of C, Ni and Cr
shall be limited in the range 5 (%C+%Cr+%Ni) 7. The lower limit is
necessary to allow chemical elements to reach minimum content to shift
CCT to the right in order to allow air-quenching. The upper limit is due to
not exceed the alloying elements to such values that would cause marten-
site transformation also by furnace cooling. In this latter case, in fact, it
would be not possible for such a steel to be heat treated in order to produce
ferrite and perlite, namely the machinable structures.
Comparing the manufacturing cycle for an air-quenched part with the cy-
cle typically employed for a quenching and tempering steel part, only two
are the differences, but so relevant:
- Full annealing is the only one allowed preliminary heat treatment
to realize ferrite and perlite, the machinable structure; normalizing
is not possible since it is an air cooling treatment, that represents
quenching for such a steel;
- The tempering temperature is low, around 200C; this is possible
because as-quenched martensite structure is not brittle as for me-
dium carbon quenching and tempering steel. This fact depends on:
a) a high percentage of Ni added in solid solution to this steel
(high percentage of Ni decrease the ductile-to-brittle temperature);
b) air-quenching determine slow cooling across the large sections,
thus it results in good homogenization of the instantaneous tem-
peratures across the whole part section (i.e. low thermal induced
stresses). As direct consequence of b), the austenite to martensite
transformation starts almost at same time, thus reducing the stress-
es induced by differential expansion in the section.
226

Pre-heat treatments Full annealing

Machining operations
Machining operations
Machining operations (e.g hot forging)

Quench

Heat treatments
Temper (200C)

Finishing operations
Finishing operations (e.g. surface finisihing,
hole drilling)

Figure 3.59 Manufacturing cycle for an air-quenching UNI EN 36NICrMo16

part.

Criteria for selection

The high percentage of Ni determines for such a steel a very high price. On
the other hand despite a raw material high cost, sometimes a pay-off is
possible when the part to be constructed is of very high added value (e.g. it
is specifically customized for the scope). For example, such a steel is safe-
solution for a non-series product, with large sections and very complicated
geometry that could be subjected to non accountable deformation or,
worst case, quenching cracks. Due to its very low sensitivity to distortion
(low residual stresses develops due to air-cooling), such a steel can prevent
unforeseeable problems that would cause economic loss because of non-
recoverable geometry by finishing operations.
Another criteria for choosing the air-quenching steel is the request for very
high strength coupled with very high toughness (e.g. torsional spring bars
equipping of passenger car bogies of some high-speed trains).
Furthermore the presence of Ni in high percentage allows this high-
strength steel to be used at low temperature, avoiding brittle behavior.
 227

Spring Steels

Spring steel is a low-alloy, medium-carbon steel or high-carbon steel with

a very high yield strength. This allows objects made of spring steel to re-
turn to their original shape despite significant bending or twisting. To in-
crease yield strength, these steels are characterized by high carbon concen-
tration that ranges 0.60-1.00% (e.g. UNI EN C60, C70 and C100). Due to
high carbon content they are non-weldable steels.
To increase toughness, the carbon content is lowered and the yield strength
increase is therefore pursued by including Si. Silicon has capability to
strengthen the -Fe lattice by solid solution strengthening mechanism,
thus it can raise the elastic limit of the steel and improve the resistance to
permanent set of springs.
The NiCrMo steel, CrMo steel with excellent hardenability were de-
veloped as steel for large-sized springs.
Table 3.7 shows the chemical compositions of spring steels designated or
recommended by several countries. Oil quenching and tempering can be
normal heat-treatments, while water quenching can be suitable for low
carbon steels whose the carbon content is limited to 0.5% (e.g. UNI EN
C55), because of risks of quenching cracks.
CrV steels have good hardenability with high toughness, and is used for
higher hardness application.
The SiCr steel is mostly used for oil tempered wire material of cold-
formed springs. CrMo steel with higher hardenability than the boron add-
ed.

Table 3.7 - Chemical composition of some spring steels.

228

Summarizing, a classification by Steel Grade is the following:

Carbon Steel
Low Alloy Steel
o SiMn Steel
o CrV Steel
o SiCr Steel
o High-Carbon SiCr
o SiCrV Steel
o SiCrNiV Steel
o SiCrVMo Steel

Or a classification by cross-sectional profile:

Round Section
Non-circular Section
o Egg-shaped profiles and similar profiles
o Trapezoid (mainly for press die)
o Rectangle (mainly for press die)

Examples of cross-sectional profiles of non-circular wire are shown in Fig.

3.60.

Fig. 3.60 - Example of cross sectional profiles of egg-shaped spring wire

 229

Heat treatments for steels and manufacturing cycle of springs

The manufacturing processes for steel springs can be divided into: a) cold
coil spring (Fig.3.61), a cold work process where wire is fed through roll-
ers and fulcrum pins and travels around a fixed mandrel to form a coil; b)
hot worked springs (wound and leaf springs) where the rolling of the
springs is performed as a hot process (Fig.3.62).

Fig. 3.61 Cold coiling of cold wound spring.

Fig. 3.62 Coiling of hot wound spring.

The general manufacturing cycle of steel made heat treated parts (i.e. pre-
heat treatments, machining operations, heat treatments, finishing opera-
tions, refer to previous section Quenching and tempering steels) is ad-
justed for cold and hot worked as illustrated in the fig.3.63.
230

Full Annealing or shperoidization Full Annealing or shperoidization

(Normalizing + soft annealing (Normalizing + soft annealing
if possible) Pre-heat treatments
if possible)

Cut to lenght Cut to lenght

Pickling Machining operations

(Cold) Coil
(Hot) Coil
Patenting
End-forming
Quench

Heat treatments
Stress relieve
Temper (450C)

Preset (if required)

Grind (if required)

Finishing operations Grind (if required)
Shot peen

Shot peen

Cold Wound Hot Wound

Spring Spring

Fig. 3.63 Manufacturing cycles of cold and hot wound spring.

Manufacturing process of leaf springs (Fig.3.64) is similar to hot wound

spring manufacturing cycle, where the hot coiling step is substituted by
forging, and assembling of leafs has to be added after finishing operations.

Fig. 3.64 Forging of a single leaf spring.

 231

Specifically regarding with heat treatments performed, most typical pre-

liminary heat treatment is spheroidizing annealing (sometimes, full anneal-
ing and normalizing can be carried out). The spheroidizing annealing is
keeping the materials around the A1 transformation temperature for a cer-
tain time and cooling to the A1 transformation temperature by the cooling
speed of 1020C/hr. The purpose is to have the cementite precipitates
changed from the lamellar or net shape to spherical shape. Since this heat-
treatment can soften the material by a great extent, this can be applied
when the formability of materials is required.
As shown in the scheme of Fig.3.63, quenching and tempering treatment is
conducted to improve the spring characteristics. During quenching, mate-
rial is heated to the temperature about 3050C higher than the A3 trans-
formation temperature, and immersed into water or oil (sometimes air
cooling in high alloy steel) and cooled rapidly, to have martensite struc-
ture. Since the solution content of carbon is high, there are many lattice de-
fects (dislocation) and the crystal structure is fine, the hardness of the mar-
tensite of medium-high carbon steel is as high as 6065 HRC. The spring
steel has a high yield point; besides suitable high ductility is required,
therefore, it is tempered at about 450C.
As shown in the fig.3.63 the pre-heating and the quenching and tempering
treatments for the spring steels are only two steps of a more articulated
manufacturing process that requires some further steps, mostly patenting,
pickling and drawing as they are shortly illustrated in the next.

Patenting
Patenting is heat treatment process eventually conducted to restore ductili-
ty resources of materials that could be highly work hardened during cold
coiling steps (work hardening causes ductility decrease that could lead to
cracks during cold coiling steps). Most frequently it is conducted on high-
carbon steel wires. By patenting, they are continuously transformed to mi-
crostructure of fine pearlite, either by isothermal cooling or continuous
cooling. In practice, wire rod, traveling continuously, is first held above
the A3 point, and subsequently cooled down below the A1 point to be
transformed to pearlite. Figure 3.64 shows a schematic of TTT diagrams of
this heat treatment. Several kinds of cooling media, used in the patenting
for the transformation of wire.
232

Fig. 3.50 - Schematic of patenting in TTT diagram.

Pickling
Pickling, either by hydrochloric acid or sulfuric acid solution, is generally
provided on patented wire and hot-rolled rod to remove their surface scale
(ferrous oxide film).

Shot peening
It is well known (refer to Chapter 2) that most fatigue failures initiate at
the surface as a crack and propagate under cycling until failure occurs. For
these cracks to initiate, the surface must be in tensile stress and they will
not propagate through a compressively stressed surface. If a residual com-
pressive stress is produced in the surface, the tensile stress created by the
applied load must first overcome the residual compressive stress before the
resultant surface stress becomes tensile.
Shot peening is the most effective and inexpensive method to produce the
desired residual compressive stress at the surface of components. This in-
volves bombarding the surface with rounded particles propelled at high ve-
locity (fig. 3.51a), 60 m/sec. Each shot particle, with controlled shape and
of uniform size, acts as a peening hammer to cold work the surface and
produce compressive stresses (fig.3.51b and fig.3.52).
 233

(a)

(b)

Fig. 3.51 Shot peening: a) process; b) scheme of effect on peened surface.

The commercial origins of the technique go back to the automobile indus-

try of about 1930, and today almost all automobiles use shotpeened valve
springs, and, in many cases, suspension springs. The peening process is
relatively inexpensive and has proven capable of increasing operating life
by five to 10 times or more when compared to unpeened springs
(Fig.3.53).
234

Fig. 3.52 Compressive stress induced in the peened surface of a shotpeened

beam (A) prevents tensile stresses from occurring after a bending moment is ap-
plied to the part.

Fig. 3.53 Shot peening applied to surfaces exposed to high bending loads, such as
carburized and hardened gear teeth, increased the life considerably. For example,
the life of teeth subjected to loading of 80,000 psi (about 500 MPa) increased from
270,000 cycles before shot peening to 3 million cycles after shot peening.
 235

Criteria selection
As the increasing in alloying element content is key cost-driver, carbon
steel are used when reduced section have to be realized and toughness is
not crucial. Carbon steel with medium and high carbon content are particu-
larly indicated for cold-worked springs.
For hot worked large section size springs, Si and Si-Cr alloyed steel are
used (increased YS and hardenability of steel).
In case high toughness value are targeted, e.g. safe component for trans-
portation, Ni- alloyed spring steels are used.

Surface hardening of mechanical components

There are some applications where it is necessary to have a hard surface

for certain depth below surface but a tough, shock-resistant inner core.
This is the case, for example, of such components that can be subjected to
contact fatigue (refer to Chapter 2) as for example, cams, gears, and shafts.
Such components require hard layers on surfaces to resist but tough inner
cores to resist shock.
As known it is not possible to match two opposite requirements for metal,
namely having high hardness and contemporarily high toughness. In fact,
while a low-carbon steel containing 0.1 wt% C will have a very tough
core, its surface hardness will be low also after quenching. On the other
hand, a euctectoidic steel containing 0.8 wt% C will have a very high sur-
face hardness after quenching, but the core will not be tough and shock re-
sistant.
Thus, to satisfy design requirements there are two approaches to this prob-
lem. One is to use a medium-carbon steel and only quench harden the sur-
face through local heat treatment. The other approach is to diffuse some
elements, namely locally adding chemical elements onto surface of a base
steel, so to strengthen the top layer surfaces acting on various metallurgy
strengthening mechanisms we will discuss in depth in the next.
Despite two approaches pursue same objective, namely increase hardness
on surface but keeping tough subsurface, they distinguish since the first
method, called surface hardening of steels, does not change the chemical
composition of steels, while the second approach needs to change local
chemical composition, in order to strengthen lattice. Changes in chemical
analysis on top layers are produced by feeding elements like carbon C and
nitrogen N to steel by a temperature-time process i.e. thermochemical
treatment - that allows to increase diffusion on steel surface. If carbon is
236

added, thermochemical process is called carburizing; if nitrogen is added,

we talk about nitriding process.

Surface Hardening by Localized Heat Treatment

It is conducted generally onto parts that have been hardened by conven-
tional quenching and tempering process in order to produce the desired
core hardness 20. The surface is then reheated into the austenitization range
and immediately quenched to produce fresh as-quenched martensite (i.e.
non tempered martensite) at the surface. Additionally to the hard surface,
the surface layer is usually in a state of compression, which improves fa-
tigue cracking resistance.
The objective of surface hardening is therefore to austenitize the steel at
and near the surface and then rapidly quench by water to produce as-
quenched martensite. Occasionally a low temperature tempering not
higher than 100C - is allowed to relief residual stresses.
Three techniques are usually employed to heat up and rapidly austenitize
surface, to prepare it to water quenching:
surface heating by a gas flame created by burning acetylene, pro-
pane, or natural gas;
induction hardening technique;
laser hardening.
Mostly the 3 techniques distinguish because of is the heating source used.

Flame hardening. It is a simple method since an operator or automated

systems - uses a torch to heat up surfaces while a quench jet follows right
behind the torch to rapidly quench surface. The relatively low thermal
conductivity of steel enables the surface regions to be austenitized using
high rates of energy input without the interior being significantly affected.
Flame hardening is a very rapid and efficient method for producing cases
as deep as 5-8 mm. However, unless the process is automated, it can be
difficult to control the case depth, and prolonged heating can result in a
case depth deeper than desired.

20 Most frequent in industry applications normalized parts instead of quenched

and tempered, are surface hardened, to reduce process costs. However, such pro-
cess is not suggested by metallurgical point of view since normalized structure are
not sufficiently homogeneous and tough, two main factors that can counteract lo-
cal distortions and surface cracks.
 237

Induction Hardening. In induction hardening, heat is supplied by surround-

ing the part with an inductor coil carrying a high-frequency current in the
range of 2 to 500 kHz. Higher frequencies result in a shallower depth of
heating and are therefore used for smaller-diameter workpieces. The coil
acts like the primary winding of a transformer. The oscillating field pro-
duced by the induction coil induces magnetic field electrical eddy currents
in the steel within a certain depth of the outer surface, called the skin depth
(Fig.3.53), which decreases as the frequency is increased. The eddy cur-
rents produce Joule resistance heating in the skin depth that rapidly raises
the surface temperature. The amount of heat released is proportional to the
square of the current such that QI2Rt also called the Joule heating
(obeying to Joules first law of conductive mean heating).

Fig. 3.53 Principle of induction heating.

As in the case of flame hardening, heating system is equipped with

quenching water jet in order to rapidly provide quenching of austenitized
surfaces (Fig.3.54). Induction hardening is generally used to produce rela-
tively thin cases. Larger depths, such as 3 mm, can be attained by leaving
the current in contact with the surface for a longer period of time and by
operating at lower frequencies. The case depth can be controlled more ac-
curately in induction hardening than flame hardening process, since the
depth can be controlled by varying the frequency of the current and the
amount of time the current is in contact with the part (the higher the fre-
quency, the more the current tends to flow over the outer surface only).
238

Fig. 3.54 Induction hardening onto a shaft. Coil and water jet system are syn-
chronized in their relative movement with the heated shaft.

Laser hardening. Laser heat treating is a highly selective hardening tech-

nique in which a spatially well-defined beam of laser light is absorbed near
the surface, causing rapid heating (heating is limited to the illuminated ar-
ea) and penetration into the bulk material is limited. Laser hardening al-
lows for a highly defined zone of influence without affecting neighboring
surfaces. High cooling rates make fine structures and high levels of hard-
ness possible. Intricate contours are easily hardened using lasers due to the
flexible beam guidance possibilities. The maximum thickness obtainable
with the laser hardening is 3 mm for steels. In the case of objects of high
precision, limiting the layer thickness to 0.2 mm positively result in con-
trolling local distortions since they are kept so low as they do not require
any post- processing treatment.

Manufacturing cycle for surface hardened product

In the following figure, Fig.3.55, it is shown the manufacturing cycle for a
surface hardened product.
 239

Full annealing (eventually

Pre-heat treatments Normalizing + soft annealing)
Basic quenching and tempering

Machining operations
Machining operations Machining operations
manufacturing cycles

(e.g hot forging)

Quench

Heat treatments
Temper (600C)

Finishing operations
Finishing operations (e.g. surface finisihing,
hole drilling)

Surface quenching

Stress relief (optional)

Fig. 3.54 Manufacturing steps for surface hardened parts.

Criteria for steel selection for surface hardening

When high hardness on surface top layer is targeted, and this is the major
objective, a high carbon content is necessary. Surface hardening processes
in fact exploits strengthening mechanisms typical of an as-quenched mar-
tensite, where the carbon content is key feature for increasing as-quenched
martensite. However too much high carbon content would result in too
much high body centered tetragonal (BCT) lattice distortions; high lattice
distortions, coupled with its own brittle behavior, can however result in
cracking of hardened surface layers. To mitigate this problem usually the
highest carbon content is limited to about 0.60 wt.% (e.g. AISI 1055).
On the opposite, if control of surface local distortions and deeper hardened
layers are favored instead very high hardness onto surface, medium carbon
content steel is preferred (ranging from 0.35 to 0.50 wt%, e.g. AISI 1035,
AISI 1045) is therefore usually selected.
Furthermore, when the hardness profile below surface, not only the hard-
ness on top layers, is a key feature for designers, alloyed steel with higher
hardenability are employed instead cheaper carbon steels. Alloyed steel
240

which are mostly used are: UNI EN 45Cr2, UNI EN 38 Cr4, UNI EN 37
CrMn4, UNI EN 41CrMo4 and UNI EN 40NiCrMo3, listed by increasing
their own hardenability and their cost. It is important to notice that, when
rapid cooling is guaranteed after heating up the parts, so rapid as critical
interval of temperatures for the tempering brittleness (450-550C) are rap-
idly passed, Mo can be eliminated from steels for surface quenching, in
order to reduce costs.

Carburizing steels
Carburizing is conducted by heating a low-carbon steel into the single-
phase austenitic field, generally around 900C, where the steel has a high
solubility for carbon. Carbon is then absorbed onto surface layers, which
increase progressively carbon content and thus hardened during the follow-
ing quenching phase, as shown in the scheme of generic carburizing cycle
in Fig. 3.55.

T Carbon adsorption

(Carburizing temperature) 920C

Ac3 (core)
(Quenching temperature) 860C Ac3 (surface )

(Tempering temperature) 180C

Time
Carburizing time Quenching Tempering
time time

Figure 3.55 Scheme of carburizing temperature vs time plot diagram.

After quenching, the part is extracted from oil chamber and moved to low
temperature furnace where it is tempered at low temperature, around
180C, in order to relieve stressed but avoiding carbon to diffuse out from
martensite tetragonal lattice, thus vanishing the carburizing and quenching
results in terms of high hardness.
The final result of carburizing process is therefore hard high-carbon case
on top of a tough low-carbon steel core.
 241

Steels used for carburizing usually have carbon contents of approximately

0.2 wt% (the lower is carbon content of base material, the higher is the
carbon diffusion rates), with carburized cases containing up to 0.8 to 1.0
wt% C.
As stated, and as it is usual for any process that involves chemical species
diffusion, the carbon concentration gradient of carburized layers is a func-
tion of the carburizing temperature, exposure time and carbon concentra-
tion of outer atmosphere.
From an analytical point of view, the result of carburizing process in terms
of hardened layer can be approximated by a simplified formula developed
by Einstein:

(eq.3.1) Case Depth = 2Dt

where D is the diffusion coefficient of carbon into iron. However, most

precisely, the process is governed by diffusion laws, the two Ficks laws.
The increasing concentration of carbon during carburizing is approximated
by the equation:

(eq.3.2)

Where:
C(x,t) is the carbon concentration at certain depth x and fixed time t;
C0 is the initial condition, namely the carbon content before carbu-
rizing starts (i.e. the carbon content of base core material);
Cp is the carbon potential of atmosphere, namely the measure of the
concentration of carbon atoms in carburizing outer atmosphere 21,

21 While carburizing can be done in a solid, liquid, or gaseous medium, gas car-
burizing processes are mostly industrially used, since they can be highly automat-
ed and controlled and for series production (here in the following we refer to this
type of carburizing process). Gas carburizing uses either natural gas, propane, or
butane as carrier gases to realize the carbon potential in atmosphere, accordingly
with following relations:
2CH4 + O2 + 4N2 2CO + 4H2+ 4N2
CO + H2 C + H2O
Fe + CH4 Fe (C) + 2H2
Fe + CO + H2 Fe (C) + H2O
242

expressed in percentage. The meaning of carbon potential Cp is the

following: it is the carbon concentration, in weight %, which can be
asymptotically obtained on top layer surface for prolonged exposure
times - e.g. carbon potential 0.7% means that the outer atmosphere
is capable to diffuse 0.7% of carbon in top layer of steel treated for
prolonged time.

As shown by the scheme in Fig. 3.56, during the carburizing phase, carbon
diffuses slowly into the bulk of the part, and a carbon concentration gradi-
ent below the surface is established. Possible carbon profiles are shown as
examples in Fig.3.57. As the 3 carbon profiles illustrates, within the steel
part, the high-carbon surface has a higher carbon potential than the low-
carbon interior, since carbon tends to diffuse from the surface toward the
center 22.

C atoms Fe- lattice

Figure 3.56 A simplified scheme of carburizing diffusion phenomena from outer

atmosphere into the steel part.

22 It is worth mentioning the carburizing atmosphere shall have a higher carbon

potential than does the surface of the steel, to avoid carbon flowing out from the
carburizing surface. Control of carbon potential is vital for correct carburizing of
surface: if, during processing, the atmosphere carbon potential should fall below
the carbon potential at the steel surface, then carbon will be removed from the
steel (decarburization).
 243

(b)

Figure 3.57 a) Scheme of carburizing process, where carbon atoms diffuses from
high-carbon concentration atmosphere (i.e. high carbon potential mean) into aus-
tenitic lattice; b) 3 different carbon profiles obtained by varying: carbon potential
of external atmosphere (i.e. 0.50%, 0,75% and 1.10%), exposure times (i.e. 2h, 4h,
8h, 16h).

Carburizing cycle description

Looking at the cycle in Fig.3.55, four main stages are recognized:
1. The carburizing phase; it is conducted in potential carbon atmos-
phere at high temperature, where carbon absorption onto steel sur-
face and diffusion to deeper layers is realized. The temperature is
set around 900C, thus as higher as possible in austenite phase to
facilitate the diffusion of carbon (i.e. the higher expansion of -Fe,
the higher is diffusion of interstitial carbon atoms), but not exceed-
ing that temperature to which grain coarsening might start (safely
temperature should be kept lower than 1000C);
2. Targeting the correct quenching temperature. The carburizing
temperature is too high for quenching stage, thus the part shall be
cooled to correct quenching temperature. Because of the surface
and core have two different carbon content, the A3 temperatures
are different. In this case it is set the correct temperature the lower
A3 of the two ones. In other words, it is preferred to target the cor-
rect quenching temperature of the high carbon content layers, as
they are more critical for quenching stage. Despite temperature in
this steady-state phase is lower than A3 for the core of parts, lim-
ited times allow to prevent austenite ferrite transformation to
start.
244

3. Once a high carbon content - approximately the euctectoidic con-

tent - is achieved on top layers, the part is oil-quenched. The
quenching phase has the scope to produce high-carbon content and
hard martensite on top layers (i.e. case hardened), while maintain-
ing low-carbon content and tough martensite within the part (i.e.
core) - at least, mixed martensite-bainite is produced at core, de-
pending on hardenability of steel and the part size.
4. The final stage consists in reheating quenched parts for tempering
treatment, which shall be conducted at low temperatures (usually
around 150-180C). Tempering is required to reduce residual
stresses develop onto surface layers by quenching.

Design aspects of carburizing

Typical case depths range from few millimeters (e.g. around 1-2 mm) to
3-4mm. in the latter case prolonged carburizing times are required. Since
carbon content on top layers is targeted around 0.8-1.1 wt.%, and because
of the low tempering temperature, surface hardness usually obtained is
about 850-900 HV (about 64-63 HRC). Effective case depth (see Fig.3.57)
is function of both carbon profile and hardenability of base steel.

HV

550 HV

Core hardness

Effective depth (mm)

Figure 3.57 Typical hardness profile for carburized part and definition of effec-
tive depth.
 245

Manufacturing cycle for carburizing steel parts

The manufacturing cycle for carburizing steel parts is shown in Fig.3.58.
Similarly to manufacturing cycle adopted for quenching and tempering
steels which can be considered our base reference parts that are carbu-
rized require additional materials to be left on parts, to mitigate distortion
problems that may occur during the critical quenching step.

Full annealing (eventually

Pre-heat treatments Normalizing + soft annealing)

Machining operations Machining operations

(e.g hot forging)

Carburizing (900C)

Quenching (860C)
Heat treatments

Tempering ( 180C)

Finishing operations
Finishing operations (e.g. surface finishing,
hole drilling)

Figure 3.58 Manufacturing cycle of carburizing steels.

Criteria for carburizing steel selection

Main criteria for orienting choice of carburizing steels are design factors
like top surface hardness, effective case depth and case hardened tough-
ness, raw material and process costs.
Cheapest solutions in terms of raw material and reduced machining costs is
represented by carburizing carbon steels, like UNI EN C10 or UNI EN
C15 (AISI 1010 and AISI 1015). However such steels have a very low
hardenability and they require to be water quenched. Despite the water
quenching is benefit in terms of further reduced process cost, instead of oil
quenching, this restrict part size to small dimensions and geometry to be as
246

simple as possible. As size and shape complexity increase, residual stress-

es produced onto part by rapid cooling might increase the risks of non-
restorable distortions and, at least, cracks (such risks are also increased be-
cause of the low mechanical strength of low carbon austenite).
A first conclusion is that, as the part size increases, oil quenching is re-
quired, and alloyed steels are therefore used. Considering toughness as ma-
jor feature together with cost reduction, the UNI EN 16MnCr5 is one pos-
sible solution; because of low carbon content, such a steel is easy to hot-
work and has good machinability (presence of higher content of Mn).
Addition of Cr increases hardenability, is compared to carburizing carbon
steel, but martensite is limited to low-medium thickness (not more than 20
mm). Since such a steel can suffer of temper embrittlement, this problem is
solved by using the UNI EN 18CrMo 4, which has similar hardenability of
UNI EN 16MnCr5.
Comparable hardenability, but higher toughness, is achieved by the UNI
EN 16NiCr4, due to presence of Ni. Costs in this case increases.
For automotive applications most frequently are used steels with higher
percentage of carbon, alloyed with Cr for increase hardenability (up to 60-
70mm), and Ni for increasing toughness, like the UNI EN 20NiCrMo2.
This steel has high carbon content (it targets 0.2% wt. limit for carburizing
steels) that increases core and surface strength, while its moderate-high
hardenability allow it is used for complicate shape.
Finally, the UNI EN 18 NiCrMo 5 and UNI EN 18 NiCrMo 7 series are
most used carburizing steel. Despite higher raw material costs, they are
considered safe materials to oil-quench due to high toughness (i.e. high Ni
content) and high hardenability with good machinability.
It is important to highlight that the low-temperature tempering stage limits
the service temperature below the tempering temperature. If higher, ser-
vice temperature would cause decay in surface hardness due to carbon dif-
fusion from BCT lattice, and its partial transformation into -Fe, the duc-
tile BCC lattice

Nitriding steels
Nitriding process has same scope of carburizing process: develop onto
tough base materials hard surface layers, to certain depth. Similarly, nitrid-
ing pursues such an objective by locally changing chemical composition of
the base steel, as it is usual for thermochemical processes. In the specific
case, the chemical specie which is absorbed onto surface is nitrogen N, a
small interstitial atom, too, capable to diffuse in iron lattice. As the N is
absorbed and it diffuses within the part, it combines with Fe to form small
 247

particles we call nitrides. Such particles are randomly dispersed into matrix
and they are capable to intercept dislocation, providing a precipitation
hardening strengthening effect. This is the strengthening mechanism by
which nitriding process increase hardness, and mechanical strength, on
surfaces.
By this fact, we can immediately recognize great differences in terms of
metallurgical strengthening phenomena existing between carburizing and
nitriding. While carburizing process strengthens the carbon-enriched sur-
face layers by exploiting lattice transformation, from austenite to marten-
site BCT lattice, by quenching, nitriding process strengthens the pre-
existing -Fe (BCC lattice) by precipitates. To make reader clear such
great difference, it is worth mentioning that nitriding is conducted at
around 500C, for one reason that will be explained soon in the next.
By this fact, instead carburizing which requires that the steel be quenched
and then tempered, nitriding is done at temperatures largely below the aus-
tenitization temperature. Some direct benefits of this fact are:
a) the distortion inherent in the martensitic transformation during harden-
ing is completely removed; thus, nitriding allows excellent dimensional
control;
b) since the nitriding temperature is below the tempering temperature of
quenched and tempered steels, nitriding can be conducted as final stage to
increase hardness onto very optimized structures that are typical of the
quenched and tempered steels.
Similar to carburizing, nitriding can be done in several different media;
here in the following we refer to industrial gas carburizing. In gas carburiz-
ing, nitriding is conducted in atmospheres that decompose ammonia NH3
to provide nitrogen to the surface by catalytic reaction:

(eq.3.2) NH3 N+3H

The nitrogen is therefore absorbed and it diffuses into the steel. At top sur-
face atomic nitrogen combines with the iron to form iron nitrides Fe2N and
Fe4N types. These phases are clearly visible in the iron-nitrogen phase dia-
gram shown in Fig.3.59. Firstly, by this diagram it is possible to explain
why nitriding temperature must not exceed around 500C. This limitation
is required to nitride steel with safe margin to keep steel below the euctec-
toidic temperature that is set at 590C. If the euctectoidic temperature is
overpassed, the structure turns into Fe- and the following cooling would
proceed by the euctectoidic transformation from Fe- into lammellar
248

euctectoidic structure, called braunite, that is too much brittle to be accept-

ed onto mechanical parts.

Phases:
N(Fe-): Nitrogen in solid solution of Iron
(Fe4N): lattice structure CFCnitrogen concentrdion max. 6%
(Fe2N): lattice structure EC, high nitrogen concentration over 10%

Figure 3.59 Iron-Nitrogen phase diagram. They are highlighted by circles the
two high nitrogen content phases that form onto surface, the ' (i.e. Fe4N) and the
(Fe2N) phases.

By diagram in fig.3.59 we can recognize:

The -Fe phase, namely nitrogen in solid solution of Fe BCC lat-
tice;
The phase, interstitial compound Fe4N, with nitrogen concentra-
tion max 6% wt;
The phase, interstitial compound Fe2N, with very high nitrogen
concentration over 10%.
FexN compounds that form onto surface during nitrogen absorption and
are also visible by metallographic analysis, as shown in Fig3.60.

POUROS ZONE

COMPACT ZONE

DIFFUSION LAYER

Figure 3.60 Nitrided layer structure: a) simplified scheme of surface structures;

b) metallography at Scanning Electron Microscope of outer layers.
 249

The metallurgical phenomena involved during surface compounds for-

mation are below summarized:
Nitrogen absorbed onto surface form compound layers, nitride
(Fe2N) and nitride (Fe4N) with minor presence of complex ni-
trides if alloying elements when alloying element with great affinity
with nitrogen are present (mainly Ti, Al, V, Cr, Mo).
The continuous decomposition of (Fe4N) at interface with diffu-
sion zone feed N for diffusion into solid solution Fe- and for-
mation of complex nitrides, when alloying element with great af-
finity with nitrogen are present (mainly Ti, Al, V, Cr, Mo).
It is clear therefore that the presence of alloying elements with great affini-
ty with nitrogen allow formation of complex and stable complex nitrides;
these nitrides are major responsible for increasing strength and hardness on
top surface layers interested by nitrogen diffusion.

Design features of nitriding parts

Due to low treatment temperature, the diffusion of nitrogen is low. This
fact limit in practice nitriding case depths, that are thin if compared to car-
burizing. Usually case depth is less than 0.80mm, even though nitriding
times can exceed 100 h.
On the contrary, the surface hardness can achieve very high values, rang-
ing from 900HV to 1200 HV, the latter when Al is added (aluminum forms
very fine AlN precipitates). Molybdenum, in addition to its contribution as
a nitride former.
During single stage nitriding treatments, in which a single nitriding atmos-
pheric composition is maintained, a white layer of iron nitride is formed
(i.e. the porous layer shown in Fig.3.60).
This iron nitride layer is hard but can crack and spall. When this is unac-
ceptable, the layer is removed by surface grinding. Alternatively, a two-
stage nitriding process can be used in which, after the first stage, the at-
mospheric conditions are changed so that iron nitride no longer forms at
the surface, and the existing layer is removed as the nitrogen dissolves into
the steel (Fig.3.61).
250

Figure 3.61 Effect of one- and two-stage nitriding on white layer. (a) Single
stage, gas nitrided for 24 h at 525C. (b) Double stage, gas nitrided for 5 h at
525C followed by second stage at 565C for 24 h.

Together with high hardness advantages (nitriding onto Al alloyed steel

produces the hardest cases) other important features can be exploits by de-
signers. No heat treatment is required after nitriding, which, along with the
low temperatures employed, minimizes warpage and distortion.
Nitrided parts have good elevated temperature resistance. Reheating parts
to 540 to 595C for short periods does not affect their hardness, while
long-term exposures to 315 to 425C will affect carburized but not nitrided
parts.
The disadvantages of nitriding are primarily the long cycle times and the
inherent cost. A 0.75 mm case depth may take several days to produce, and
ammonia gases are more expensive than the natural gases used for carbu-
rizing.
Other disadvantages include some size growth that occurs during nitriding,
and the extreme hardness produced precludes machining after nitriding.
However, this problem is well mitigated by skilled heat treaters, since the
increase in volume during nitride formation is homogeneous and without
distortion (it depends only by formation of nitrides inside lattice, and not
because of structure transformation). Thus, heat treater is capable to ana-
lyze by preliminary sampling how much will be expansion of surface lay-
ers, so allowing designer to take into account this final volume expansion.

Manufacturing cycle for nitriding parts

In the following Fig.3.62 is shown the manufacturing cycle for nitride
parts. As it is shown, due to absence of distortions and temperature below
 251

600C, the nitriding process can be conducted as final stage, onto finished
parts.

Full annealing (eventually

Quenching and tempering manufacturing cycle

Pre-heat treatments Normalizing + soft annealing)

Machining operations
Machining operations
Machining operations (e.g hot forging)

Quench

Heat treatments
treatments
Temper (600C)

Finishing operations
Finishing operations (e.g. surface finisihing,
hole drilling)

Nitriding (500C)

Figure 3.62 Manufacturing cycle for nitride parts.

Criteria for nitriding steel selection

Nitriding steels are commonly high hardenability steels, since they have
features that are typical of medium-carbon and alloyed quenching and
tempering steel. The presence of elements like Al, Ti, V, Cr and Mo to
avoid temper brittleness have double positive effect: they increase harden-
ability by usual shifting to the right the CCT curves, and they form dis-
persed and highly stable nitrides.
Among nitriding steels, UNI EN 31CrMo12 has lower hardenability than
the most used UNI EN 41CrAlMo7, and lower surface hardness.
When higher toughness at core is required with high surface harness, the
UNI EN 34CrAlMo7 is usually employed as substitute of the UNI EN 41
CrAlMo7 since it has less carbon that causes higher toughness in the BCT
martensite.
252

Regarding with the industrial practices, despite UNI EN 42CrMo4 is not a

nitriding steels but a quenching and tempering steel, it is mostly used in ni-
triding process of automotive parts because of satisfying surface hardness
obtained. Despite 900 HV surface hardness is actually similar to what it is
usually obtained by carburizing, one advantage is nitriding allows to avoid
any distortions. This fact is relevant in case of high-reliable large series
production. Furthermore, due to higher hardenability and higher carbon
content of martensite at core, higher strength are achieved than typical car-
burizing parts.
 253

Chapter 4 Tool Steels

Tool steels are very special steels used to shape, cut, and form an extreme-
ly wide variety of metals and other materials under demanding conditions.
The earliest tool steels were based on plain carbon steel, but in the mid-
19th century and early in the 20th century , highly alloyed tool steels were
developed to meet very stringent requirements for specific applications.

Classification of tool steels

Tool steels have been organized into groups that have evolved to perform
specific functions, such as:
forging,
cold working,
die casting,
high -speed machining,
in a variety of operating conditions. Within each group may be many
grades that differ slightly from one another to accommodate somewhat dif-
ferent processing requirements, operating conditions, or work materials.
Various systems are used to classify tool steels. The most widely used sys-
tems are the American Iron and Steel Institute (AISI) and in Europe the
UNI EN standard for classifying alloying steels.

The AISI classification

AISI arranges tool steels into groups that are based on prominent charac-
teristics such as alloying, application, or heat treatment. Table 4.1 lists nine
main groups of tool steels and their identifying letter symbols.
254

Table 4.1. Main Groups of Tool Steels and AISI Letter Symbols.

Important properties required for various applications

As defined by their classification - accordingly to Table 4.1 - the field of
application of tool steels includes machining, cutting, forming by stamp-
ing, pressing or forging, forming of shapes from the molten state in glass,
plastics, or metals, and die casting.
Therefore, tool characteristics are provided by heat treatment, quenching
and tempering. Final properties thus depends on tempered martensite mi-
crostructure and a variety of fine carbides, due to chemical elements add-
ed.
Specifically, the important properties of tool steels are:
constant hardness at low and high temperatures,
hardenability,
retention of hardness (at operational temperature);
high compression strength and pressure resistance,
fatigue strength,
toughness at operational temperatures,
wear resistance at room and high temperatures,
thermal fatigue resistance,
corrosion resistance

Hardness is the most important characteristic of steels from which their po-
tential application can be recognized. The wear resistance of tool steels in-
creases with increasing hardness, and toughness is reduced with increasing
hardness. Normal hardness values vary between about 200 HV for glass-
mold steels at the lower level, and 900 HV for forming and machining
tools at the upper level.
Carbon content and elements with higher carbon affinity such as Mo, Cr,
V and W are the dominant factor controlling the strength of tempered mar-
tensite, as they can form fine dispersed carbides during tempering stage
(refer to Chapter 3, as basics of quenching and tempering strengthening
phenomena are described). However, while the hardness for steels usually
rapidly decreases with increasing temperature, as Class 1in Fig.4.1 shows,
tool steels exhibit various behavior (see Class 2 to 4).
 255

Figure 4.1 - Four major types of hardness versus tempering temperature in

tool steels.

Particularly we observe tht:

Class 1 is typical of carbon and low-alloy tool steels in which the
hardness is decreasing progressively with increasing temperature
due to the precipitation and coarsening of cementite, or of other
low-alloy carbides (this is also typical of quenching and tempering
steel);
Class 2 is characteristic of medium - to high-alloy cold-working
die steels in which the alloying addition retards carbide precipita-
tion and related softening. Curves between Class 1 and Class 2
could be obtained for low - to medium-alloy steels.
Class 3 is representative of highly alloyed high-speed steels in
which secondary hardening occurs at high-tempering tempera-
tures. The final hardness of these steels could exceed that in the
untempered condition.
Class 4 is representative of the medium - to high-alloy hot
working tool steels that exhibit a secondary hardening, as is the
case with Class 3. In Class 4, the as-quenched hardness is lower
than that of Class 3 due to its lower carbon content.

Secondary hardening of tool steels

256

Secondary hardening is a result of the transformation of retained austenite

to martensite on coo ling from the tempering temperature, and of precipita-
tion of an ultrafine dispersion of alloy carbides. Tungsten, vanadium ,
chromium, and molybdenum that are the strong carbide forming elements
are most commonly used to achieve secondary hardening. To take ad-
vantage of their precipitation characteristics, they must be dissolved in aus-
tenite during the austenitizing treatment in order to be incorporated into the
martensite formed during quenching with sufficient supersaturation for
secondary hardening during tempering. for secondary hardening during
tempering. Figure 4.2 through Figure 4.3 show the effect of strong carbide
-forming elements on the secondary hardening of 0.5% C tool steel.
The tempering treatment should be performed as soon as possible after
quenching, and heating to tempering temperatures should be slow to en-
sure temperature homogenization within the tool steel and the prevention
of cracking. Slow cooling in still air is also recommended to minimize the
development of residual stresses.

Figure 4.2 - Secondary hardening caused by alloy carbide precipitation produced

by V additions.
 257

Figure 4.3 - Secondary hardening caused by alloy carbide precipitation produced

by chromium additions.
Manufacturing cycle of tool steels
The manufacturing cycle of tool steel requires heat treatments is similar to
quenching and tempering steel cycle.
Compared with the manufacturing cycle of a quenching and tempering
steel, for such steels three aspects are of importance to tool steels.
The first is homogenization (or reduction) of microstructure heterogeneity
that is produced by segregation phenomenon during solidification; the sec-
ond is dissolving large complex and stable carbides formed during the re-
finement of grains, the third is the refinement of coarse grains that would
appear as result of high temperature annealing and austenitizing tempera-
tures. In fact, when no prolonged hot working operations with high reduc-
tion are foreseen, a full annealing shall be conducted at high temperatures.
But such a high temperature annealing is detrimental for grain size coars-
ening; thus, a homogenizing treatment, normalizing usually followed as a
grain refinement step.
When required, to enhance hot ductility, spheroidization treatment can be
conducted instead of or following the normalizing treatment for grain re-
finement.

Criteria for selection of tool steels for specific applications

258

Tool steels that are included into the nine groups by Table 4.1, are in the
following classified into 4 main categories of specific applications. Each
application requires specific properties to be enhanced.

1. Steels for plastic molds. During the formation of plastics, dies are sub-
jected to heat and pressure. The temperature of the dies is as high as 250C
and the strength of about 100 MPa. In this case, hardness retention and
strength requirements are of minor importance, instead high machinability
properties and a low degree of distortion in hardening of plastic molds are
very important. The P20 steel (0.30% C, 1.70% Cr, 0.40% Mo, Table 4.1)
is a good choice for molds due to its low degree of distortion and good
machinability. In the case of abrasive plastics, the molds are made of steels
oil-hardening cold working steel (see Table 4.1) as O1 (0.90% C, 1.0
1.4% Mn, 0.50% Cr, 0.50% Ni, 0.50% W) that can be hardened to about
57-61 HRC thanks to a low tempering (between 100C and 350C). The
low tempering temperature defines the low temperature for such steels that
are suitable for tools used to cut or form materials that are at low tempera-
tures.

2. Steels for high-pressure die casting molds. In die casting, tools are heat-
ed to about 500C and are subjected to high mechanical forces and erosion.
Most important property in this case is hardness retention at high tempera-
ture. Steels that exhibit secondary hardening are required, low carbon and
moderate to high alloy that provide good hot hardness and toughness and
fair wear resistance due to a substantial amount of carbide (class 4 of
fig.4.1). Dies used for light metal casting are therefore commonly made of
H-type steels, as H11 (0.33% C; 4.75%Cr; 0.3% Ni; 1.10% Mo; 0.3% V).

3. Steels for cold-forming tools and machining. Cold-forming processes

such as cold rolling, stamping, deep drawing, extrusion, and bending have
the advantage of making parts with high-dimension accuracy and good
surface quality that does not need machining. As well, tools for high speed
machining, as turning, requires abrasive wear resistance and hardness at
high temperature, for not prolonged time. In such processes, tools are sub-
jected to high stresses (from pressure and friction) and possible localized
high temperature, due abrasive forces. Tool steels with a high hardness are
used in these applications. The M-type tool steels, namely the Molyb-
denum high-speed tool steels, are used due to high strength and hardness
also retained at temperatures up to or exceeding 760 C. For example, the
M2 high-speed steel with 0.85% C; 4.10% Cr; 5.00% Mo; 6.40% W;
 259

1.80% V achieves 61HRC by tempering at 650C and it can withstand

high temperature, around 700C, for not prolonged time.

4. Steels for hot working. Forging hammers and hot extrusion dies are ex-
amples of hot working process tools. The tool steels H11 and H13 of H-
types, based on a chromium content of 5% and medium carbon (0,38% C)
are suitable for the forging and extrusion of light metals. In the case of
heavy metals, such as copper and steels, Ni-base super alloy steels are
more suitable.
260

Steels for Special Applications Specialty Alloyed

Steels23

High-Fracture-Toughness Steels

Main feature for such steels is their high toughness with high strength
properties. This is achieved by limiting carbon content, that is kept at low-
er value than reference quenching and tempering medium-carbon steel
AISI 4340 (similar to UNI EN 40 Ni Cr Mo 7). As known, the lower car-
bon content significantly contributes to their better ductilities and higher
fracture toughness that is also increased by high nickel contents.
Further addition of alloying elements, as Co and Cr, provide deep harden-
ing and specifically cobalt helps to prevent retained austenite. For a further
increase in toughness, all these steels are vacuum melted so to avoid hy-
drogen, oxygen and residual inclusions highly detrimental for tough prop-
erties of steels that usually contaminate steel in steelmaking refining pro-
cess steps 24.
Three are the high-fracture-toughness steels, classified AISI:
HP-9-4-30,
AF1410,
AerMet 100,

The mechanical properties for HP-9-4-30, AF1410, and AerMet 100 are
given in Table 4.2. These alloys are not corrosion resistant, and parts must
be protected with a corrosion-resistant coating.

Heat treatments, mechanical properties and applications

All these steels are quenched and tempered, to achieve high strength and
high toughness due to tempering martensite structure with fine carbides.
The high toughness provided by high nickel content and relative lower
carbon content allows to temper quenched martensite to lower tempera-
tures than quenching and tempering steels.
The HP-9-4-30 nominally contains 0.30 wt% C, 9 wt% Ni, and 4 wt% Co.
It was developed as high-fracture-toughness steels capable of being heat

23 Main reference for this section, F.C.Campbell, Elements of Metallurgy and

Engineering, ASM International, 2008, Chapter 20.
24 Vacuum degassing is used to remove hydrogen from liquid steel. Particular-

ly, vacuum deoxidization is also being used to eliminate oxygen that yield cleaner
steel with a lower inclusion content.
 261

treated to high strength levels in thick sections. Due to high hardenability

provided by alloying elements, it is capable of being hardened in sections
up to 15 cm thick to an ultimate tensile strength level of 1520 to 1655 MPa
while maintaining a fracture toughness, KIc, of 110 MPa. Double temper-
ing is normally employed to prevent retained austenite.
The alloy AF1410 has nominal composition 14 wt% Co, 10 wt% Ni, 2 wt%
Cr, 1 wt% Mo and 0.15 wt% C. Its lower carbon content than the HP-9-4-
30 assures higher weldability. Furthermore the higher toughness at cryo-
genic temperatures and has high strength and stability at temperatures up
to 425C.
AerMet 100 is a nickel-cobalt high-strength steel containing 0.23 wt% C,
3.1 wt% Cr, 1.2 wt% Mo, 11.1 wt% Ni, 3.4 wt% Co. AerMet 100 is re-
placing older steels such as 4340 in many applications due to its good
combination of strength (ultimate tensile strength is 1965 MPa) and tough-
ness (KIc is 110 MPam). Other advantages include good toughness at
cryogenic temperatures, a critical flaw length of nearly 6.3 mm, and an op-
erating temperature up to 400C.
Examples of applications for such steels include armor, fasteners, airplane
landing gear, jet engine shafts, structural members, and drive shafts.

Table 4.2 - Typical properties of high-fracture-toughness steels.

262

Mar-Aging Steels

Maraging steels are a class of high-strength steels with very low carbon
contents (0.030 wt% maximum) and additions of substitutional alloying
elements that produce age hardening of iron-nickel martensites. The term
maraging was derived from the combination of the words martensite and
age hardening.
Maraging steels have high hardenability and high strength combined with
high toughness. The maraging steels have a nominal composition by
weight of 18% Ni, 7 to 9% Co, 3 to 5% Mo, less than 1% Ti, and very low
carbon contents.
The commercial maraging steels, 18Ni(200), 18Ni(250), 18Ni(300), and
18Ni(350), have nominal yield strengths after heat treatment of 1380,
1725, 2070 and 2415 MPa (200, 250, 300, and 350 ksi), respectively.
The name derives from the combination of nominal content of Ni and the
average UTS in ksi. Typical properties of maraging steels are shown in
Table 4.3

Table 4.3 Typical properties of Mar-Aging steels.

Heat treatments, mechanical properties and applications

Heat treatment consists of solution annealing, air cooling, and then aging.
Solution annealing is usually conducted at 815C for 1 h. Since the nickel
content is so high, austenite transforms to martensite on cooling from the
austenitic temperature.
The martensite start temperature (Ms) is approximately 155 C, and the
martensite finish temperature (Mf) is approximately 100C .
The formation of martensite is not affected by cooling rate, and thick sec-
tions can be air cooled and still be fully martensitic. Since the martensitic
 263

transformation involves only an austenite-to martensite transformation of

iron-nickel and does not involve carbon 25 to any considerable extent, the
martensite formed is relatively soft (30 to 35 HRC), which can be easily
machined or formed is relatively ductile. Before aging, maraging steels
have yield strengths in the range of 655 to 830 MPa. They are then aged to
high strength levels at 455 to 510 C for times ranging from 3 to 9 h. The
effect of aging temperature on 18Ni(250) is shown in Fig. 4.4.
Since high stability of their low-carbon martensite structure at relatively
high temperature, they can be used up to 450C.
The properties of high malleability and machinability in annealed state, the
high stability at relative high temperatures and very high toughness with
high strength make them suitable for engine components, such as crank-
shafts and gears, and the firing pins of automatic weapons that cycle from
hot to cool repeatedly while under substantial load.

Fig.4.4 - Effect of aging temperature on 18Ni(250) maraging steel.

25 In these Fe-alloys, carbon is considered an impurity and kept to as low a lev-

el as possible to minimize the formation of titanium carbide (TiC), which can ad-
versely affect ductility and toughness.
264

High-Strength Low-Alloy Steels

Conventional hot rolled mild steels have rather low strengths but are readi-
ly weldable. As the carbon content is increased to increase strength, the
amount of lamellar pearlite increases, reducing weldability and toughness
and increasing the ductile-to-brittle transition temperature (DBTT). The
development of high strength low-alloy (HSLA) steels in the early- 1980s
provided an answer to this dilemma.
High-strength low-alloy steels are a hybrid between plain carbon steels and
alloy steels and are often considered to be a separate class of steel. They
contain alloying elements; however, the alloy content is usually on the or-
der of only 0.1 wt% and is referred to as microalloying.
The HSLA steels are essentially low-carbon steels (0.03 to 0.1 wt% C)
containing approximately 1.5 wt% Mn and less than 0.1 wt% of niobium,
titanium, and/or vanadium, which have been hot rolled under controlled
conditions to produce ultrafine ferrite grain sizes of less than 5 to 10 m.

Mechanical properties, heat treatments and applications

They attain yield strengths of 275 to 550 MPa and tensile strengths of 415
to 690 MPa, with a DBTT of approximately 75 C. They are hot rolled un-
der controlled conditions to produce ultrafine ferrite grain sizes of less than
5 to 10 m (Fig.4.5b). This is the result from the control of the austenite
grain size at rolling temperature (i.e. austenitic grain pinning) by the for-
mation of carbides, carbonitrides, and nitrides realized by presence of
small addition of Nb, Ti, V.

Fig.4.5 - Fine grain size in; a) common plain carbon steel; b) high-strength low-
alloy (HSLA) steel.
 265

These fine precipitates pin the austenite grain boundaries, hindering grain
growth. At still lower rolling temperatures, they inhibit recrystallization of
the severely deformed austenite grains. The elongated and pancaked grains
can then rapidly transform to fine ferrite. These fine precipitates also pro-
vide additional locations for ferrite nuclei to form during cooling, resulting
in an even finer ferrite grain size. In addition, as shown in Fig. 4.6, nuclei
locations are also formed within the austenite grains at locations of de-
formed shear bands.

Fig.4.6 - Microstructure development in low-carbon steels.

High-strength low-alloy steels are primarily hot rolled into the usual
wrought product forms (sheet, strip, bar, plate, and structural sections) and
are commonly furnished in the hot rolled condition. In addition to hot
rolled products, HSLA steels are also furnished as cold rolled sheet and
forgings.
Since HSLA steels do not contain a large percentage of alloying elements,
they can be competitively priced against plain carbon steels.
The HSLA steels are extensively used as structural beams for bridge con-
struction, off-shore oil and natural gas platforms, ship hull and deck plate,
and electrical transmission towers and poles. In automobiles, HSLA steels
are used for safety applications such as ultrahigh-strength impact door
beams and energy-absorbing bumper assemblies and for increasing fuel
economy through thinner and lighter-weight chassis sections (Fig.4.7).
266

Fig.4.7 Application of HSLA steel in automobiles .

Recent developments about good nitridability of types of HSLA steels

when nitride in the bainite condition resulted from air-cooling of forged
parts would lead to use such steels to reduce manufacturing costs of con-
ventional nitriding steels (or the mostly used quenching and tempering
UNI EN 42CrMo 4 steel, finally nitrided) by reducing manufacturing cycle
steps (Fig.4.8).

Quenching
42CrMo4 Forging LMUmachining and LMUfinishing
tempering

Nitriding

25MnCrSiVB6 Forging LMUmachining

Fig.4.8 Application of HSLA steel in alternative nitriding of automobile crank-

shaft.
 267

Dual-Phase Steels

A dual-phase steel is one that consists of islands of hard martensite em-

bedded in a tougher continuous ferrite matrix. This mixture of fine ferrite
and austenite grains is produced by heating into the two-phase a+c field,
followed by quenching to convert the austenite to martensite (Fig.4.9). The
microstructural constituents that can be present in dual-phase steels after
processing are therefore a fine grained ferrite matrix, some proeutectoid
ferrite that formed from the austenite during cooling, and martensite or
lower bainite, depending on the alloy content and the Ms temperature.

Fig.4.8 Microstructure of dual-phase steel.

Mechanical properties, heat treatments and applications

The unique characteristic of dual-phase steels is the continuous yielding
behavior during deformation; that is, there is a lack of a yield point during
deformation. This provides increased uniform elongation and work harden-
ing so that parts produced from a dualphase steel actually gain strength
during the forming operation. Dual-phase steels yield at relatively low
stresses and then work harden rapidly. Any retained austenite usually
transforms to martensite during deformation. The tensile strength varies
approximately linearly with the amount of martensite or lower bainite.
Typical values are 550 MPa for 10% by volume rising to 760 MPa at 30%.
Elongations of approximately 20% are typical (Fig.4.9).
268

Fig.4.9 Stress-strain curves for plain carbon, high strength low-alloy (HSLA),
and dual-phase steels.

To be successful, the hat treatment of these steels requires suitable contin-

uous cooling transformation characteristics and controlled cooling rates, as
shown in the scheme of Fig.4.10.

Fig.4.10 Scheme of heat treatment cycle for dual-phase steels.

 269

Dual-phase steels are used in applications such as automobile wheel rims

and wheel disks. Because of their energy-absorbing characteristics, dual-
phase steels are also used in critical locations of automobiles for safety to
protect the occupants in the event of a crash.

TRIP Steels

The term TRIP is derived from the mechanism of transformation-induced

plasticity. The nominal composition by weight of these steels is 0.25% C,
2% Mn, 2% Si, 10% Cr, 9% Ni, and 5% Mo. They contain a high percent-
age of retained austenite (10 to 15%). The austenite transforms to marten-
site during forming of the part, thus providing enhanced formability, or it
transforms on impact, as in an automotive crash.

Mechanical properties, heat treatments and applications

Similar to dual-phase steels, TRIP steels are annealed in the intercritical
region, but instead of direct cooling to room temperature to form marten-
site, they are isothermally treated. The isothermal hold during heat treat-
ment is specifically designed to produce large, dispersed volume fractions
of retained austenite in the ferrite matrix after intercritical annealing. Thus
products of transformation therefore include bainite and retained austenite.
The scope of dispersed retained austenite is comprehensible when these
steels are cold worked or plastically deformed. During cold plastic defor-
mation, the unstable retained austenite transforms to martensite, hence the
term transformation-induced plasticity.
The strain induced martensitic transformation increases strain hardening;
furthermore, it helps to delay necking instability during forming opera-
tions.
Due to dynamic increase of strength during impact, similarly to Dual-
Phase steels they are suitable for safety components to absorb impact ener-
gy in automotive crash.
270

Chapter 5 Stainless Steels26

Introduction
Under favorable environmental conditions the iron in steels tends to return
to its former state of iron oxide as it is available in nature by forming rust
or scale. Since the corrosion product is not effective protection, once cor-
rosion mechanism starts, the steel will continue to rust. In case of high
temperature, oxidation can occur, the oxide scale spalls off, and oxidation
will continue as long as the steel is hot. Other corrosion processes, such as
dissolution in electrolyte as differential aerated water or dilute acids pro-
ceeds with corrosion products formation, that similarly will progressively
detach from surface. In the former case we talk about dry corrosion, in lat-
ter case about humid corrosion. Whichever mechanisms of corrosion you
consider, the addition of chromium in solid solution of iron dramatically
improves the corrosion and oxidation resistance of steel. Chromium onto
top surface layer immediately reacts with oxygen in environment to oxi-
dize and forms a thin, tightly adherent layer of oxide (Cr2O3) on the sur-
face. This layer is spontaneously created, transparent, adherent, self-
healing when damaged and moreover is capable to prevent or minimizes
further corrosion to proceed, by isolation of subsurface metal and external
oxygen, key-factor necessary for corrosion mechanisms to advance.
To achieve formation of such protective layer, namely for being stainless,
steel must contain at least 11.5 wt% Cr at least, 12 wt% Cr in aqueous
solutions and even higher chromium content is necessary for corrosion re-
sistance in nonaqueous solutions.
Few stainless steels contain more than 30 wt% Cr or less than 50 wt% Fe.
Other important alloying elements include nickel, molybdenum, copper, ti-
tanium, aluminum, silicon, niobium, nitrogen.
Stainless steels are used in a wide variety of applications. Most of the
structural applications are in the chemical and power engineering indus-
tries, which account for more than a third of the market for stainless steel
products. These applications include an extremely diversified range of us-
es, including nuclear reactor vessels, heat exchangers, oil industry tubes,
components for chemical processing and pulp and paper industries, fur-
nace parts, and boilers used in fossil-fuel-fired electric power plants.

26 Reference: M.Boniardi, A.Casaroli, Stainless Steels, Gruppo Lucefin Edi-

tion, 2014 (free version available at: http://www.lucefin.com/wp-
content/files_mf/stainlesssteels_low.pdf).
 271

Classification of stainless steels

There are five types of stainless steels: austenitic, ferritic, duplex, marten-
sitic, and precipitation-hardening steels. These five types of stainless steel
have a somewhat simplified AISI classification system (mostly diffused in
industry), that is also supplemented by the EN designation system for high
alloyed steels (i.e. the code with X devoted to distinguish steels with at
least one element with wt.% higher than 5%) as follows:
Austenitic stainless steels: 3xx series (AISI 2xx series for low
nickel alloys) which are Cr-Ni high alloyed steels in EN designa-
tion, such as X5CrNi18-10;
Ferritic stainless steels: 4xx series or Cr high alloyed steels in EN
designation, such as X6Cr17;
Duplex stainless steel: Manufacturers designation is frequent or
EN designation such as such as X2CrNiMoN22-5-3;
Martensitic stainless steels: 4xx series or Cr high alloyed steels in
EN designation such as X30Cr13;
Precipitation-strengthening stainless steels: xx-x PH; this type is
not defined by the metallurgical structure of the steel at ambient
temperature but rather, as per tradition, by the heat treat-
ment/strengthening mechanism used to produce it (precipitation
hardening).

Before dealing in detail with the relevant metallurgical and mechanical

characteristics, the main types of stainless steel available on the market can
be summarized in a simple tree view (see figure 5.1).

Figure 5.1 - Schematic of the evolution of stainless steels starting from plain car-
bon steels: the stainless steel tree structure.
272

To begin with we consider a common heat-treatable plain steel, such as

steel grade C30: to make this steel stainless it is sufficient to add a set con-
tent of chromium (~13%) to obtain an initial possible version of stainless
steel. This is grade X30Cr13. A steel with this type of chemical composi-
tion can undergo heat treatment (in fact this is a heat-treatable steel) and,
after tempering and quenching (hardening), it takes on a tempered marten-
sitic structure at ambient temperature. It also offers the benefit of offering
good resistance to corrosion, combined with good mechanical resistance.
With the aim of further increasing corrosion resistance of stainless steel as
proposed above, a larger quantity of chromium needs to be added, while
the presence of carbon should be reduced. In this case the steel grade ob-
tained will be X6Cr17, with a ferritic structure at ambient temperature, due
to the significant presence of chromium, with notable ferrite forming prop-
erties. The level of corrosion resistance of the new steel will be greater
than that of the X30Cr13 steel; on the contrary the mechanical resistance
of the X6Cr17 will be much more limited as no hardening heat treatment
will be possible. To obtain a steel with even greater corrosion resistance
than the two grades described above, the addition of nickel and molyb-
denum will be necessary, and possibly a further increase in chromium con-
tent. In this case, there are two alternative procedures:
starting with the X6Cr17, nickel could be added to obtain
stainless steel grade X5CrNi18-10 or both nickel and molybdenum
to obtain the grade X5CrNiMo17-12-2: this will thus obtain an
austenitic structure at ambient temperature, due to the austenite
stabilizing properties of nickel that predominate over the ferrite
stabilizing effect of Cr (we talk about austenitic steels);
alternatively, again starting with X6Cr17, smaller quanti-
ties of nickel can be added, along with greater quantities of chro-
mium, with a set percentage of molybdenum, to obtain the stain-
less steel grade X2CrNiMoN22-5-3: this solution obtains a mixed
(or two-phase) structure of ferrite and austenite, and we talk about
Duplex Stainless Steels.
 273

Ferritic Stainless Steels

Ferritic stainless steels (the AISI 4xx series) are essentially iron-chromium
alloys with body centered cubic (bcc) crystalline structures. Ferritic stain-
less steels contain 11.5 to 30 wt% Cr, with most compositions containing
17 to 26 wt% Cr. The presence of high percentage of Cr modifies the iron-
carbon diagram as depicted in Fig.5.1. chromium stabilizes ferrite and
forms a gamma () loop in which austenite is the stable phase. When the
chromium content exceeds 12 wt%, it is possible for ferrite to exist at all
temperatures 27. The ferritising effect of the chromium is no longer com-
pensated for by the austenitizing action of the carbon and the structure of
the stainless steel will be ferritic at ambient temperatures: this is precisely
what occurs on steel type X6Cr17 (similar to AISI 430), the progenitor of
ferritic stainless steels.

Fig.5.2 - Iron-chromium phase diagram.

In table 5.1 some typical ferritic steels are The relative designation in ac-
cordance with the standard EN 10088 refers to alloyed steel type, with X
followed by carbon content in percentage and other alloying elements, e.g.
Cr, with their own actual weight percentage. The last column provides the
most appropriate AISI designation for such steels.

27 The phase diagram shows that for some compositions with Cr below 12%wt., solid

solutions can be transformed into austenite by heating them into the gamma loop, and,
when cooled, austenite transforms into ferrite. As shown in the following, this transfor-
mation forms the basis for the heat treatable martensitic stainless steels.
274

Table 5.1 - Chemical composition of some of the main types of ferritic stainless
steels from EN 10088 and AISI designations.

Figure 5.2 illustrates the metallurgic logic that led to the creation of the
main types of ferritic stainless steels present on the market, starting from
type X6Cr17. The first family, to which the X6Cr17 belongs, has a chro-
mium content ranging from 15.5% to 18%: this family is the most numer-
ous in terms of the quantity of alloy types present on the market. There are
a further two families, one characterized by chromium content ranging
from 11.5% to 14.5% (ferritic stainless steels with low chromium content)
and the other with a chromium content of more than 18% (known also as
superferritic stainless steels).
In all three of the above families - with low, medium and high carbon
chromium content - other alloy elements may also be present: these in-
clude aluminum and silica, aimed at stabilizing the ferritic structure and
improving resistance to oxidation under heat, molybdenum, necessary to
improve corrosion resistance, titanium and niobium, to prevent precipita-
tion of the harmful chromium carbides, as below described.
 275

Figure 5.2 - Schematic of the main types of ferritic stainless steels, starting from
X6Cr17 (similar to AISI 430), progenitor of this family.

Box The intergranular corrosion induced by carbide precipitations

A metallurgical problem typical in stainless steels, including ferritic, is related

to the precipitation of chromium carbides, type Cr23C6. This occurs due to the
high level of affinity between the chromium and carbon. Chromium carbides
usually deposit on the grain boundary and leading to a localized, i.e. within the
boundary of the grain itself, depletion of chromium: a consequence of this pro-
cess is that the chemical composition of the metal mass falls below the pas-
sivation threshold (10.5% chromium) giving rise to intergranular corrosion, also
in only slightly aggressive environments. The scheme of such a phenomenon is
shown in Fig. 5.3. The entity of corrosion depends both on the quantity of car-
bide precipitation and the lesser or greater ability of the chromium to spread in
the steel lattice: in the crystalline structure of the steel, this causes short or long
range depletion of the chromium with differing effects in terms of material dete-
rioration. As the solubility of carbon in the body-centered cubic lattice is signif-
icantly limited, the precipitation of chromium carbides in ferritic stainless steels
is practically impossible to eliminate. On the other hand, due to the high diffu-
sivity of chromium in the lattice of phase , the chromium gradients in the vi-
cinity of the ferritic grain boundary are much less pronounced with respect to
what occurs in austenitic stainless steels (refer to Fig.5.3a): as a consequence
the problems of intergranular corrosion in ferritic stainless steels, under the ef-
276

fect of carbide precipitation on the grain boundary, are less marked with respect
to the same phenomena in austenitic stainless steels.

Figure 5.3 - Trends in chromium concentrations at a grain boundary where chromium

carbide precipitation occurs: a) in the case of ferritic stainless steel (high diffusivity of
chromium); b) in the case of austenitic stainless steel (low diffusivity of chromium).

With the exception of the case in which high mechanical properties are required
(such as the case of martensitic stainless steels), this problem is avoided by min-
imizing the carbon content or attempting to neutralize the effect of the latter, by
combining it with other chemical elements, such as titanium and niobium. Also,
as explained further in the section below, the semi-finished products should also
undergo a complete annealing heat treatment before being used.

Heat treatments
The only heat treatment possible for the family of ferritic stainless steels is
complete annealing or simply annealing: its role is to optimize corrosion
resistance of the steel, aiding a uniform distribution of the chromium in the
crystalline structure of the semi-finished part. Great care is taken in select-
ing the temperature and hold time, as this family of materials is particular-
ly sensitive to the phenomena of crystalline grain enlargement. Annealing
 277

of ferritic stainless steels also has another important characteristic. If the

material to be treated is in the hardened state, the heat treatment would al-
so serve to re-crystallize the microstructure, i.e. to reform new crystalline
grains, starting from the original grains that have extended under the effect
of cold plastic deformation. In general, these newly formed grains are finer
that the original hot formed grains in the semifinished part. This is normal-
ly referred to as recrystallization annealing (Fig.5.4).

Figure 5.4 - Effect of recrystallization annealing on ferritic stainless steels.

Physical and mechanical properties

The resistance properties of ferritic stainless steels are not particularly sig-
nificant; in fact these steels are made up of uniform ferrite grains and are
used in an annealed state. The unitary value of tensile strength Rm ranges
between 450 MPa and 600 MPa, according to the chemical composition,
with hardness values of 150-220 HB. As already mentioned, ferritic stain-
less steels cannot be hardened by means of a quenching heat treatment: the
only way to increase mechanical resistance is by means of cold plastic de-
formation processes, such as cold drawing or rolling, which harden the
steel: in this case the unitary value of tensile strength can reach up to 900-
1000 MPa.
In addition to the chromium content, as shown in Fig. 5.5a, the resistance
to brittle fractures also depends on the combined effect of other metallur-
gical parameters, thus it increases with the increase in contents of intersti-
tial elements (carbon and nitrogen) and decreases under the effect of a re-
duction in the average size of the crystalline grain; the thickness of the
semi-finished part also has an interesting effect on the brittle fractures of
the ferritic stainless steels (see Fig. 5.5b).
278

(a)

(b)

Figure 5.5 a) Effect of chromium content on transition curves of iron-chromium

alloys (the carbon content is ~ 0.01); b) Effect of thickness of semi-finished part
on the transition temperature of two ferritic stainless steels.

Main applications
Steel grade X6Cr17 (similar to AISI 430) is used for machine parts in the
industry for the production and transformation of nitric acid (tanks, con-
densers, pipelines, coils, etc.); it is also widely used for cracking and re-
forming plants in the oil sector, for the production of low cost cutlery,
household applications, decorative elements and furnishing accessories for
interiors, coverings for bar counters and tables, and kitchen extractor
hoods. It is also used in a number of applications in the cheese/milk dairy
sector and for manufacture of train carriages and buses. Ferritic stainless
steel grade X6Cr17 is also used in components operating at temperatures
up to 750-800C due to its optimal resistance to oxidation under heat. In
more aggressive environments, the ferritic stainless steel X6CrMo17-1
(similar to AISI 434) can be used, in which the presence of molybdenum
 279

improves resistance to corrosion due to pitting; as well as for exhaust sys-

tems in the automotive sector, these steels are also used for internal clad-
ding of buildings, on escalators, lifts and conveyor belts, for drinking wa-
ter pipelines or as supports for photovoltaic cells.

Austenitic stainless steels

If the chromium content is increased to at least 17-18% and at the same
time nickel is added to a percentage of 8% to 9%, the steel will have an
austenitic structure at ambient temperature. For better understating, you
may refer to Fig. 5.6 that shows the simplified phase diagram of a steel
with 18% chromium and 8% nickel on variation in carbon content, namely
the grade X5CrNi18-10 (similar to AISI 304) progenitor of the family of
austenitic chromium-nickel stainless steels. The significant austenitizing
effect of the nickel predominates over the ferritizing action of the chromi-
um. An significant aspect of the phase diagram of austenitic stainless steels
is the absence of critical points, as no transformation temperature are
visible. After initial solidification at very high temperatures in phase + ,
the stainless steel becomes completely austenitic (phase ) and remains in
this state through to ambient temperature, without the inevitable chromium
carbides.

Fig.5.6 Fe-C binary section of Fe-Cr-Ni-C quaternary diagram with Cr =18%

and Ni = 8%; C1 are carbides type (Cr,Fe)23C6.
280

To limit carbide formation and detrimental effect on intergranular corro-

sion (refer to Box The intergranular corrosion induced by carbide pre-
cipitations) the carbon content is fixed to very low values, usually it ranges
0.02-0.06%. The combination of chromium and nickel in the alloy obtains
a stainless steel with an austenitic structure, i.e. with a face-centered cubic
lattice, highly resistant to atmospheric corrosion and water-based solu-
tions 28.
In austenitic stainless steels, added corrosion resistance can be achieved by
increasing the nickel content up to 11-12% or adding molybdenum to val-
ues of 2-3%. The latter action leads to another widely used stainless steel,
i.e. the X5CrNiMo17-12-2 (similar to AISI 316), progenitor of the second
family of austenitic stainless steels, i.e. chromium-nickel molybdenum 29.
Finally, a further possibility to obtain an austenitic structure in a stainless
steel consists in replacing the nickel part with manganese 30, the element
which otherwise would only act as a deoxidant in the alloy. This solution
was developed in the 1950s, with the aim of limiting production costs; the
progenitor of the family of austenitic stainless steels with chromium-
manganese-nickel is the X12CrMnNiN17-7-5 (similar to AISI 201).
Figure 5.6 illustrates the metallurgical logic, which led to the creation of
two main types of austenitic stainless steels available on the market: one is
chromium-nickel stainless steels such as X5CrNi18-10 and the other is the
chromium-nickel-molybdenum such as X5CrNi17-12-2 and their respec-
tive by-products.

28 In air and water-based solutions, even partially contaminated by chlorides (generally

up to 500ppm of ions Cl-) the corrosion resistance of austenitic stainless steel X5CrNi18-10
is superior with respect to martensitic and ferritic types such as X30Cr13 and X6Cr17.
29 The austenitic chromium-nickel-molybdenum stainless steel X5CrNiMo17-12-2 (sim-
ilar to AISI 316) is suitable for applications in contact with sea water (Cl- 20,000ppm =
2%) or with water-based solutions strongly contaminated by chlorides.
30 The alternative to manganese with respect to nickel is based on the austenitizing ef-

fect that both elements show if added to Fe-C alloys: as the austenitizing effect of the man-
ganese is equal to half that of nickel, around 2% of Mn needs to be added for each 1% of
replaced Ni.
 281

Fig. 5.7 - Schematic of main types of austenitic chromium-nickel and chromium-

nickel-molybdenum starting from X5CrNi18-10 and X5CrNiMo17-12-2.

The sensitization of austenitic steels

The phenomena of carbide precipitation, also known as sensitization for
austenitic stainless steels occurs at temperatures between 450C and 900C
and at highly variable exposure times: the most critical conditions are
found at around 700C for time intervals of just a few minutes. As already
discussed (refer to Box The intergranular corrosion induced by carbide
precipitations), sensitization of austenitic stainless steels leads to a decline
of chromium in the immediate vicinity of areas where the carbides form,
i.e. on the boundaries of the crystalline grains: consequently, the chromium
content of the grain boundaries is below the passivation limit of the steel,
leading to local deterioration in corrosion resistance and the phenomena of
inter-crystalline corrosion, even in only slightly aggressive environments
(Fig.5.3b). A method of intervention, in many ways simpler than the first,
consists in minimizing the carbon content of the steel down to values of
around 0.02-0.03%. As a consequence the time required for incubation and
the formation of chromium carbides changes from a few minutes to several
hours, which practically renders sensitization of the material negligible, as
shown by sensitization curves in Fig.5.7. the time required to sensitize the
steel depends, as well as on the exposure temperature, on the carbon con-
tent in the alloy: for example, if the carbon content is 0.08%, the time for
carbide precipitation is around one minute, while this can extend to several
hours if carbon is reduced to 0.02%.
282

On the basis of the C curves austenitic steels with low carbon content
have been developed, such as X2CrNi18-9 (similar to AISI 304L27) or
X2CrNiMo17-12-2 (similar to AISI 316L) which are virtually insensitive
to the phenomena of chromium carbide precipitation.

Fig.5.7 - Time-temperature diagram (C curve) showing precipitation of chromi-

um carbides on variation of the carbon content, for austenitic stainless steels with
18% chromium and 9% nickel.

Further but quite more expensive method to prevent sensitization consists

in adding titanium or niobium, as for the ferritic stainless steels, too. Tita-
nium and niobium leads the formation of very stable Ti- and Nb- base car-
bides, thereby preventing carbon to engage chromium to form chromium-
based carbides.

The heat treatments

Due to absence of critical phase-transformation temperature, the only fea-
sible heat treatment is solubilization, also known as negative quenching or
austenitic quenching: this treatment is normally performed on semi-
finished products and finished products in austenitic stainless steel, down-
line of the various manufacturing processes. The treatment is performed at
high temperatures (approximately in the range 1000C to 1100C), for a
sufficient time to ensure homogenization of the chemical composition of
the steel. Scope of treatment is to cancel microstructural irregularities and
moreover allowing full solubilization of chromium carbides to avoid to put
into service a sensitized stainless steel. After solubilization, austenitic
 283

stainless steels must be cooled rapidly in water, moreover in case of thick

parts. Particularly for steels subjected to sensitization, cooling rate must be
rapid in the range 450C-900C to prevent carbide formation (remember
that sensitization is temperature-time dependent phenomenon). In the case
of thin parts, a high pressure flow of nitrogen can also be used, although
cooling is preferable.
On the other hand a special treatment is used on Ti and Nb added austenit-
ic stainless steels, named stabilization. This consists in maintaining the
steel at temperatures between 850C and 950C for times ranging from 1
to 4 hours depending on the dimensions of the semi-finished part. During
treatment, precipitation of the titanium and niobium carbides occur and
fixes carbon, thus preventing carbon to subtract Cr from matrix to form
chromium carbides. The subsequent cooling is in air.

Physical and mechanical properties

The linear heat expansion of austenitic stainless steels, for example, is 50-
60% greater than that of ferritic or martensitic stainless steels, as well as
the thermal conductivity, which on the contrary is 40-50% lower. These
particular properties must be taken into consideration in an industrial con-
text: in the heating and cooling during thermal treatment, the dimensional
variation of the stainless steel pieces will be much greater than in common
steels, but heat exchange will be much more limited.
Austenitic stainless steels have nonmagnetic behavior, this characteristic
makes them well suited to some military applications (but, as a result of
cold plastic deformation operations, the semi-finished products tend to be-
come slightly ferromagnetic).
The mechanical characteristics of austenitic stainless steels are rather lim-
ited, due to the high deformability of the austenite matrix. In an annealed
condition, these steels provide a tensile strength UTS of 550-650 MPa and
a yield stress YS of 220-280 MPa. Conversely, the austenitic microstruc-
ture has high ductility, with percentage values of elongation at break of 40-
50% and hardness of 160-200 HB.
The only way to increase the traction resistance of austenitic stainless
steels is through work-hardening; by cold plastic deformation (rolling,
drawing etc.) it is possible to obtain a tensile strength UTS 1500-1800
MPa and yield stress YS 1300-1600 MPa, much greater values than those
that would be obtained using a low carbon common steel.

Main applications
The X5CrNi18-10 (similar to AISI 304) is widely used in various applica-
tions: boilers, pressure tanks, vessels, heat exchangers, fluid transport
284

pipes, plumbing, elevators and signs. It is also used in building and urban
furnishings, in domestic utensils (cookware, cutlery, appliances), in sinks
and cabinets, as well as in the chemical, petrochemical, nuclear and phar-
maceutical industries as well as for the production of milk, beer, canned
food, paper and pulp, colorants and explosives. Due to its high toughness
at low temperatures, it is also widely used in the cryogenics sector for the
storage and transport of liquefied gases.
the types X6CrNiTi18-10 (similar to AISI 321) and X6CrNiNb18-10 (sim-
ilar to AISI 347) are the stabilized versions with titanium and niobium. As
these materials have a high resistance to corrosion comparable with that of
X5CrNi18-10, they are used in the same applications, especially for the
production of large sized and/or very thick items that are subjected to
welding operations.
X2CrNi18-9 (similar to AISI 304L) is actually the low carbon version of
X5CrNi18-10: this composition is also used to solve issues of the precipi-
tation of chromium carbides during welding and is a good alternative to
the previously indicated stabilized types.
The stainless steel X5CrNiMo17-12-2 has high resistance to corrosion in
seawater, in contact with process waters contaminated with halides (Cl-, I-,
F-), with acid condensates and with waste water; it has excellent behavior
in the presence of organic acids or alkaline solutions, also showing a small
resistance in dilute sulphuric, hydrochloric or phosphoric acid solutions.

Martensitic stainless steels

The martensitic family of stainless steels is characterized by limited chro-
mium content (normally between 11.5% and 18%) and carbon contents
among the highest of the stainless steels most commonly used (generally
between 0.1% and 1%).
Chromium, a highly ferritising element, and carbon, an austenitising ele-
ment, are balanced so that the steel has an austenitic structure at high tem-
perature and a martensitic structure at ambient temperatures after temper-
ing.
It must be pointed out that the presence of a high content of carbon, re-
quired to ensure a good level of hardness and mechanical resistance for the
steel, also tends to aid the formation of chromium carbides. Consequently
martensitic stainless steels are, among all types, the least resistant to corro-
sion; their field of application in fact is limited to only slightly aggressive
environments. Fig. 5.8 illustrates the metallurgical logic that has led to
the creation of the main types of martensitic stainless steels, starting with
 285

X30Cr13 (similar to AISI 420B), the progenitor of this family, and still to-
day widely used in the knife sector.

Fig. 5.8 - Schematic of the main types of martensitic stainless steels, start-
ing from X30Cr13 (similar to AISI 420B), progenitor of this family.

When such steels are heated to temperatures above the critical points, their
original microstructure transforms completely into austenite plus carbides,
to then become martensite plus carbides under the effect of cooling the
steel in oil or in air. Given the existence of critical points, it is therefore
possible to trace the isothermal transformation curves (TTT) and aniso-
thermal curves (CCT) of the austenite: these curves are shown in fig. 5.9
for a martensitic stainless steel grade.
Due to similarities of heat treatments conducted onto martensitic stainless
steels and to hardened and tempered steels, their manufacturing cycle are
very similar, too.
286

Figure 5.9 - Isothermal transformation curves (TTT) and anisothermal transfor-

mation curves (CCT) for martensitic stainless steel type X39Cr13 (similar to AISI
420C).

Heat treatments
If no substantial differences exist in heat treating martensitic stainless
steels and common quenched and tempered steels, actually some peculiari-
ties should be taken into account. In case of martensitic stainless steels,
heating phase must be carefully conducted since stainless steels has very
low conductivity. To avoid permanent deformation of parts, or crack for-
mation, a worst case, the heating phase must be controlled with pre-heating
 287

between 550C and 800C, especially in the case of large size parts and/or
parts with complex geometry.
As regards the subsequent austenitization phase, a higher temperature must
be envisaged with respect to common quenching and tempering steels, thus
it should be as higher as possible to solubilize carbides. However, grain
coarsening phenomena may occur at high temperatures, that leads to con-
sequent reduction in resistance properties of the steel. For these conflicting
objectives, the optimized austenitizing temperature shall be chosen, de-
pending on specific steels, in the range 950 C 1100 C.
Martensitic stainless steels can be tempered either at low temperatures (be-
low 400C) or at high temperatures (over 640C). However, temperature
range of 450- 600C must be avoided. This interval is considered critical
as it reduces resistance
to brittle fractures (a type of temper brittleness) and significantly reduces
corrosion resistance.

Physical and mechanical properties

The physical properties of martensitic stainless steels are very similar to
those of the common quenching and tempering steels, sharing the same
martensitic tempered microstructure. In the hardened state most martensit-
ic stainless steels have a unit resistance under traction Rm of between 700
MPa and 1700 MPa depending on the chemical composition and temper-
ing conditions; the fatigue limit in air remains around the value 0.45Rm.
The ductile to brittle transition behavior is similar to that of special heat-
treatable steels used frequently in industrial applications.

Main applications
The martensitic stainless steels most commonly used in industrial sectors
are X30Cr13 (similar to AISI420B) and X12Cr13 (similar to AISI 410):
among the two, the first will guarantee hardness with a higher carbon con-
tent, while the second features increased strength.
These two steels are widely used where high mechanical resistance and
wear resistance is required. Corrosion resistance is good, especially in ru-
ral environments, fresh water not contaminated by chlorides, in contact
with foodgrade substances, or with weak acids (such as organic acids),
with petrol products (crude and intermediate) and with oxidating saline so-
lutions (chromates, permanganates, etc.).These are frequently used for the
production of table knives, industrial cutting knives, surgical instruments,
rasors, scissors, calipers, machine gun barrels, brake disks for motor vehi-
cles; they are also used in the sector of moulds for plastic materials and for
springs.
288

Type X17CrNi16-2 (similar to AISI 431) is must more resistant to corro-

sion with respect to those described above, due to the increased chromium
content in the alloy: it also offers increased strength due to the presence of
nickel (not present in types X30Cr13 and X12Cr13). The steel type
X17CrNi16-2 is used in particular for shafts on marine engines, propeller
shafts, pump parts, hydraulic machinery shafts, valves, turbine blades and
wear-resistant components in reforming oil plants.

Austenitic-Ferritic (Duplex) Stainless Steels

Austenitic-ferritic stainless steels (also called duplex or biphasic) owe their
name to the presence of a mixed structure of austenite and ferrite at ambi-
ent temperature. This is the result of the combination of chromium and
nickel suitably balanced in the chemical composition of the alloy: typical-
ly, duplex stainless steels have a chromium content between 22% and
25%, nickel content between 4% and 7%, with added molybdenum (3-4%)
and nitrogen (0.1-0.25%) in many cases.
The commercial name originally developed by Sandvik is most commonly
used: it includes two pairs of numbers of which the first indicates the
chromium content and the second the nickel content (for example 2205 in-
dicates a biphasic stainless steel containing 22% chromium and 5% nick-
el). Duplex stainless steels allow the combination of the specific properties
of resistance to corrosion of the austenitic and ferritic stainless steels;
however, they also share a number of specific problems, typical of both,
such as the precipitation of chromium carbides and the presence of a harm-
ful phase that forms at around 800C as well as an embrittlement issue at
475C.

Heat treatments
An annealing treatment before being put into operation is required in tem-
perature interval of 1050-1150 C; it is then rapidly cooled in water to op-
timize the austenite ferrite ratio that should be close to unity.

Physical and mechanical properties

Most of the physical properties are all comparable with those of austenitic
stainless steels (specific heat, conductivity, resistance and elastic modu-
lus); the only exception is thermal expansion between austenitic and ferrit-
ic stainless steels. When it is exposed to magnetic fields, the duplex com-
ponent is ferromagnetic, similar to what happens for ferritic stainless
steels.
The peculiar biphasic microstructure of such steels allows high values to
be obtained of both the yield stress (which is around double that of austen-
 289

itic stainless steels) and the tensile strength. Furthermore, they have an ex-
cellent behavior in terms of DBTT, due to transition temperature set to
around -80C.

Figure 5.10 - Effect of the microstructure of the resilience of some families of

stainless steels ( = austenite; + = ferrite and austenite; = ferrite).

Main applications
X2CrNiN23-4 (type 2304) was the first of the low alloy biphasic stainless
steels: this steel was developed to economically compete with the most
common austenitic stainless steels used in applications where mechanical
resistance and resistance to corrosion in chloride environments are essen-
tial. It is used in the production plants of nitric acid and for plants in con-
tact with caustic substances (concentrations <30%), with organic acids or
aqueous solutions rich in chlorides.
The steel X2CrNiMoN22-5-3 (type 2205) is most used duplex stainless
steel, thanks to its high mechanical resistance and excellent anti-corrosion
characteristics. It is largely used in the petrochemical and chemical field,
in environments contaminated by chlorides and in the presence of carbon
dioxide CO2 or hydrogen sulphide H2S; it is widely used in desalinisation
plants and plants where steel parts shall be in contact with dilute and con-
centrate solutions of sulphuric, phosphoric, acetic and formic acids.
290

Precipitation Hardening Stainless Steels

Precipitation hardening (or PH) stainless steels were developed to improve
mechanical properties of martensitic stainless steels, especially low frac-
ture toughness and to increase the resistance to corrosion at the same time.
They are classified based on the microstructure achieved through their heat
treatment, thus they are divided into: martensitic, semi-austenitic and aus-
tenitic. The hardening phase (after annealing) involves cooling the material
through the finely dispersed precipitation of intermetallic compounds and
interstitials in the crystalline matrix of the steel. For this purpose, alloy el-
ements are added such as aluminum, copper, titanium and niobium which
give rise to compounds of the type Ni3(Al, Ti), Ni3Ti and NiAl or Fe2(Mo,
Nb) or even carbonitrides type M(C, N) with M = Nb, Ti, Cr.
Nickel is always present in precipitation hardened stainless steels, both to
improve resistance to corrosion and to make the metal mass tough; it usu-
ally has very low carbon content (C0.1%) and molybdenum is often add-
ed for anti-corrosion.

Heat treatments, physical and mechanical properties

After the annealing treatment, semi-finished products have good cold plas-
tic deformability and good machinability; the work piece is then subjected
to the aging treatment namely, the precipitation hardening treatment - to
obtain mechanical properties aimed to withstand operating stresses.
Martensitic type precipitation hardening stainless steels, such as for exam-
ple X5CrNiCuNb16-4 (also called 17-4 PH), are usually annealed at
1030-1060C and then cooled in air: a low carbon martensitic structure is
obtained with low hardness and good deformability.
At the end of the operations of forming and machining operations, the
semi-finished product is subjected to aging treatment at temperatures be-
tween 480C and 630C and for times ranging 1 to 4 hours. By this way it
is possible to obtain a tensile strength that ranges 850-1400 MPa, with an
elongation A% ranging 25% to 12% (see Fig. 5.11); resilience at ambient
temperature ranges 40- 100J.
 291

Fig.5.11 - Steel X5CrNiCuNb16-4 (also called 17-4 PH) annealed at 1050C in

air, then aged according to various methods: curves .

Semi-austenitic precipitation hardening stainless steels, such as for exam-

ple X7CrNiAl17-7 (also called 17-7 PH), have a predominantly austenitic
structure after annealing at ambient temperature and cold-working opera-
tions, such as cold rolling, can be more easily conducted. After annealing
the austenitic structure is unstable so that either cold plastic deformation
operations or post heat treatment transform microstructure into martensite.
The aging heat treatment will be performed on the martensitic structure ob-
tained in this way, similarly to what happens in normal martensitic PH
stainless steels.

Main applications
Precipitation hardening stainless steels are generally commercialized onto
market in form of long products, round or hexagonal section bars, plates
and sheets. Thanks to high mechanical resistance and resistance to corro-
sion, they are employed in many sectors to fabricate valves, shafts, bear-
ings and turbine and compressor blades. They are also used in applications
for load cells, sprockets, firearms, utensils, springs and surgical instru-
ments.
292

Chapter 6 High-Temperature Resistant Alloys: Steels

for High Temperatures, Ni-Base Alloys and Ni-
Superalloys 31

Introduction
Main problems metals suffer at high temperatures are related usually to
both creep phenomena (refer to Chapter 2) and progressive deterioration of
surface oxidized layers that is typical of hot-corrosion damage mecha-
nisms. In Chapter 2 we already discussed about the creep damage mecha-
nisms, and the main approaches for design against creep phenomena, such
as the selection of materials with a high melting temperatures 32, the selec-
tion of face-centered cubic (fcc) metals 33 and the possibility to place inert
particles, such as fine carbides, on either grain boundaries, so to helps to
pin the grain boundaries sliding (in case diffusion creep dominates) or in-
side grains, so to counteract dislocation movements (in case dislocation
creep dominates).
On the other side, hot corrosion is the second important damage phenome-
non that may occurs in components that works at high temperatures. Main
problems are in this case related to hot-oxidation or gaseous corrosion,
namely all those damage mechanisms which basically refer to the reaction
of metal surface with oxygen at high temperatures usually in the absence

31 Main reference: F.C. Campbell, Elements of Metallurgy and Engineering Alloys,

ASM International, 2008 (Chapters 15, 29, 30).

32
Diffusion coefficients on which the creep rate depends are proportional to the homol-
ogous temperature (T/Tm).
33
Face-centered cubic (fcc) structures generally have superior creep resistance to body-
centered cubic (bcc) metals at equivalent homologous temperatures due to their slightly
more open bcc structure (i.e. fcc, at same temperature, has higher compaction factor than
bcc, namely 0.74 against 0.68) that results in greater diffusivity of solution atoms (e.g. Fe,
in steels) in bcc than fcc. This fact implies that solution atoms can diffuse easily and thus
creep diffusion mechanisms are favored compared to such crystal lattice with lower diffu-
sivity of solution atoms. Finally, to avoid misunderstanding, it is necessary to distinguish
the solution atom diffusivity from interstitial atom diffusivity; typical is the case of iron-
alloys: it is known (refer to Chapter 1) that fcc structure has higher capability to host inter-
stitial carbon atoms than bcc at same temperature; you may refer to Fe-C diagram for for
quick check: at 800C, for example, for a 0.30 C %wt. both Fe and Fe exist; the percent-
age of carbon dissolved in Fe is much lower than percentage of carbon hosted in Fe. As
consequence of higher compaction factor of fcc above discussed, the number of interstitial
sites (namely, the available spaces for hosting carbon) are higher in fcc than bcc. This ex-
plains the higher carbon diffusivity in fcc in iron alloys, notwithstanding the lower self-
diffusivity (i.e. solution atom Fe diffusivity) of fcc than bcc.
 293

of moisture (for that, we also call it dry-corrosion). For example, one of

the requirements of a high-temperature material in a turbine blade, or a su-
per-heater tube, was that it should resist attack by gases at high tempera-
tures and, in particular, that it should resist oxidation. Turbine blades do
oxidize in service, and react with H2S, SO2 and other combustion products.
In such environments, an oxidation film forms onto surface and its grow-
ing rate and its solubility in dry and hot environments are two important
factors to evaluate hot corrosion rate of metal alloys 34. Some films are
more protective than others; it is known that protective films are those with
low diffusion coefficients, namely those ones with high melting points.
That is one reason why A12O3 protects aluminum, Cr2O3 protects chromi-
um and SiO, protects silicon so well, whereas Cu2O and even FeO (which
have lower melting points) are less protective. Furthermore, as the oxide
film thickens, due to an intrinsic brittleness, it may develop cracks and it
either totally or partly lifts away from the material. Figure 6.1 shows how
this can happen. Generalizing, if the volume of the oxide is much less than
that of the material from which it is formed, it will crack to relieve the
strain (oxide films are usually brittle); conversely, if the volume of the ox-
ide is much greater, the oxide will tend to release the strain energy by
breaking the adhesion between material and oxide, and springing away. By
this way, the protective barrier offered by oxides to metal surface does not
become any more effective as oxidation proceeds. For protection, then, we
need an oxide skin which is neither too small and splits open (like the bark
on a fir tree) nor one which is too big and wrinkles up (like the skin of a
rhinoceros), but one which is just right.

34
When designing with oxidation-prone materials, it is obviously vital to know how fast
the oxidation process is going to be. Intuitively one might expect that, the larger the energy
released in the oxidation process, the faster the rate of oxidation. For example, aluminium
oxidizes much more slowly than iron. If you heat a piece of bright iron in a gas flame, the
oxygen in the air reacts with the iron at the surface of the metal where the oxygen and iron
atoms can contact, creating a thin layer of iron oxide on the surface, and making the iron
turn black. The layer grows in thickness, quickly at first, and then more slowly because iron
atoms now have to diffuse through the film before they make contact and react with oxy-
gen. If you plunge the piece of hot iron into a dish of water the shock of the quenching
breaks off the iron oxide layer, and you can see the pieces of layer in the dish. The iron sur-
face now appears bright again, showing that the shock of the quenching has completely
stripped the metal of the oxide layer which formed during the heating; if it were reheated, it
would oxidize at the old rate. Thus, the important thing about the oxide film is that it acts as
a barrier which keeps the oxygen and iron atoms apart and cuts down the rate at which
these atoms react to form more iron oxide. Aluminum, and most other materials, form ox-
ide barrier layers in just the same sort of way - but the oxide layer on aluminum is a much
more effective barrier than the oxide film on iron is.
294

Fig. 6.1 Breakdown of oxide films, leading to linear oxidation behavior.

Due to common main factor which contributes to both creep and hot corro-
sion damage mechanisms, the high temperature, when we talk about high-
temperature resistant alloys we have necessarily to talk about alloys that
are capable to resist both to creep and hot oxidation phenomena.
Generalizing, for metals, Cr2O3 is a good protective oxide, thus the level of
oxidation resistance at temperatures below 980 C for metal alloys is a
function of the chromium content. High-temperature nickel alloys can con-
tain 8 to 48% Cr. At temperatures above 980 C, the aluminum content be-
comes an important component in metals, as Al2O3 becomes the dominant
oxide protector, especially when thermal cycling is involved.
Furthermore chromium and aluminum can contribute in an interactive
manner to provide oxidation protection to metals, namely the higher the
chromium content, the less aluminum that may be required.
Alloys that are designed as heat-resistant materials include:
among ferrous alloys: chromium-molybdenum, chromium-
molybdenum-vanadium steels and stainless steels;
among non-ferrous alloys: nickel alloys and nickel superalloys.
In the following a brief description of these main heat resistant alloys is
provided.

Chromium-molybdenum and chromium-molybdenum-vanadium

steels
The chromium content increases oxidation resistance, while molybdenum
increases elevated temperature strength because it serves to prevent de-
composition of iron carbides (such a phenomenon is also called iron-
graphitization) up to 500C. For this reason, creep resistance is adequate
when steels are exposed for prolonged times just below this temperature,
 295

since molybdenum is effective for these steels against coarsening of car-

bides in such temperature range.
Among chromium-molybdenum structural steels, low alloyed CrMoNiMn
are weldable ferritic steels. The 8CrMoNiNb9-10 (equivalent to ASTM
A335 grade P24) series are the mostly used for seamless alloy-steel pipe
for high-temperature service.
The increase of chromium to above 7% in CrMo steels leads to a group of
steels containing also martensite. This microstructure introduces a new el-
ement of structural hardening, despite ferritic steels, due to its a fine lath
structure with stabilized fine carbides dispersed in matrix. Thus, structural
hardening by martensite is responsible for the large increase in strength of
X11CrMo9-1, as compared to 8CrMoNiNb9-10, as shown by Fig.6.2.
Further improvements, especially of the creep strength, have been
achieved by alloying with vanadium, niobium, tungsten and boron, as also
shown in Fig. 6.2b. The introduction of X20CrMoNiV11-1 at the begin-
ning of the sixties allowed major increases in power plant efficiency. The
transformation behavior and microstructure of this alloy are comparable to
those of X11CrMo9-1. The higher creep-rupture strength of
X20CrMoNiV11-1 results mainly from the larger volume of dispersed
M23C6 carbides in the microstructure, a result of the alloy's higher carbon
content. The best results in terms of elevated-temperature strength are ob-
tained by quenching and tempering to produce a microstructure consisting
of upper bainite.
Both the chromium molybdenum and the chromium-molybdenum vanadi-
um steels extend the operating range up to 540C.
296

(a)

(b)

Fig.6.2 - Creep-rupture strength of some Cr-Mo and Cr-Mo-V heat-

resistant steels.

Stainless steels for high temperatures

Stainless steels are also used for elevated temperature applications. Mar-
tensitic stainless steels are used at temperatures up to 540 to 650C, but
they must be tempered at approximately 55C higher than the operating
temperature so to prevent softening in service (due to coarsening of car-
bides formed during previous tempering treatment).
Due to their higher chromium contents, ferritic stainless steels have the
best scaling resistance, but they are limited to service temperatures of ap-
proximately 370C to avoid the precipitation of the embrittling phase
(refer to Chapter 5, Fig. 5.2).
Austenitic stainless steels have the best creep resistance of the stainless
steels and are used at temperatures up to 870C. In austenitic stainless
steels, strengthening mechanism for enhancing creep resistance is related
 297

to both the limited diffusivity of iron in austenitic matrix - which is smaller

than in a ferritic matrix - and precipitation hardening by fine intermetallic
phases or carbonitrides as they are capable to counteract dislocation creep
mechanism. Particularly, small quantities of Nb and Ti that are added to
stabilize austenitic stainless steels by subtracting carbon to chromium by
forming fine Nb- and Ti-types carbides (refer to Chapter 5) are also bene-
ficial in reducing creep rate, due their intrinsic high-temperature stability
(they do not coarse for high temperature prolonged exposure, so they rep-
resent an effective barrier to dislocation movements). However, a major
problem with the austenitic grades is their high coefficients of thermal ex-
pansion, which must be compensated for during design. For these reason,
austenitic stainless steels are frequently used in the power generation in-
dustry at temperatures greater than 650 C in low-stress part (limited
around 50 MPa or some higher) which are expected to remain in service
for more than 100,000 h.

Ni-base alloys
Nickel and nickel alloys have an excellent combination of corrosion, oxi-
dation, and heat resistance, combined with good mechanical properties.
They are used extensively in aggressive environments, such as in the
chemical processing, pollution control, power generation, electronic, and
aerospace industries.
Nickel is ductile and can be made by conventional processing methods into
castings, powder metallurgy parts, and various hot- and cold-worked
wrought products. Commercially pure nickel has a moderately high melt-
ing temperature (1468C), a density of 8.89 g/cm3, and low elastic modu-
lus of 209 Pa. Nickel is used principally as an alloying element to increase
the corrosion resistance of ferrous and copper alloys, with only approxi-
mately 13% of the annual production used for nickel-base alloys. Approx-
imately 60% is used in stainless steel production, with another 10% in al-
loy steels and 2.5% in copper alloys.

Basics of Nickel Metallurgy

As a result of its face-centered cubic (fcc) crystal structure, nickel has ex-
cellent ductility and toughness. Alloying is used to further improve corro-
sion and heat resistance. Austenitic nickel matrix can be strengthened by
solid-solution hardening, carbide precipitation, precipitation hardening,
and/or work hardening.
Solid-solution hardening is provided by cobalt, iron, chromium, molyb-
denum, tungsten, vanadium, titanium, and aluminum. Iron, cobalt, titani-
um, chromium, and vanadium are weaker solid-solution-hardening ele-
298

ments. Although nickel itself is not a carbide former, the presence of car-
bon as an alloying element leads to the formation of carbides. The carbides
most frequently found in nickel alloys include MC, M6C, M7C3, and
M23C6, where M is the carbide-forming element or elements, such as
chromium, which forms Cr7C3. In general, carbides and fine particles im-
prove the elevated-temperature strength if they are located on the grain
boundaries as discrete particles. However, if they form continuous grain-
boundary films, they can cause embrittlement.

Nickel-Chromium-Iron Alloys.
This family of alloys was developed for high-temperature oxidizing envi-
ronments. They typically contain 50 to 80 wt% Ni, which permits the addi-
tion of other alloying elements to improve strength and corrosion re-
sistance while maintaining toughness. The Ni-Cr-Fe alloys contain
chromium ranging from 14 to 30 wt% and they form a protective surface
film of Cr2O3, they have excellent corrosion resistance in many severe en-
vironments, including immunity to chloride ion stress corrosion cracking.
They also have good oxidation and sulfidation resistance along with good
strength at elevated temperatures.
Among variety, the alloy 800 commercially known as INCOLOY is an Ni-
Cr-Fe alloy austenitic, solid-solution alloy. Titanium nitrides, titanium car-
bides, and chromium carbides normally appear in the alloys microstruc-
ture. The nitrides are stable at all temperatures below the melting point and
are therefore unaffected by heat treatment.
At elevated temperatures it offers resistance to oxidation, carburization,
and sulfidation along with rupture and creep strength. It is widely used ma-
terial for construction of equipment requiring corrosion resistance, heat re-
sistance, strength, and stability for service up to 816C. For applications
requiring greater resistance to stress rupture and creep, especially at tem-
peratures above 816C, INCOLOY alloys 800H and 800HT 35 are used.
INCOLOY is approved under the Boiler and Pressure Vessel Code of the
American Society of Mechanical Engineers (ASME).

35 Incoloy 800, 800H and 800HT are identical except for the higher level of
carbon in alloy 800H compared to 800 series and the addition of up to 1.20 per-
cent aluminum and titanium in alloy 800HT, compared to 800 and 800H. Incoloy
800 was the first of these alloys and it was slightly modified into Incoloy 800H.
This modification was to control carbon (0.05-0.10%) and grain size to optimize
stress rupture properties. Incoloy 800HT has further modifications to the com-
bined titanium and aluminum levels (.85-1.20%) to ensure optimum high tempera-
ture properties.
 299

Ni-Superalloys
Ni-superalloys are heat-resistant alloys of nickel, iron-nickel that are fre-
quently used at temperatures exceeding 540C. However, some superal-
loys are capable of being used in load-bearing applications in excess of
85% of their incipient melting temperatures. They exhibit the best combi-
nation of high strength, good fatigue and creep resistance, good corrosion
resistance, and the ability to operate at elevated temperatures for extended
periods of time (i.e., metallurgical stability). Their combination of elevated
temperature strength and resistance to surface degradation is unmatched by
other metallic materials. Superalloys have been used in aircraft, industrial,
and marine gas turbines, nuclear reactors, aircraft skins, spacecraft struc-
tures, petrochemical production, orthopedic and dental prostheses, and en-
vironmental protection applications. Todays modern, high-performance
aircraft jet engine could not operate without the major advances made in
superalloy development over the past 50 years. Thanks to superalloys, in-
creases in engine operating temperatures over the last 50 years have been
gradual but significant, from approximately 400C to 1290C, that result-
ed increase in operating temperature translates into improved engine effi-
ciency. Typical applications for superalloys in a jet engine are shown in
Fig. 6.3.

Fig.6.3 - Typical materials selection for jet engine components.

300

The main strengthening mechanisms for nickel and iron-nickel superalloys

are solid solution hardening and precipitation hardening. In addition, grain-
boundary carbides are important in providing high-temperature stability.
The microstructure consists of fine carbides, the Ni3Al particles, dis-
persed in a fcc nickel-rich solid solution; thus, this alloy is mainly
strengthened by a combination of solid solution (addition of alloying ele-
ments) and the precipitates dispersed as high-temperature stable carbides
into matrix, to prevent dislocation creep phenomena, and formed at grain
boundaries, to prevent diffusion creep phenomena (see Fig.6.4).

Fig.6.4 - Microstructure of a precipitation-strengthened nickel-base superalloy.

Actually the precipitate morphology is determined by degree of lattice mismatch
between the ' precipitate and the matrix, ranges from spherical precipitates
when lattice mismatches is in the order of 0 to 0.2%, cubical as in the figure - for
mismatches of 0.5 to 1%, and platelike at mismatches above approximately
1.25%.

The high coherency between the precipitate and matrix is maintained to

high temperatures, and the precipitate coarsens very slowly, so that the
precipitate overages slowly, even at temperatures as high 0.7 Tm. Nickel-
base superalloys have the best creep resistance of the superalloys and are
used as turbine blades in engines operating at temperatures as high as
1290C (T/Tm=0.9). Among commercial superalloys, we mention:
 301

Hastelloy series, solid-solution-strengthened nickel-base superal-

loys primarily developed for low-temperature service, often in cor-
rosive environments.
Inconel 718, a superalloy that contains niobium which is strength-
ened primarily by phase (i.e. Ni3Nb particles); it rapidly loses
strength in the range of 650 to 815C because of the instability of
the precipitates. However a widespread use of Inconel 718 is
due to its excellent combination of mechanical properties, moder-
ate price, and ease of processing, including weldability. Inconel
718 may account for as much as 60 wt% of the total consumption
of superalloys.

An example of application: Ni-superalloy made turbine blade

Improved high-temperature material properties are largely responsible for
the increase in the engine operating temperature. Some improved material
performance has come about from minor alterations in alloy chemistry,
and some has resulted from processing changes. For example, the major
stress axis in a turbine blade is parallel to the blade axis. In a polycrystal-
line blade, this stress is normal to some grain boundaries, and this causes
voids, precursors to fracture, to initiate on the boundaries (Fig.6.5).

Fig. 6.5 Creep cavitation mechanisms.

Directional solidification (i.e., solidifying the material sequentially from

the blade bottom to its top) results in columnar grains having boundaries
aligned along the blade axis. This significantly reduces the cavitation prob-
lem. Further improvements came with the casting of single crystal blades.
Increasing the superalloy grain size from 100 mm to 10 mm (the order of
the thickness of a turbine blade) reduces the creep rate by approximately 6
302

orders of magnitude when Coble creep 36 is the dominant creep mechanism,

as it often is under typical blade operating conditions.

Fig.6.6 - Creep comparison of a nickel-base superalloy for different casting proce-

dures.

For further increase in creep resistance, the turbine blades made of superal-
loys are coated with thermal barrier coating. To insulate blade of Ni-
Superlloy, overlay protective coatings are generally deposited on deposited
on top surface of base Ni-superalloy metal; MCrAl or MCrAlY, zirconia
layers (0.3-0.4mm thick) coatings, are derived directly from the deposition
process. They do not require diffusion for their formation. The constituent
denoted M in these designations has, at various times, been iron, cobalt,
nickel, or combinations of nickel and cobalt. Overlay coatings are usually
applied by physical vapor deposition (PVD) in vacuum chambers. They al-
so may be applied by plasma spray techniques.

Temperature C

Fig.6.5 - Thermal barrier coating for turbine blades.

36Coble creep is a diffusion creep mechanism that consists in diffusion of atoms in a ma-
terial along the grain boundaries, which produces a net flow of material and a sliding of the
grain boundaries.
 303

Chapter 7 Non-Ferrous Structural Alloys: Magnesi-

um Alloys 37
Introduction: the search for lightweighting in automotive
A 2013 KPMGs study (KPMGs Global Automotive Executive Survey
2013) conducted to automotive market and trend shows the automotive in-
dustry is being shaped by various driving forces. Environmental pressures
are leading to more efficient engines either via e-mobility or improvements
to internal combustion engine (ICE) traditional technologies. With an in-
creasing proportion of the worlds people, increasing BRICs economies,
emerging markets demand are pushing for request of increased mobility
for overcrowded cities. In old Europe many cities are limiting downtown
pollutions and traffic congesting by closing large urban areas to pollutant
vehicles. New, smaller, urban friendly vehicles are necessary while car-
sharing and other mobility concepts are rapidly growing in popularity, as
shown in Table 7.1.

Table 7.1 The major driving forces for competing on today automotive market.

Recent changes to the Corporate Average Fuel Economy (CAFE) are driv-
ing automakers to seek more aggressive methods for fuel consumption re-
ductions. Lightweighting of vehicles will be a factor in meeting these re-

37 Main reference: F.C. Campbell, Elements of Metallurgy and Engineering Alloys,

ASM International, 2008 (Chapters 27).

304

quirements due to the inherent relationship between mass and fuel con-
sumption. In addition, lightweighting may benefit other advanced fuel-
saving but load constrained technologies, such as battery-powered vehi-
cles.
The ability to introduce new lightweight materials into vehicles is not a
trivial matter. Many see a new concept, or limited production, vehicle in-
troduced to the market with lightweight space-aged materials and feel
that adoption by mass produced vehicles is a simple matter of remove and
replace. However, this is not the case; factors such as existing infrastruc-
ture, material cost, and high volume capacity become of great importance
for mass production vehicles. In addition, many of the low production ve-
hicles incorporate these lightweight materials as a method for gaining ex-
perience on their performance. Without significant data to support durabil-
ity, the risk-averse automotive culture will not adopt new materials.
Therefore it often takes many years to implement lightweight technology
in mainstream production vehicles.
Today, there is a high emphasis on greenhouse gas reductions and improv-
ing fuel efficiency in the transportation sector, all car manufacturers, sup-
pliers, assemblers, and component producers are investing significantly in
lightweight materials Research and Development and commercialization.
All are moving towards the objective of increasing the use of lightweight
materials and to obtain more market penetration by manufacturing compo-
nents and vehicle structures made from lightweight materials. Because the
single main obstacle in application of lightweight materials is their high
cost, priority is given to activities to reduce costs through development of
new materials, forming technologies, and manufacturing processes. Yet the
weight reduction is still the most cost-effective means to reduce fuel con-
sumption and greenhouse gases from the transportation sector. The reason-
ing behind this is simple; it takes less work to accelerate and move a light-
er object. It has been estimated that for every 10% of weight eliminated
from a vehicle's total weight, fuel economy improves by 7%. This also
means that for every kilogram of weight reduced in a vehicle, there is
about 20 kg of carbon dioxide reduction. In terms of lifecycle manage-
ment, the use cycle of the vehicle typically dominates the overall CO2
emissions generation of the vehicle (see Figure 4). Lighter weight materi-
als have the advantage of providing sustained greenhouse gas emission re-
ductions over the use cycle of the vehicle. Conventional steels have been a
dominant force in the material selection of automotive parts. A combina-
tion of high-strength, low cost and capacity to be produced in high vol-
umes has made mild steel a very attractive material in automotive applica-
tions. However, as technology changes and fuel economy increases in
 305

importance, other materials are gaining acceptance in the automotive in-

dustry. Materials such as high-strength steel, aluminum, composites, and to
date to a much lesser extent magnesium have increased their overall utili-
zation over the past 30 years, while mild steels have seen a steady decline
(see Fig.7.1). At the same time, regular steel and iron castings have also
seen a steady decline.

Figure 7.1 Vehicle Material Composition by Percent Mass.

Box Requirements of the materials in automotive

Generally speaking, the materials used in automotive industry need to fulfil

several criteria before being approved. Some of the criteria are the results of
regul tion and legislation with the environmental and safety concerns and
some are the requirements of the customers. In many occasions different
factors are conflicting and therefore a successful design would only be pos-
sible through an optimized and balanced solution. Below four main key-
factors are addressed:
Lightweighting capability. To reduce part weight onboard, all car
306

manufacturers, suppliers, assemblers, and component producers are

investing significantly in lightweight. Actually it is better to refer to
specific strength, strength limit (fatigue limit, for example, in fa-
tigue design) versus density for selection of candidate weight-
saving materials. On the other hand, often the industrial application
of lightweight materials is the higher cost of part made of an un-
conventional materials (for the specific purpose/components) than
conventional one. The unitary cost of the lighter re-designed part
usually increased since increased costs accounted for product de-
velopment with new material, not fully optimized/mature forming
and joining technologies that contribute to increase final manufac-
turing process costs. At the present state, the replacement of steel is
being pursued with aluminum, magnesium, carbon fiber composites
and foams. Further key-issues related to the recycling and recovery
of end-of-life vehicles have been addressing by automakers since
recovery target of 85% of material used in manufacturing phase is
driving the auto industry to adopt lightweight materials and manu-
facturing and assembling technologies capable to meet such ambi-
tious targets. It is worth of notice that constant automakers efforts
in development and adoption of design approaches that pursue se-
lection and use of easy-to-recycle materials and assembling tech-
nologies is not only limited to decrease the environmental impact
of product life cycle, but it is also an effective way to mitigate costs
of manufacturing cycles for new products made of higher unitary
price materials (i.e. dollars per kg of material used).
Cost. One of the most important consumer driven factors in auto-
motive industry is the cost. Since the cost of a new material is al-
ways compared to that presently employed in a product, it is one of
the most important variables that determines whether any new ma-
terial has an opportunity to be selected for a vehicle component.
Cost includes three components: actual cost of raw materials, man-
ufacturing value added, and the cost to design and test the product.
This test cost can be large since it is only through successful vehi-
cle testing that the product and manufacturing engineers can
achieve a level of comfort to choose newer materials for applica-
tion in a high-volume production program. For these reasons steels
with their wide range of yield strength combined with high modu-
lus together with ease of manufacture and low cost have largest
share of the market. The higher unitary cost of alternative materials
such as aluminum or composites mean that steels position as the
first-choice material could be still secure for years [Corus Automo-
tive Eng. 2010]. As historic lightweight materials, aluminum and
magnesium alloys are the usual solutions for replace steels and cast
 307

irons. As already mentioned, the ability to approach the total cost of

the competition, therefore, must be associated with lower compo-
nent manufacturing costs. For this reason, notwithstanding alumi-
num and magnesium have much higher unitary price (i.e. dollars
per kg), compared to cast irons, a well-designed and properly sized
part in either cast aluminum or magnesium components are poten-
tially less costly. This is based on their reduced manufacturing cy-
cle times, better machinability, ability to have thinner and more
variable wall dimensions, closer dimensional tolerances, reduced
number of assemblies, more easily produced to near net shape thus
decreasing finishing costs, and less costly melting/metal-forming
processes. This suggests not to refer to unitary price of materials in
viability studies conducted by a R&D department, but an economic
assessment based on the entire product value chain for the conven-
tional and alternative scenarios should be conducted to evaluate
(actualized) costs of new products, accordingly to New Product
Development (NPD) best practices today employed. In any case
wrought aluminum and magnesium components are almost always
more costly to produce than their ferrous counterparts, but lighter
and usually competitive in terms of GHGs emissions over the
product life (refer to Figure 7.2). Since cost may be higher, deci-
sions to select light metals must be justified on the basis of im-
proved functionality, weight saving objectives and environmental
impact capability. Government regulations mandate reductions in
exhaust emissions, improved occupant safety, enhanced fuel econ-
omy, reductions in workplace emissions, increased safety require-
ments, and requirements for toxic materials handling and disposal.
Also the high manufacturing costs, the lower productivity (a carbon
fiber composite manufactured part requires batch process hardly to
automate) and the reduced recyclability is one of the major barriers
in use of the carbon fiber composite materials.
308

Figure 7.2 - Total Greenhouse Gas Emissions during Various Phases of the Vehicle
Lifecycle.

Safety, crashworthiness. The ability to absorb impact energy and be

survivable for the passengers is called the crashworthiness of
the structure in vehicle. There are two important safety concepts in
automotive industry to consider, crashworthiness and penetration
resistance. Crashworthiness is defined as the potential of absorption
of energy through controlled failure modes and mechanisms that
provides a gradual decay in the load profile during absorption. The
current legislation in design of the automobiles requires that, in the
case of an impact at speeds up to 15.5 m/s with a solid, immovable
object, the occupants of the passenger compartment should not ex-
perience a resulting force that produces a net deceleration greater
than 20g. The current trend of materials in car industry is towards
replacing metal parts more and more by polymer composites in or-
der to improve the fuel economy and reduce the weight of the vehi-
cles. The behavior of composite failure in compression is the oppo-
site to metals. Most composites are generally characterized by a
brittle rather than ductile response to load. While metal structures
collapse under crush or impact by buckling and/or folding in accor-
dion (concertina) type fashion involving extensive plastic defor-
mation, composites fail through a sequence of fracture mechanisms
involving fiber fracture, matrix crazing and cracking, fiber-matrix
de-bonding, de-lamination. The actual mechanisms and sequence of
damage are highly dependent on the geometry of the structure, lam-
ina orientation, and type of trigger and crush speed, all of which
can be suitably designed to develop high energy absorbing mecha-
nisms. Several aspects are considered in design for improved
crashworthiness including the geometrical and dimensional aspects
 309

which have key role in different stages of crash. However the mate-
rials deformation and progressive failure behavior in terms of stiff-
ness, yield, strain hardening, elongation and strain at break are also
very important in the energy absorption capacity of the vehicle.
[Witteman, 1999].

Recycling and life cycle considerations. One of the major growing

concerns in all the industries including automotive, is an increased
awareness for environment. Issues such as protection of re-
sources, reduction of CO2 emissions, and recycling are increas-
ing the topics of consideration. While the United States has not is-
sued regulations concerning automotive end-of-life requirements,
European Union (E.U.) and Asian countries have released stringent
guidelines. European Union legislation implemented in 2006 dic-
tates that a significant percentage of the vehicle should be re-used
or recycled. The End of Life Vehicles (ELV) Directive from envi-
ronment agency aims to reduce the amount of waste produced from
vehicles when they are scrapped. Around two million vehicles
reach the end of their life in the UK each year. These vehicles are
classed as hazardous waste until they have been fully treated. The
directive requires ELV treatment sites to meet stricter environmen-
tal standards. This would mean that the last owner of a vehicle must
be issued with a Certificate of Destruction for their vehicle and they
must be able to dispose of their vehicle free of charge. Vehicle
manufacturers and importers must cover all or most of the cost of
the free take-back system. It also sets higher reuse, recycling and
recovery targets and limits the use of hazardous substances in both
new vehicles and replacement vehicle parts. [Environment agency,
2010]. As the results of the new legislations, no discussion of new
materials in the automotive industry should conclude without a
consideration of recycling. Considerable R&D efforts are now fo-
cused on developing materials with greater potential of recycling
and re-use or developing ways of recycling and re-use of the cur-
rent materials. This includes both metal and composite materials.
The composition and forming processes of the metal materials are
changing to accommodate this recycle and re-use demand. This al-
so justifies the great attention towards natural fiber based compo-
sites and new high temperature resistant thermoplastic resins. Tra-
ditionally the design of the part/components has mainly been the
responsibility of the OEMs. Recently, however, manufacturers have
begun to shift design responsibility to part/component suppliers.
After the manufacturing stage, the vehicle spends a long period of
time in the use phase of the life cycle. In the past, the median life of
310

a vehicle has been reported to be 1213 years [Libertiny,1982,

1993]. Lately, the median life has increased to around 16 years with
as many as 5% of the vehicles still remaining on the road after 30
years of operation [Davis, 2004].

Roskill UK, leader in international metals and minerals research, estimates

that consumption of magnesium reached a new peak in 2012, 1.1Mt, with
demand having grown by 5.5%py over the last decade. The largest end-
uses for magnesium are die-cast magnesium and aluminum alloys, each
accounting for a third of total consumption. On the other hand, the trans-
portation industry is the largest consumer of die-cast magnesium and the
second largest consumer of aluminum-magnesium alloys behind packag-
ing.
 311

Magnesium Alloys for Structural Applications

Magnesium has the lowest density (1.738 g/cm3) of the structural metals,
with a density of approximately 2/3 that of aluminum and 1/4 that of steel.
Although magnesium alloys have only moderate tensile strengths, in the
range of 140 to 345 MPa, and a modulus of elasticity of only 45 GPa, due
to their low densities, they exhibit favorable specific strengths (tensile
strength/density) and specific moduli (modulus/ density) comparable to
other structural metals. Magnesium and its alloys are used in a wide varie-
ty of structural applications, such as automotive, industrial, materials han-
dling equipment, kitchen appliances, hand-held tools, luggage frames,
computer housings, cellular phones, and ladders. Magnesium is relatively
inexpensive 38 and easy to cast, machine, and weld; its electrical and ther-
mal conductivity and heat capacity are relatively high. Magnesium alloys
have very good damping capacity, and castings have found applications in
high vibration environments.
Over the years, one of the major drawbacks 39 of magnesium alloys has
been corrosion. Magnesium occupies the highest anodic position on the

38 Despite magnesium is commonly thought as an expensive metal, unitary price of

magnesium over time periods varies so much to be either less expensive of or more expen-
sive of its direct competitor in lightweighting transport sector strategy. The problem is more
precisely related to high volatility of magnesium price, instead of its temporary shock uni-
tary price. Magnesium price has been varying since first appearance on market and it is
strictly related to availability on marketplace of magnesium supplying to satisfy current
demand. Prior to World War I, Germany was the only significant producer of magnesium,
but during the war other countries recognized the strategic importance of this metal and
built plants to meet their inner military demands. The interest of governments in magnesi-
um production during wartime caused relatively prolonged stable price. The use of expen-
sive Mg metal decreased after World War I; the beginning of World War II resulted again
in increased Mg demand: the consequence was higher prices since low availability on mar-
ket. U.S. Government implemented plant production in the period 1943-1945, thus stabiliz-
ing the price. Various other period of fluctuant price of magnesium were therefore due to
mismatch between demand and supply: high unitary price are expected when magnesium is
recognized as strategic, primarily by automotive sector, but recent low demand period have
led to reduced production, thus low supplying capacity of magnesium producers. Low
magnesium price periods were due to over production of magnesium against current request
on market; thus, highly fluctuant unitary prices are direct consequence of a microeconomics
economic model that determine price of any goods by supply and demand relationships.

39 One other major drawback that has been considered over the years is the supposed
high ignitability of magnesium. If it is dust or fine particles of magnesium are highly ignit-
able in air, due to high reactivity of magnesium to oxygen, it is not quite different from the
affinity and reactivity of aluminum fine powders or dust to oxygen. What is really different
and more hazardous for magnesium is that, when ignited, it cannot be extinguished simply
removing heat sources that has brought magnesium to melt point and flame ignition condi-
312

galvanic series and, as shown in Fig. 2.56 of Chapter 2 can be subject to

rather severe corrosion. The
corrosion problem is mainly due to the impurity elements iron, nickel, and
copper that act as galvanic microcells (refer to Chapter 2). However, the
use of higher-purity magnesium alloys has led to corrosion resistance ap-
proaching that of some of the competing aluminum casting alloys.

Basics of Magnesium Metallurgy

Pure magnesium has a hexagonal close-packed crystalline structure that re-
stricts slip at room temperature to the basal planes (see Fig.7.3). Magnesi-
um alloys work harden rapidly at room temperature, and their ductility is
low. Since additional slip planes become operative at elevated temperature,
wrought magnesium alloys are normally formed at temperatures greater
than 205C, normally in the range of 345 to 510C, depending on the spe-
cific alloy.

Figure 7.3 The hexagonal close-packed crystalline structure, schematic represen-

tation on the left, actual spatial occupancy of Mg atoms o the right.

Magnesium also has a rather low melting point (650C), which increases
its susceptibility to elevated-temperature creep. However, through im-

tion. However, recent developments by Koreans researchers has led to put onto marketplace
new magnesium series added with CaO that make magnesium alloy self-extinguishable in
case of flame ignition. These magnesium modified alloy series are called Eco-Magnesium
and when they are produced by adding over 0.5~0.7wt% CaO they can be considered fire-
retardant and fire-proof.
 313

proved alloying techniques, the creep resistance of magnesium alloys has

been significantly improved.

Alloying Elements

The most important alloying additions are aluminum, zinc, and zirconium.
Aluminum provides solid-solution strengthening and widens the freezing
range, making the alloy easier to cast. As aluminum is added to magnesi-
um, the strength continuously increases as the aluminum content is in-
creased up to 10 wt% Al, but the elongation peaks at approximately 3 wt%
Al. Mg alloys with 3 wt% Al have the highest ductility, and those with 9%
Al have the best strength, but those with approximately 6 wt% provide the
best combination of strength and ductility.
This phenomenon is explained by the Mg-Al phase system, as it is shown
in Fig.7.4. This system is an eutectic system between the solid solution
and a brittle intermetallic compound (Mg17Al12).

Figure 7.4 - The magnesium-rich end of the magnesium-aluminum phase diagram.

In the magnesium-aluminum phase diagram (Fig. 7.4), there is a eutectic

between the terminal solid solution and the brittle intermetallic compound
b (Mg17Al12). The eutectic structures contain more compound than a solid
314

solution, and since the compound is brittle, alloys with a eutectic network
are also brittle. When the aluminum content exceeds 8%, discontinuous
precipitation of the phase occurs at the grain boundaries as shown in
Fig.7.5, leading to a decrease in ductility. The phase diagram also shows
that aluminum has a maximum solubility of 12.7 wt% at 436C, which de-
creases down to approximately 2 wt% at room temperature. While this
type of solubility would seem to indicate that these alloys would be ame-
nable to precipitation hardening, unfortunately the resulting precipitate is
coarse and results in only moderate hardening. While many of the alloying
additions to magnesium form eutectics with decreasing solid solubility that
lead to precipitation hardening, the strength that results from this harden-
ing mechanism is much less than that observed with the precipitation hard-
ened aluminum alloys. Since the response to precipitation heat treatment is
poor, most of these alloys are used in either the as-cast.
Zinc behaves in a manner similar to aluminum; the ductility reaches a
maximum at a 3 wt% addition, and a good combination of strength and
ductility occurs with 5 wt% Zn. It also improves the corrosion resistance
by combining with the harmful impurities iron and nickel. Zinc is also
used in conjunction with zirconium, rare earths 40, or thorium to produce
precipitation-hardenable alloys.
Zirconium is a powerful grain refiner. However, zirconium cannot be
used in combination with aluminum or manganese because it forms brittle
intermetallic compounds that destroy ductility.

Harmful elements
The elements iron and nickel are harmful impurities that greatly reduce
corrosion resistance. Copper is also often considered, along with iron and
nickel, as an impurity but is actually used as an alloying addition in some
magnesium alloys. Iron is by far the most troublesome of the three, be-
cause nickel and copper are more readily controlled by selecting the purity
of the starting materials.

The ASTM designation of Mg alloys and most used Mg alloys

In the following, an example of ASTM designation of magnesium alloys is
shown and thus commented as practical example (all magnesium alloys are
designated by this scheme):

AZ91D

40Rare earth (RE) elements are potent solid solution strengtheners in magnesi-
um alloys.
 315

The code above shown represent:

The first two letters, A and Z in the example, indicate respectively
the alloying elements with higher content. The Table 7.2, first col-
umn, gathers all the possibilities for codifying the two alloying el-
ements added in chemical composition;
The two following numbers indicate respectively the round per-
centage of two elements (in the example, 9% and 1% for Al and
Zn respectively).
Third letter indicates different type of same alloy (in terms of pu-
rity).
Fourth letter indicates supplying condition.

Table 7.2 - ASTM International designation for magnesium alloys.

In the following, most used commercial alloys are mentioned.

Casting Alloys
Magnesium has excellent die-filling properties and large, thin-walled and
complex components can be cost-effectively produced by casting rather
than by joining smaller parts together made of wrought Mg alloy parts.We
mention among variety:
Mg-Al casting alloys, the AM series. When higher ductility is re-
quired, a low aluminum content is pursued in order to decrease
316

amount of phase around grains there are some alloys with

lower aluminum contents, such as AM20 (Mg-2Al-0.5Mn), AM50
(Mg-5Al-0.3Mn), and AM60 (Mg-6Al-0.2Mn).
The Mg-Al-Zn casting alloys, the AZ series. They are Mg-Al-Zn
casting alloys. Addition of Zn also helps to strengthen the alloys
by a combination of solid solution - like Al effect - and precipita-
tion hardening, thanks to Zn capability in refining precipitates that
form during ageing treatment (after solution treatment). The addi-
tion of zinc must be balanced by a concurrent decrease in the alu-
minum content to keep the total below approximately 11 wt%. For
example, comparing the AZ63 (6%Al-3%Zn) to AZ91 (9%Al-
1%Zn), both them containing less than 11% of Al and Zn.
Both AM and AZ series can be used at temperatures less than 120
C, since they are susceptible of low-temperature creep phenome-
na. Creep in magnesium alloys occurs primarily by grain-boundary
sliding: as the temperature in these alloys increases, the phase at
the grain boundaries softens and it cannot prevent grain-boundary
sliding.
The creep resistant Mg-Al-Si: the AS series. For better creep re-
sistance, Si is added. It forms fine, hard particles of Mg2Si along
the grain boundaries to help retard grain boundary sliding. Exam-
ples are the alloys AS21 (Mg-2Al-1Si-0.4Mn) and AS41(Mg-4Al-
1Si-0.3Mn). In any case they cannot compete with creep resistance
of cast heat treated aluminum alloys.
The Mg-Zn-Zr casting alloys: the ZK series. The remarkable grain-
refining ability of zirconium led to development of high strength
and high ductility alloys such as ZK51 (Mg-4.6Zn-0.75Zr) and
ZK61 (Mg-6Zn-0.7Zr). Both ZK51 and ZK61 produce fairly high
strength levels when heat treated to the T5 (i.e. part is cooled from
an elevated temperature shaping process then artificially aged to
form precipitates) or T6 (i.e. part is solution heat treated, then arti-
ficially aged) tempers, respectively.
The Mg-Rare Earth-Zn-Zr casting alloys: the ZE series. RE ele-
ments (La, Ce, etc.) are added. On aging during precipitation heat
treatments, fine precipitates can be formed. They enhance creep
resistance due to the combined strengthening effects of grain-
boundary phases and precipitates within the grains. One common
alloy is ZE41 (Mg-4Zn-1.3RE-0.7Zr), which has moderate
strength in the T5 condition that is maintained up to 150 C.
 317

The Magnesium-Yttrium casting alloys: the WE43 series. Most recently

developed high-temperature alloys that contain approximately 4 to 5 wt%
Y, they exhibit high strength with good creep resistance at temperatures up
to 300 C and superior corrosion resistance comparable to some alumi-
num-base casting alloys. However Y is very expensive and hard to mix in
melting phase. For this reason a mischmetal containing 75 wt% Y in REs
is used instead of pure yttrium. An example is the alloy WE43 (Mg-4Y-
3.25RE-0.5Zr) that keep strength high up to 200C. Recent commercial
type Elektron 21 has been introduced by Magnesium Electron UK.

Wrought Magnesium Alloys

Wrought magnesium alloys are produced as sheet and plate, extruded bars,
billets, shapes, and, to some limited extent, forgings. Despite the hexago-
nal close-packed structure and its low number of active slip planes, when
forming process is conducted at recommended temperatures (345 to 510
C), Mg alloys exhibit very high formability. In fact, a number of slip
planes become active at this temperature interval and a number of standard
forming processes can be used with such correct forming temperatures.
Among variety, the AZ31B (Mg-3Al-1Zn-0.3Mn) is the most widely used
sheet and plate alloy.
This alloys is strengthened by a combination of solid-solution strengthen-
ing, grain size control, and cold working.
Some advantages of hot forming of Mg are:
forming process can usually be conducted in one step without the
need for intermediate anneals;
parts can be made to closer tolerances;
hardened steel dies are not necessary for most forming processes.

Box Manufacturing operations

Machining operations. Mg is the easiest of all of the metals to machine. Ma-

chining is usually conducted dry, using large depths of cut and high feed
rates. Very tight dimensional tolerances are easily achieved, with surface
finishes. Although machining is usually conducted dry, cutting fluids can be
used to reduce the chances of distortion and minimize the danger of fire
when chips are fine, as during finish machining. When magnesium chips ig-
nite, they burn with a brilliant white light and flame is not self-
extinguishing. It is very important to remind that water cannot be used for
extinguish flame, since Mg melt react with hydrogen contained in water
with explosive reaction.
Joining techniques. Mg alloys are welded by traditional techniques that use
318

gas-shielded arc welding processes (MIG/TIG), although processing param-

eters and equipment used for aluminum welding have to be modified. In au-
tomotive sector, the most promising method for welding thin Mg sheets is
laser or electron beam, while friction stir welding is a more recent develop-
ment suitable for joining materials that are more difficult to weld or even for
joining dissimilar materials like magnesium or aluminum alloys.
Corrosion protection. For ordinary outdoor applications, substantial im-
provement over the earlier alloys are sufficient. On other side, seacoast loca-
tions involving direct contact with salts are definitely corrosive to magnesi-
um alloys. The optimal corrosion protection (in terms of thickness and
resistance) is provided by an anodizing treatment, followed by the applica-
tion of an organic paint system chemical conversion coatings or anodizing
treatments, are required. A number exist, such as the older Dow 17 and HAE
and the newer and improved Tagnite, Keronite, and Magoxid treatments. In
many cases it is sufficient to simply coat the counterpart and leave the mag-
nesium uncoated (if it is no view part). This to prevent a defect in a coating
on magnesium would result in an enhanced localized corrosion attack of the
magnesium component. No contact corrosion of magnesium is caused by
anodized AlMg3 alloy. Conventionally galvanized steel bolts can be at-
tached to magnesium by using a silicate sealing. The silicate sealing of gal-
vanized steel bolts was successfully applied by Audi and VW at the B80
magnesium gear housing.

Box Alternative manufacturing processes for Mg parts to compete

with Al parts for lightweighting

Despite enormous market share of aluminum, a continuous request for using

further lighter materials in several sectors like automotive, aeronautics,
transportation in generals, has been pushing to adoption of magnesium al-
loys, being magnesium 30% lighter than aluminum. Traditional magnesium
die-casting is however not practicable for safe and structural related reasons
since:
lower ductility and toughness than cast aluminum, not acceptable
for several sector standards;
lower elastic modulus and lower strength of conventional magnesi-
um casting alloys than aluminum cast alloys, not compensated by
magnesium lower density, in structural component;
complex and expensive equipment is necessary because of using
cover gases to prevent hazardous reactions of molten magnesium
with air (it is well known that the continuous oxidation and result-
ant burning of Mg alloy occur, at high temperature over 500 C).
However, impressive advancements have been recently introduced by: i.
 319

adding CaO to conventional Mg alloys; ii. a non SF6 (and other GHGs cover
gases) die-casting is possible; iii. just safe and clean nitrogen enriched at-
mosphere is required for prolonged time, while for short process cycle time
casting can be done in air. These novel Mg-CaO added alloys are available
on the market, known as Eco-Magnesium alloys.
As alternative shaping technology, semisolid processes have been research-
ing to produce parts that can compete with die-cast aluminum parts.
A semisolid process relies on the behavior of metals that, stirred in interme-
diate liquid and solid phase, exhibit a remarkable decrease of its viscosity
[1]. Scientifically referred as thixotropic behavior [2-6], this phenomenon in
metals is well explained because spheroidal rather than a dendritic micro-
structure forms during agitation of semisolid slurry [7]: rounded solid parti-
cles are suspended in the liquid fraction, thus viscosity drops. Consequently,
a laminar not turbulent flow is possible to fill semisolid material into high
complexity cavities with smooth mold filling preventing air entrapment, as it
is usual in conventional die-casting. The absence of air/gas entrapment re-
sults in:
higher integrity of the parts, due to absence of internal gas porosi-
ties, with superior mechanical properties;
possibility to conduct post-heat treatments to increase furthermore
mechanical properties, not possible for the cast alloys (gas en-
trapped causes blistering phenomena during heat).
The state-of-the art recognizes for aluminium alloys two semisolid routes,
Rheocasting and Thixocasting, while for magnesium alloys, only a
commercial semisolid process route is possible, and it is called Thixomold-
ing:
i. Thixocasting: consists in the manufacture of billets of the desired
globular microstructure - usually by continuous casting and induc-
tion stirring. The billet are fully solidified in globular shaped mi-
crostructure and used as feedstock material for a subsequent reheat-
ing in semisolid state and final shaping.
ii. Rheocasting: the semisolid slurry is prepared directly by spilling
out from furnace into a heated crucible equipped with a stirrer;
once the semisolid slurry is ready, it is gravity poured into the die
or pressure injected. The advantage against Thixocasting is that
avoids the re-heating of thixotropic state billet, as happens in the
Thixocasting process. The advantage is reduced energy per kg of
finished product.
iii. Thixomolding: employs a machine similar to injection molding of
polymers. Room temperature magnesium alloy feedstock (i.e.
chips) are fed into the a heated barrel through feeder. A screw in-
side the barrel agitates and shears chips while they are heated up to
semi-solid temperature range. The semisolid slurry once ready is
320

injected into die.

References

[1] Z. Fan, International Materials Reviews, vol. 47, no. 2, pp. 4985, 2002.
[2] M. C. Flemings, Metallurgical Transactions A, vol. 22, no. 5, pp. 957981, 1991.
[3] A. R. A. McLelland et all, Materials Science and Engineering A, vol. 232, no. 1-
2, pp. 110118, 1997.
[4] M. Modigell et all, Journal of Materials Processing Technology, vol. 111, no. 1
3, pp. 5358, 2001.
[5] D. Brabazon et all, Materials Science and Engineering A, vol. 356, no. 1-2, pp.
6980, 2003.
[6] B. P. Gautham et all, Materials Science and Engineering A, vol. 393, no. 1-2, pp.
223228, 2005.
[7] A. Blanco et all, Transactions of Nonferrous Metals Society of China, vol. 20, no.
9, pp. 16381642, 2010. [13] D. Liu et all, Acta Materialia, vol. 53, no. 14, pp.
38073819, 2005.
[8] Kim, S. et all, Magnesium Conference (IMA-2009), San Francisco, May 2009,
IMA, USA
[9] R.Burapa et all, Trans. Nonferrous Met. Soc. China 20(2010) s857-s861
 321

Chapter 8Titanium Alloys 41

The primary advantages of titanium alloys are their combination of rela-
tively low densities 4.5 g/cm3 (approximately half as heavy as steel and
nickel-base superalloys), high strengths that are aligned with steels (yield
strengths vary from 480 MPa of pure titanium to 1100 MPa for structural
Ti alloys). Low density and high strength place titanium specific strength
(i.e. strength versus density) at very high value, so it is qualified as light
metal. Furthermore titanium alloys have much better fatigue strength than
the other lightweight alloys, such as those of aluminum and magnesium.
Titanium alloys can be used at moderately elevated temperatures, as high
as 370 to 595C, depending on the specific alloy. In addition, some alpha
titanium alloys (refer to section Metallurgy of Titanium), especially the
low interstitial grades, can be used in cryogenic applications because they
do not exhibit a ductile-to-brittle transition.
As a result of their attractive combination of properties, titanium alloys are
used extensively in aerospace for both airframe and engine components. In
commercial passenger aircraft engines, titanium alloys are used for the fan,
the low pressure compressor, and approximately 2/3 of the high-pressure
compressor.
Although titanium is a highly reactive metal, a very stable and highly ad-
herent protective oxide film forms on its surface. This oxide film, which
forms instantly when fresh metal surfaces are exposed to air and/or mois-
ture, provides the excellent corrosion resistance of titanium that can be su-
perior to austenitic stainless steels. For this reason, Titanium alloys are
frequently used in chemical processing equipment as a result of their ex-
cellent corrosion resistance.
They also have outstanding biocompatibility42 with the human body and
are used for prostheses and dental implants.
The biggest disadvantage of titanium alloys is their relatively high cost.
Since titanium is a very reactive metal with a high melting point (1720

41 Main reference: F.C. Campbell, Elements of Metallurgy and Engineering Alloys,

ASM International, 2008 (Chapters 28).

42 Titanium is considered the most biocompatible of all metals due to its ability
to withstand attack from bodily fluids, stay inert in the human body, be compatible
with bone growth and stay strong and flexible during use. The TiO2 protective
film that forms onto titanium metal when titanium is exposed to air (i.e. oxygen in
air) is insoluble and chemically non transportable so that it makes such titanium
highly resistant to body environments, preventing any immune reaction from oc-
curring.
322

C), ingot casting and primary fabrication procedures are complicated and
expensive. Secondary fabrication processes, such as forming and machin-
ing, are also usually more costly than those for other competing metals.

Titanium Metallurgy
Pure titanium at room temperature has an alpha () hexagonal close-
packed (hcp) crystal structure, which transforms to a beta () body-
centered cubic (bcc) structure at a temperature of approximately 885C.
This transformation temperature, known as the beta-transus temperature,
can be raised or lowered depending on the type and amount of impurities
or alloying additions.
As a result of the hcp crystalline structure, alloys with appreciable amounts
of alpha must be formed at elevated temperatures, while those with pre-
dominantly bcc structures exhibit varying degrees of room temperature
formability. At room temperature, commercially pure titanium is com-
posed primarily of the alpha phase. As alloying elements are added to tita-
nium, they tend to change the amount of each phase present and the beta-
transus temperature in the manners shown in Fig. 8.1.

Fig.8.1 - Phase diagrams for binary titanium alloys.

 323

Specifically:
Addition of alpha-stabilizer elements, such as aluminum, oxygen, nitro-
gen, and carbon, increases the beta-transus temperature by stabilizing the
alpha phase (see Fig.8.1, upper left box);
Addition of beta-stabilizer elements, such as molybdenum, vanadium,
tantalum, and niobium, that are miscible in the beta phase decreases the
decrease the beta-transus temperature and stabilizes the beta phase (see
Fig.8.1, upper right box);
Addition of eutectoid-forming elements, such as manganese, iron, chro-
mium, cobalt, nickel, copper and silicon, that forms an eutectoid reaction
with Ti (see Fig.8.1, bottom left box).
Titanium has a great affinity for interstitial elements, such as oxygen and nitrogen,
and readily absorbs them at elevated temperatures, which increases strength and
reduces ductility.
Hydrogen has detrimental effect, and it always must be minimized in titanium al-
loys because it causes hydrogen embrittlement by the precipitation of hydrides.
The maximum limit allowed is approximately. 0.015 wt% (~100 ppm). Absorp-
tion of several hundred ppm of hydrogen results in embrittlement (Fig. 8.2) and
the possibility of stress cracking. Note that the addition of 20 ppm does not cause
embrittlement, but when the hydrogen content goes up to 250 ppm, the reduction
in area is seriously impaired.

Figure 8.2 - Effect of hydrogen content (ppm) on ductility of alpha titanium.

324

Titanium Alloys
Titanium alloys are classified according to the amount of alpha and beta
retained in their structures at room temperature. Classifications include
commercially pure, alpha and near-alpha, alpha-beta, and metastable beta.
While these classifications are useful, many of them are actually very close
to each other in the total amount of beta stabilizer present, as illustrated
in the Fig. 8.3 phase diagram. For example, Ti-6Al-4V is classified as an
alpha-beta alloy, and Ti-6Al-2Sn-4Zr-2Mo is classified as a near-alpha al-
loy, yet they differ little in the total amount of beta stabilizer concentra-
tion.
The properties of a number of commercially important alloys are given in
Table 8.1.

Fig. 8.3 - Pseudobinary titanium phase diagram.

 325

Table 8.1 - Properties of selected titanium alloys.

Commercially Pure Titanium

Commercially pure titanium wrought products are used primarily for ap-
plications requiring corrosion resistance (such as corrosion-resistant tub-
ing, tanks, and fittings in the chemical-processing industry.). They are also
useful in applications requiring high ductility for fabrication but relatively
low strength in service (yield strengths range from 170 to 480 MPa). In the
higher strength grades, oxygen and iron are intentionally added to the re-
sidual amounts already in the sponge to provide extra strength. On the oth-
er hand, carbon and nitrogen usually are held to minimum residual levels
to avoid embrittlement. Conversely, when good ductility and toughness are
desired, the extra-low interstitial (ELI) grades are used. In ELI grades, car-
bon, nitrogen, oxygen, and iron must be held to acceptably low levels, be-
cause they lower the ductility of the final product.

Alpha and Near-Alpha Alloys

Aluminum is the principal alloying element in the alpha and near-alpha al-
loys. Aluminum provides solid-solution strengthening and oxidation re-
sistance and reduces density. They are slightly less corrosion resistant but
higher in strength than unalloyed titanium. They have medium formability
and are weldable. Actually the Ti-5Al-2.5Sn is the only true alpha alloy
that is commercially produced (the remainder of the commercially availa-
ble alloys are near-alpha alloys). Since it is a single-phase alloy containing
326

only alpha, it cannot be strengthened by heat treatment. Except for cryo-

genic applications, the use of Ti-5Al-2.5Sn has declined as alloys with bet-
ter forming properties and higher creep resistance have been developed.
Near-alpha alloys contain small amounts beta phase dispersed in an other-
wise all-alpha matrix and they generally contain 5 to 8 wt% Al. The
amount of aluminum that can be added as an alloying element is limited 43
since an excess of aluminum content forms the brittle intermetallic com-
pound -2 (Ti3Al) forms, which adversely affects ductility.
The near-alpha alloys (such as Ti-6Al-2Sn-4Zr-2Mo-0.25Si) retain their
strength to high temperatures and have good creep resistance in the range
of 315 to 595C; furthermore they have good cryogenic behavior.

Alpha-Beta Alloys
They contain both the alpha and beta phases. Again, aluminum is the prin-
cipal alpha stabilizer that strengthens the alpha phase but beta stabilizers,
such as vanadium, are added and they also provide strengthening and al-
low these alloys to be hardened by solution heat treating and aging. An ex-
ample is the widely commercial available Ti-6Al-4V, which is the work-
horse of the aerospace industry.
Although the metallurgy of titanium heat treatment is complex, the re-
sponse to heat treatment of alpha-beta alloys is a result of the instability of
the high-temperature beta phase at lower temperatures. You may refer
again to Fig.8.3, and consider the Ti-6Al-4V as major example. Heating
such an alloy, to the solution treating temperature (above martensite start,
Ms, line), produces a higher ratio of beta phase. During rapid cooling 44, i.e.
quenching, the beta is transformed to beta and titanium martensite or
phase, the acicular structure shown in Fig.8.4a.
During subsequent aging (i.e. reheating at low temperature) treatment,
strengthening effects may occur together 45:
a. the decomposition of the unstable martensite into beta-plus-alpha
microstructure (it is defined as the first stage of hardening) visible
in Fig.8.4b;

43 The maximum aluminum content is actually calculated considering other elements

that promote a-2 phase formation; thus, the maximum aluminum content must be account
considering the aluminum equivalent content that is determined by summing the following
weight percentages of alloying elements: Aleq = Al+1/3Sn+1/6Zr+10 (O+C+2N).
44 Since the response to heat treatment is a function of cooling rate from the solution

temperature, the section sizes that can be through hardened are limited.
45 The martensite formed in titanium alloys is not like the extremely hard and strong

martensite formed during the heat treatment of steels.

.
 327

b. The precipitation of ordered 2 particles (type Ti3Al) in the alpha

phase, that is also defined second stage of hardening.

(a) (b)

Figure 8.3 - Microstructure of Ti-6Al-4V: a) after quenching from solution treat-

ing temperature; b) after aging treatment.

The weldability of the alpha-beta alloys is not as good as the near-alpha al-
loys, but their formability is better. The alloys that contain smaller per-
centages of beta stabilizers, known as lean alloys, are more weldable. As
the amount of beta stabilizers increases, the weldability decreases.

Beta Alloys
Beta alloys are sufficiently rich in beta stabilizers and lean in alpha stabi-
lizers that the beta phase can be completely retained with appropriate
cooling rates. Beta alloys are metastable, thus the precipitation of alpha
phase in the metastable beta is usual and it is also a method used to
strengthen the alloys. Beta alloys contain small amounts of alpha stabiliz-
ing elements as strengthening agents, such as Ti-10V-2Fe-3Al. such alloys
are high-strength alloys that can be heat treated to tensile strength levels
approaching 1380 MPa. Heat treatment consists in solution treating and
aging hardening treatment, as for the alpha-beta alloys. Since their better
response to solution and aging treatment than the alpha-beta alloys, heavier
sections can be treated. The aging sequence, including temperature and
time, is important in producing a uniform precipitation without the occur-
rence of grain-boundary alpha. In fact, an excessive grain-boundary alpha
precipitation is detrimental to alloy ductility, fatigue strength, and stress-
corrosion cracking resistance.
328

They exhibit better room-temperature forming and shaping characteristics

than alpha-beta alloys; higher strength than alpha-beta alloys at tempera-
tures where yield strength, instead of creep.

Basics of fabrication of titanium alloys

Titanium is difficult to form at room temperature and exhibits a high degree of
shrinking due to its yield-strength-to-modulus ratio. To compensate for the shrink,
titanium must be extensively overformed or, as is done most frequently, hot sized
after cold forming.
Hot forming, conducted at temperatures from 595 to 815C, is normally used to
form titanium alloys. Hot forming allows the material to deform more readily,
simultaneously stress relieves the deformed material, and minimizes shrinking.
Titanium also tends to creep at elevated temperature, and therefore, creep forming,
performed by holding the part under load at the forming temperature, is another al-
ternative for achieving the desired shape without having to compensate for exten-
sive shrinking.
Heating or plastic deformation at temperatures above the normal aging tempera-
ture for solution-treated Ti-6Al-4V causes overaging to occur, and, as a result,
mechanical properties decrease.
Titanium is difficult to machine because of its high reactivity, low thermal con-
ductivity, relatively low modulus, and high strength at elevated temperatures.
When machining titanium, it is important to use slow speeds, maintain high feed
rates, use flood cooling, maintain sharp tools, and use rigid setups.
Adhesive bonding, mechanical fastening, metallurgical bonding, and welding are
used to join titanium and its alloys. The first three processes do not affect the
properties of these metals as long as joints are properly designed. Titanium alloys
can be welded by gas tungsten arc welding in an inert atmosphere or electron
beam or laser welded. Electron beam and laser welds are normally made without
filler metal, and weld beads have high depth-to-width ratios. This combination al-
lows excellent welds to be made in heavy sections, with properties very close to
those of the base metal.
 329

Chapter 9 Steelmaking process: basics of primary

fabrication and secondary operations 46
Introduction

A general diagram for the production of steel from raw materials to finished mill
products is shown in Fig. 9.1. Steel production may start either with the reduction
of iron ore in a blast furnace into pig iron by employing as main additional raw
material coal, to produce pig iron 47, to be refined and purify into steel in a second
step (refer to Steelmaking furnaces Basic Oxygen Furnace) and thus it is pro-
cessed in an electric arc furnace to refine steel to desired chemical composition,
also reducing the carbon content of less than 1 wt%.
The main differences in primary metallurgy process for steel making is clearly
shown in the left part of the scheme in Fig.9.1, that shows the upstream process
steps from raw materials to primary steel products, i.e. blooms, billets and slabs. If
any primary steelmaking processes conduct to same primary products (i.e. blooms,
billets and slabs), this final output is achieved in two different pattern, depending
on plant architecture and by raw materials used:
Primary steelmaking production from iron ore. If steelmaking process
starts from iron ore, plant is equipped to satisfy the necessary steps to re-
duce iron ore with carbon (provided in the form of coke) into pig iron; in
this case a blast furnace (Fig.9.2, unit identified by 1) is present. It is
essentially a tall, hollow, cylindrical structure with a steel outer shell
lined on the inside with refractory brick. In such a vertical furnace, liquid
metals in form of pig iron (highly carbon content liquid with many impu-
rities) by the reaction of: 1) a flow of heated air (i.e. oxygen) introduced
under pressure into the bottom of the furnace with a mixture of metallic
ore, coke, and flux fed into the top to process according to general equa-
tion (eq. 9.1) Fe2O3 + 3CO 2Fe + 3CO2 where the CO necessary is pro-
duced by high temperature reaction between coke and oxygen. After the
pig iron is produced, it is necessary to be converted into steel, thus car-
bon content must be reduced to level of steel, before it is cast into ingots
or continuously cast into billets. This secondary conversion process is
conducted outside the blast furnace into a Basic Oxygen Furnace or BOF
(see Fg.9.1, refer to unit 2), where main process of reducing carbon
content takes place; as result, steel is produced with acceptable carbon
content so to be ultimately refined to final chemical composition (also in

46 Main reference: F.C. Campbell, Elements of Metallurgy and Engineering Alloys,

ASM International, 2008 (Chapter 28).

47 Pig iron is in the range of 3 to 4.5 wt% of carbon, thus exceeding the maximum 2.11

wt% carbon content of steels. This requires pig iron must be further refined (and purify in
terms of inclusions) in a basic oxygen furnace, or BOF, as described in the following.
330

terms of chemical alloying elements) into further furnace, the Ladle Fur-
nace or LF (see again Fig.9.1, refer to unit 3);
Primary steelmaking production from steel scraps. Because the raw ma-
terial used is already steel, the upstream stages conducted into Blast Fur-
nace and Basic Oxygen Furnace are not necessary. The steelmaking pro-
cess in this case starts from the melting of steel scraps into an Electric
Furnace (EF); melt steel is therefore spilled out to the Ladle Furnace (see
again Fig.9.1, refer to unit 3), where chemical composition refinement
takes place.

Note from above that, despite two different steelmaking processes are required if
you start from either iron ore or recycling scraps, the steps that follow the unre-
fined steel production in either BOF or EF are the same: the unrefined steels shall
be turned into desired chemical composition in the Ladle Furnace.
When steel is refined, it can be cast into ingots or continuously cast into billets,
blooms or slabs, depending on section shape and size 48 (see again the scheme in
Fig.9.1).
Cast semifinished products are therefore hot worked to improve homogeneity, re-
fine the as-cast microstructure, and fabricate desired product shapes. All these
downstream steps are those we call secondary steelmaking process and, by gener-
alizing, they start from initial hot deformation processes (e.g. forging or rolling)
can proceed in further refinement of section, shape and size of products. Some
products therefore derives directly from hot rolling operations, and they are used
in the hot rolled condition, some others are heat treated to obtain specific proper-
ties.
Some other steel products are fabricated by secondary working by hot forging into
semifinished shapes or hot extruding.
For some other products thin sections, close clearances and good surface quality is
required for example to fabricate cold drawn pans, wound cold springs, etc. In this
case the hot deformed semifinished products are further cold worked to achieve
final shape, size and surface quality.
In the following sections, some further details on main units of the upstream pri-
mary steelmaking production for both the iron-ore and recycled steel scraps pat-
tern routes are provided.

48 Continuous casting process can produce semifinished products that can be: a) billets,
namely long semifinished products with round or square cross-section and with section ar-
ea less than 230 cm2; b) blooms, similar to billets except the cross-sectional area that is
greater than 230 cm2; c) slabs, long semifinished product with rectangular cross-section ar-
ea.
 1
2
3

Primary production from steel scraps

Primary production from iron-ore Secondary production

Fig.9.1 - Principal steps in steelmaking..

 Box Brief History of Steel

Steel started to replace bronze in approximately 1200 B.C. Cast iron alloys
predate steel because cast iron, with its higher carbon content, melts at lower
temperatures. Early steel alloys were produced by solid-state smelting that
produced iron with a low carbon content and high density of entrapped slag
inclusions. Heavy hammering or forging was used to fragment and disperse
the inclusions. In approximately 350 B.C., wootz steel was produced in In-
dia by adding carbon to wrought iron and then carburizing it in crucibles
with charcoal. During this period, similar processes evolved in other parts of
the world. Since these early processes provided both an economic and mili-
tary advantage, they were closely guarded secrets. Despite the drawbacks of
these early processes, early blacksmiths produced remarkable objects, such
as the Damascus and Japanese swords that had sharp cutting edges, high
hardness and strength, good fracture resistance, and were also objects of
great beauty. Damascus swords, first produced in approximately 500 A.D.,
were forged from blocks of high-carbon wootz steel and were known for
their highly decorative surface patterns caused by fine bands of dispersed al-
loy carbides. Japanese swords, which evolved about the same time, were
made by welding alternating layers of low- and high-carbon steel together in
multiple forging steps. However, it was not until the middle of the 19th cen-
tury that a large-scale process emerged for making steel, when, in 1856,
Bessemer patented a process in which hot air was blown through molten pig
iron to reduce the carbon and silicon contents. In 1858, Siemens first suc-
cessfully operated an openhearth furnace in which liquid pig iron and scrap
were melted with a hot gas flame. The key factor in both the Bessemer and
Siemens processes was the oxidation and removal of carbon, silicon, and
other impurities by oxides, such as CO in the case of carbon.

Blast Furnace
As mentioned, the first step in making steel from iron ore is to make iron
by chemically reducing the ore (iron oxide) with carbon, in the form of
coke, according to the general equation:

(eq. 9.1) Fe2O3+3CO 2Fe+3CO2

This reaction takes place in a blast furnace, shown schematically in Fig.

9.2.
 333

Blast furnace main units - 1: Iron ore + Calcareous sinter; 2: coke; 3: conveyor belt; 4: feeding open-
ing, with a valve that prevents direct contact with the internal parts of the furnace; 5: Layer of coke; 6:
Layers of sinter, iron oxide pellets, ore; 7: Hot air (around 1200C); 8: Slag; 9: Liquid pig iron; 10:
Mixers; 11: Tap for pig iron; 12: Dust cyclon for removing dust from exhaust gasses before burning
them in 13; 13: air heater; 14: Smoke outlet (can be redirected to carbon capture & storage (CCS)
tank); 15: feed air for Cowper air heaters; 16: Powdered coal 17: cokes oven 18: cokes bin 19: pipes
for blast furnace gas.

Fig.9.2 Scheme of blast furnace Blast Furnace as it is placed in an installation.

For a video describing Blast Furnace operation click here.

The stack inside the blast furnace is kept full with alternating layers of
coke, ore, and limestone admitted at the top during continuous operation
(see Fig.9.2, details 1, 2 and 4). Coke is ignited at the bottom and
burned rapidly with the forced air from the tuyeres 49 (see Fig.9.2, detail
7). The iron oxides in the ore are chemically reduced to molten iron by
carbon and carbon monoxide from the coke. The slag formed consists of
the limestone flux, ash from the coke, and substances formed by the reac-
tion of impurities in the ore with the flux; it floats in a molten state on the
top of the molten iron; see the detail 8 in Fig.9.2, as it represents the slag
that floats it is lighter than metal - onto upper part of molten metal. The
slag is periodically purified from molten metal by the opening outlet in
8, thus eliminated for recycling by 8. On the opposite side, from the
49 From the French, tuyer is an opening water-cooled nozzle through which air is blown

into a blast furnace to facilitate combustion.

334

outlet 9 the molten pig iron is spilled out and loaded onto torpedo cars
(see Fig.9.2, detail 11) for transferring it quickly to the next station, the
Basic Oxygen Furnace, where conversion from pig iron into steel takes
place.
Hot gases rise from the combustion zone, heating fresh material in the
stack and then passing out through ducts near the top of the furnace.
Finally exhaust gases must be captured by pipes (see Fig.9.2, detail 19),
cleaned by dust by use of cyclone for removing dust (see Fig.9.2, detail 12)
so to burn them in an air heater (see Fig.9.2, detail 13) and finally trans-
ferred to smoke outlet (in modern plant, this can be redirected to carbon
capture & storage CCS tank to reduce CO2 emissions).
Modern blast furnaces range in size from 20 to 35 m, have hearth diame-
ters of 6 to 14 m, and can produce from 1,000 to almost 10,000 tons of pig
iron daily.

Basic Oxygen Furnace

Basic Oxygen Furnace (BOF) or Basic Oxygen Converter is a steel making
furnace, in which molten pig iron and steel scrap convert into steel due to
oxidizing action of oxygen blown into the melt under a basic slag. Typical
basic oxygen furnace is shown in fIg.9.3a. It has a vertical vessel lined
with refractory lining. Actually only 8-12% of the furnace volume is filled
with the treated molten metal. A careful balance between the relative
amounts of pig iron and scrap charged into the converter is maintained as a
means of controlling the temperature and to ensure that steel of the re-
quired specification is produced.
A water-cooled lance is then lowered into the vessel (see Fig.9.3), through
which very pure oxygen is blown at high pressure. The oxygen interacts
with the molten pig iron to oxidize undesirable elements, including excess
carbon, manganese, and silicon from the ore, limestone, and other impuri-
ties such as sulfur and phosphorus.
Oxidation of the molten metal and the slag is complicated process proceed-
ing in several stages and occurring simultaneously on the boundaries be-
tween different phases (gas-metal, gas-slag, slag-metal), however finally
the reactions may be presented as follows. The lance "blows" 99% pure
oxygen over the hot metal, igniting the carbon dissolved in the steel, to
form carbon monoxide and carbon dioxide, and causing the temperature to
rise to about 1700C. This melts the scrap, lowers the carbon content of the
molten iron and helps remove unwanted chemical elements.
After a sample has been taken to verify the chemical composition of the
steel, the vessel is tilted to allow the molten steel to flow out. The steel is
 335

tapped into a ladle where further composition adjustments are made.

The process which takes place in BOF is the most powerful and effective
steel making method. About 67% of the crude steel in the world is made in
the Basic Oxygen Furnaces (BOF). The typical capacity of the Basic Oxy-
gen Furnace is 250-400 t.

(a)

(b)

Fig. 9.3 A Basic Oxygen Furnace: a) scheme of equipment; b) the BOF, the
converter, while it is loaded by pig iron transferred from torpedo car (see upper-
right corner) and when steel is spilled out from converter to steel ladle, to reach
the next station, the Ladle Furnace. For a video describing Basic Oxygen Furnace
operation click here.
336

Electric Arc Furnace

Unlike the BOF, the electric arc furnace (Fig. 9.4) does not use molten pig iron but
uses steel scrap 50. Thus, this furnace is the primary stand of steelmaking process
that use steel scrap as raw material, instead iron ore (refer to pattern route Prima-
ry production from steel scraps in the scheme in Fig.9.1). Scraps are charged into
the furnace from an overhead crane, and a lid is swung into position over the fur-
nace. The lid holds graphite electrodes that are lowered into the furnace. An elec-
tric current is passed through the electrodes to form an arc, which generates the
heat necessary to melt the scrap.
During melting, alloying elements are added to the steel to give it the required
chemical composition 51. After samples have been taken to check the chemical
composition, the furnace is tilted to allow the floating slag to be poured off. The
furnace is then tilted in the other direction, and the molten steel is tapped into a la-
dle, where it either undergoes secondary steelmaking or is transported to the caster
(see the phases in the scheme of Fig.9.5).
The modern electric arc furnace typically makes approximately 136,000 kg of
steel in about 90 min.

Fig. 9.4 Scheme of an Electric Arc Furnace .

50 Since the electric arc furnace has a relatively low capital equipment cost and uses

steel scrap, this process is used where local supplies of steel scrap are available and has
given rise to what are known as mini mills.
51 The electric arc furnace is also used for producing alloy steels that contain apprecia-
ble amounts of easily oxidized alloying elements, such as chromium, tungsten, and molyb-
denum. It can also be used to make steels requiring very low sulfur and phosphorus con-
tents. Special slags are used to lower the sulfur and phosphorus levels and to protect against
oxidation of alloying elements.
 337

Fig. 9.4 Electric arc furnace main operations. For a video describing Electric Arc
Furnace gen Furnace operation click here.

Ladle Furnace
Molten steel have to be refined to desired chemical composition in a de-
vice called Ladle Furnace (LF). From BOF the unrefined steel is poured
into a ladle that moved quickly to next stand, the Ladle Furnace, where it
is placed under a cover equipped with three graphite electrodes connected
to a three-phase arc transformer. The scheme of a Ladle Furnace stand is
illustrated in Fig.9.5; notice the ladle visible under the cover with three
electrodes.

(a) (b)
Fig.9.5 (a) Scheme of a Ladle Furnace stand; (b) section of Ladle Furnace with
main functions.
338

The ladle bottom has a porous refractory plug, which is connected to the
argon supply pipe at the Ladle Furnace stand. The LF stand is also
equipped with an addition hopper mounted on the cover and a lance for in-
jection of desulfurizing agents. Fumes formed during the operation are ex-
tracted through the cover.
Molten steel treated in Ladle Furnace is covered by a layer of desulfurizing
slag. The graphite electrodes are submerged into the slag, which protects
the ladle lining from overheating produced by the electric arcs. The arcs
are capable to heat the steel at the rate about 3C/min. During the treat-
ment process argon is blown through the bottom porous plug providing
continuous metal stirring. Stirring results in distribution of heat produced
by the arcs, chemical homogenization and desulfurization of the steel by
the slag. Alloying elements are therefore added through the addition hop-
per.
Ladle Furnace primary functions are those to permit the secondary refining
of molten steel before to final cast, such as: temperature homogenization
or adjustment; chemical adjustments for carbon, sulfur, phosphorus, oxy-
gen and precise alloying; inclusion control; degassing, and others.
The function of the porous plug is to provide inert gas stirring of the mol-
ten metal to promote homogenization. Normal stirring operations are per-
formed by percolating argon gas through a purge plug arrangement in the
bottom of the ladle.
Vacuum degassing is also possible with the steel in a ladle, and argon
lances can be used to stir the steel to make the composition more homoge-
neous. Vacuum degassing produces ultra low-carbon steels, with carbon
contents as low as 0.002 wt%. Vacuum degassing also removes hydrogen
that can result in hydrogen flaking and porosity.

From Ladle Furnace to Casting Process

Whichever is the raw material used and relative patter route employed, ei-
ther the iron-ore or recycled steel scrap, the ladle refining operations must
be completed in the Ladle Furnace (such phase, crucial for steel refining, is
also called ladle metallurgy).
From the ladle furnace station, the liquid steel is moved by ladle to be cast
to produce ingots or continuously cast long product (in a continuous cast-
ing machine).

Ingot Casting
During ingot casting, the ladle is moved by an overhead crane so that is
can be tapped or teemed into individual upright-standing molds on rail
 339

cars. The metal can be poured into the mold either from the top of the
mold or from the bottom through a connecting channel. In the first case,
the steel is poured from the ladle directly into the mold (Figure 9.6a). After
the mold is filled, the ladle opening is closed and the ladle is moved by
crane to the next mold, where the process is repeated. In bottom pouring,
several molds (from two to 60) can be filled with steel simultaneously.
Here, the molds are mounted on a stool having channels lined with refrac-
tory brick. The steel from the ladle descends through the fountain into the
channels of the stool and then enters the mold from the bottom (Figure 9-6
b). The pouring method used depends on such factors as the steels grade
and weight and the intended use of the ingots.

(a) (b)

Fig.9.6 Ingot casting through: (a) top-pouring and (b) bottom-pouring processes;
(1) ladle with metal, (2) mold, (3) stool, and (4) fountain.

Continuous Casting
Although ingot casting has been the traditional method, continuous casting
has rapidly evolved as the method of choice because of cost and quality
advantages.
In the continuous casting process (Fig. 9.7), the ladle of molten steel is
transported to an elevated casting platform above the casting machine. The
molten steel is poured into a rectangular trough, called tundish, which acts
as a reservoir for the steel. From a spout in the bottom of the tundish, the
molten steel is poured into a water-cooled mold with a movable temporary
bottom. As the molten steel enters the mold, the metal at the surface of the
mold solidifies, forming a thin skin. The skin thickens as the metal passes
through the mold, and the temporary bottom is slowly lowered to allow
340

metal to be continuously poured into the mold. The remaining metal in the
center of the ingot is solidified by spraying cold water onto the ingot as it
leaves the mold. The solid metal billet is pulled by rollers so that a long,
continuous steel slab is produced.
At the end of the machine, it is straightened and cut to the required length.
Fully formed slabs, blooms, and billets emerge from the end of this con-
tinuous process. The continuous casting process runs for days or weeks as
ladle after ladle of molten steel feeds the casting machine.
The advantages of the continuous casting process include reduced costs,
improved quality, increased yield, lower energy costs, and less pollution. It
is now the process of choice for high-volume, low-cost plain carbon steels.
Quality improvements include less variability in chemical composition,
both through the thickness and along the length of the continuously cast
slab. The surface quality of the slab is also higher than for an ingot, having
fewer surface defects such as seams and scabs.
The yield for continuous casting is also higher, since it is not necessary to
crop the ends of continuously cast slabs. Energy savings are achieved,
since the continuously cast slabs are sent directly to rolling mills and do
not require soaking pits for reheating. In addition, since the thickness of
continuously cast slabs is approximately half the thickness of individual
ingots, much less hot rolling is required.

Fig.9.7 Continuous steel casting, architecture and main equipment for the opera-
tions. For animation video describing all process steps from recycling scrap to
continuous casting click here.
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The cast product microstructure

A metal cast into a mold, such as continuous casting rectangular shaped billet
shown in Fig.9.8, can have up to two or three distinct zones: a chill zone, a zone
containing columnar grains or dendritic grains, and a center-equiaxed grain zone.

Fig.9.8 Freezing sequence for an alloy casting.

These zones form because of metallurgy phenomena which develop for rapid so-
lidification that can be generalized by the scheme in Fig.9.9; the scheme illustrates
which is basic phenomena that lead to formation of a series of columnar, or col-
umn shaped, grains that are oriented almost parallel to the heat flow direction. Be-
cause each metal grows more favorably in one principal crystallographic direction,
only those grains favorably oriented with their growth direction most perpendicu-
lar to the mold wall will grow into the center of the casting. The axes of the co-
lumnar grains are parallel to the direction of heat flow, and they grow along spe-
cific crystalline planes.

Fig.9.9 Columnar growth from mold wall

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As freezing progresses, the thermal gradient decreases, and this causes the den-
drites to become very long. Breakdown of columnar growth may occur as a result
of fracturing of the very long dendrite grains by convection currents in the melt.
These broken arms can then serve as nuclei for new grains, as shown in Fig. 9.10
that refers to typical ingot product that solidifies.

Fig.9.10 Formation of equiaxed zone in alloy casting.

The amount of the final cast structure that is columnar or equiaxed depends on the
alloy composition and on the thermal gradient at the liquid-solid interface during
solidification 52.
As freezing progresses, there is a buildup of the solute in the liquid that freezes
last, such as at the center of the casting. Such long-range variations in composition
are called macrosegregation. Normal segregation frequently occurs when the di-
rection of growth is inward, as in columnar growth.
Furthermore, solidification shrinkage occurs especially in ingot casting. Shrinkage
porosity often forms in areas that the liquid metal from the risers cannot reach. For
example, it is difficult to effectively feed metal into the interdendritic areas where
shrinkage is occurring. Because this type of porosity occurs late in solidification,

52 It should be noted that all three zones do not always occur. For example, pure

metals can exhibit a chill zone and a columnar zone but not contain a center-
equiaxed zone. The amount of the final cast structure that is columnar or equiaxed
depends on the alloy composition and on the thermal gradient at the liquid-solid
interface during solidification. The thermal gradient is most easily controlled by
controlling the rate of heat extraction from the casting, or the cooling rate.
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especially in alloys with wide freezing ranges and a large mushy zone, it is partic-
ularly difficult to eliminate.
The primary casting microstructure is thus made of:
Large grains;
Non-equiaxic structure;
Non homogeneous chemical composition due to macrosegrations and mi-
crosegregations;
Gas porosities and shrinkage porosity.
As result, the mechanical properties of primary casting structure are:
Very low mechanical strength (low YS and UTS);
Very low toughness (low KV and KIc);
namely those features that do not allow products to be put in service directly cut-
ting from ingots, blooms, slabs and billets.

Box - Solidification interfaces growing and morphology of industrial

cast products

The solidifying solid-liquid interface can exhibit one of three types of inter-
facial growth in the liquid: planar, cellular, or dendritic. As shown in Fig.
9.11, the type of growth is controlled by the manner in which heat is re-
moved from the system. When the liquid ahead of the solid-liquid interface,
x0, has a positive temperature gradient, heat is removed from the liquid by
conduction through the growing solid. Since the temperature gradient is lin-
ear and uniform perpendicular to the interface, a smooth interface is main-
tained, and the growth is planar into the liquid (Fig. 9.11a). When there is a
temperature inversion and the temperature decreases ahead of the solid-
liquid interface, then either dendritic (Fig. 9.11b, c and Fig.9.12) or cellular
(Fig.9.13) will occur.
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Fig.9.11 Effects of undercooling on solidification structures.

Fig.9.12 Dendrite formation in succinonitrile-4% acetone solution.

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Fig.9.13 Columnar cells formation in round billet continuously cast.

Primary metalworking hot processes: the bulk deformation processes

Primary metalworking processes, such as the bulk deformation processes

used to conduct the initial breakdown of cast ingots, are always conducted
hot. The term bulk deformation implies large amounts of material move-
ment, such as in hot rolling or forging53.
Bulk deformation changes the shape of a workpiece by plastic deformation
through the application of compressive forces, as for the typical bulk de-
formation processes in Fig. 9.14.

53 They have to be distinguished from secondary processes, which are used to

produce the final product shape, that are conducted either hot or cold (such as
sheet forming) and that do not involve large amounts of deformation.
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Fig.9.14 Bulk deformation processes.

Bulk deformation has therefore a double intent: to change the shape of a

workpiece by plastic deformation through the application of compressive
forces and to refine the inhomogeneous structure resulting from semifin-
ished steelmaking products, such as cast ingots and continuously cast
slabs, billets and blooms. Such products are therefore typically hot worked
by hot deformation processes (as those ones shown in Fig.9.14) into inter-
mediate product forms, such as plates, bars, and sheet. Large plastic de-
formation in combination with heat - bulk deformation processes are con-
ducted at minimum 0.5Tm, in austenitic state - and they are necessary to:
Reduce dendritic structure, braking original dendrite structure and
promoting dynamic recrystallization in fine grains;
Reduce inhomogeneity of microstructure, by promoting at high
temperature the reflowing of metal and diffusion of chemical ele-
ments, thus eliminating macro-segregations;
Close all residual porosities and shrinkage cavities;
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in order to enhance all mechanical properties of hot worked microstruc-

ture.
For processes such as hot rolling, hot extrusion, and hot forging, the time
within the deformation zone is usually short, and grain refinement is usual-
ly accomplished by (static) recrystallization after hot working. A high level
of hot deformation followed by holding the workpiece at an elevated tem-
perature causes static recovery and recrystallization, resulting in a fine
grain size.
The hot rolling scheme in Fig. 9.15 generalizes what happens when billet
section is reduced under two rolling cylinders, and finally recrystallization
occurs when it slowly cools to room temperature.

Fig.9.14 Recrystallization during hot rolling.

Similar phenomena occurs also for other bulk metalworking operations,

such as rolling ring, forging of rolls, hot rolling mill (see Fig.9.15).
Products from primary metalworking process may be suitable for its in-
tended application, but in many cases, it provides the starting material for
secondary deformation processes such as drawing, hot or cold forging, and
sheet metalworking.
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(a)

(b)

(c)

Fig. 9.15 Example of bulk hot metalworking: a) rolling mill plant for plate roll-
ing (click on figure or click here for video); b) forging of primary continuously
cast billet into rolls (click on figure or click here for video); c) ring rolling pro-
duced from slab (click on figure or click here for video).
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